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Journal of Cleaner Production 16 (2008) 833e841


www.elsevier.com/locate/jclepro

Cleaner production in the Solvay Process: general strategies


and recent developments
Georg Steinhauser*
Atominstitut der Osterreichischen Universitaten, Vienna University of Technology, Stadionallee 2, 1020 Vienna, Austria
Received 2 February 2007; received in revised form 14 April 2007; accepted 19 April 2007
Available online 13 June 2007

Abstract
The Solvay Process aims at the production of soda ash. The solid and liquid effluents from the soda ash production have been a target of
investigation since decades or centuries, often attempting to make use of the wastes. In this paper, all sources of waste from the Solvay Process
and their environmental impact are reviewed and possible applications are discussed. It could be shown that, upon disposal into waterways, solid
and insoluble wastes have a much higher environmental impact than salt solutions. The results of this study allow the conclusion, that cleaner
production in this field can be achieved primarily by the use of cleaner raw materials or by technologies aiming at the avoidance of (solid) wastes
or at the increase of the conversion rate of the raw material sodium chloride, whereas the utilization of by-products made from the industrial
wastes often faces technical or economical problems.
2007 Elsevier Ltd. All rights reserved.
Keywords: Ammonia-soda process; Industrial waste; Sodium carbonate; Sodium chloride; Brine purification; INAA

1. Introduction
The Solvay Process, named after its inventor Ernest Solvay
(1838e1922), aims at the production of soda ash (sodium carbonate, Na2CO3), which is a major commodity and an essential raw product for many industrial applications (above all:
the production of glass) and even used in household applications (e.g. detergents). Thus, the Solvay Process is one of the
most important inorganic chemical processes. Where no natural
sodium carbonaceous minerals (e.g. trona, Na2CO3$NaHCO3$
2H2O; or nahcolite, NaHCO3) or natural occurring sodium
carbonate-bearing brines [1] are available, there is no real
alternative to the production of soda ash in the Solvay Process.
In 2000, 59% of the worldwide soda ash production was synthesized in the Solvay Process, 30% were produced by processing
natural sodium carbonate minerals, and 11% were produced
using other methods [2].

* Tel.: 43 1 58801 14189; fax: 43 1 58801 14199.


E-mail address: georg.steinhauser@ati.ac.at
0959-6526/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jclepro.2007.04.005

In the 19th and 20th century, the implementation of the Solvay Process was an important step towards the ecologization
of the production of soda ash. Compared with historical processes synthesizing soda ash, in particular the extraction of
plant ashes or the Leblanc process, the Solvay Process marked
a milestone in cleaner production. In the Leblanc process, soda
ash was synthesized using the following reactions:
2NaCl H2 SO4 / Na2 SO4 2HCl

Na2 SO4 4C / Na2 S 4CO

Na2 S CaCO3 / Na2 CO3 CaS

It caused the onset of large amounts of wastes such as CO,


HCl and CaS (causing the emission of H2S when getting into
contact with acid rain). Furthermore, the high energy consumption was a profound disadvantage. For a historical review
of the production of sodium carbonate, see Ref. [3]. A detailed
summary of technological aspects of the soda ash production
was written by the European Soda Ash Producers Association
[2]. A short summary is given here.

G. Steinhauser / Journal of Cleaner Production 16 (2008) 833e841

834

In the Solvay Process (ammonia-soda process), Na2CO3


is produced from NaCl and limestone (CaCO3), by participation of ammonia (NH3), which can be recovered.
First of all, NH3 is absorbed in the saturated and purified
NaCl-brine. Precipitation of sodium bicarbonate (NaHCO3)
is performed by carbonization using CO2, which is obtained
by burning of limestone. In this step, aqueous ammonium
chloride (NH4Cl) solution is produced as a by-product.
Calcination leads to the decomposition of NaHCO3 and to
the formation of Na2CO3, H2O, and CO2, which is used for
carbonization again. Like CO2, calcium oxide (CaO) is produced
by calcination of limestone. It is used in the form of milk of lime
(suspension of calcium hydroxide, Ca(OH)2) for the recovery of
NH3 in the so-called ammonia distillation (DS). All reactions can
be summarized as follows:

Table 1
Composition of the solid wastes of the Solvay Process
Brine purification sludge
CaCO3
CaO (dead-burned)
CaSO4$2 H2O
Mg(OH)2
Clay minerals

7740
n.d.
16 046
7000
n.d.

Distillation sludge
35 700
899
35 700
8200
4000

Data presented are the daily emissions (kg dry matter/d) of the soda ash fac sterreich GmbH Ebensee, Austria, in 2002 (personal communitory Solvay O
cation with Solvay Ebensee).
a
7740 kg CaCO3 is the overall onset of CaCO3 during brine purification.
Addition of CO2
3 bearing mother liquor to the crude brine and Ca(OH)2 to
the HCO
3 containing crude brine leads to crystallization of 1140 kg/d
CaCO3. Addition of soda ash to the magnesium-free brine precipitates
6600 kg/d CaCO3.

2NH3 2CO2 2H2 O $ 2NH4 HCO3

2NH4 HCO3 2NaCl / 2NaHCO3 Y 2NH4 Cl

Furthermore, CaCO3 is precipitated: addition of Ca(OH)2


to the solution saturated with dissolved NaHCO3 influences the equilibrium

2NaHCO3 / Na2 CO3 CO2 [ H2 O


2
HCO
3 OH $ CO3 H2 O

CaCO3 / CaO CO2 [

CaO H2 O / CaOH2

2NH4 Cl CaOH2 / 2NH3 [ CaCl2 2H2 O

and thus causes the onset of solid CaCO3. See Table 1 for
a typical composition of the DS waste, as well as Refs. [2]
and [4]. Although magnesium hydroxide (Mg(OH)2), originating from magnesite (MgCO3; a common impurity of
limestone), is a weak base, it partly contributes to the decomposition of NH4Cl in the DS-reaction:
2NH4 Cl MgOH2 $ MgCl2 2H2 O 2NH3

2NaCl CaCO3 / Na2 CO3 CaCl2

13

10

In general, the Solvay Process causes the onset of liquid


and solid wastes. Both are usually discharged to rivers, lakes
or the sea, because the enormous volume produced by a single
soda ash factory cannot be deposited in a conventional disposal site. Concerning wastes from the Solvay Process, possible applications or modifications of the process aiming at their
avoidance, have been intensively discussed in the literature.
A few of those propositions will be discussed later in this
paper. However, the most important chemical wastes from
the Solvay Process are the following.
(1) Distillation wastewater
It contains CaCl2 as the main dissolved component. Another important constituent is NaCl, due to the fact that
only approximately 70% of NaCl are precipitated in the
form of NaHCO3. Furthermore, the wastewater contains
suspended particles, which partly originate from reactions
during NH3-distillation and are partly impurities of the
limestone (clay minerals, an excess calcium hydroxide
and dead-burnt calcium oxide) that is used for the production of milk of lime. During DS, gypsum (CaSO4$2H2O)
is precipitated upon the addition of Ca2+ in the form of
milk of lime to the sulfate containing DS-solution, causing
an excess of the solubility product constant of gypsum:
Ca2 SO2
4 2H2 O / CaSO4 $2H2 OY

12

11

The DS wastewater therefore, always contains small


amounts of dissolved magnesium chloride (MgCl2) too.
As a sparingly soluble compound, most of the Mg(OH)2
are present as a part of the waste suspension, together
with the clay minerals, CaCO3, CaSO4, and dead-burned
CaO. These particles form the solid distillation wastes,
which sediment as sludge on the bottom of the water,
when the distillation wastewater suspension is disposed
of into rivers, lakes or the sea. Since this mixture of solids
has no technical application, it is usually not separated
from the liquid, before the DS waste is disposed of. The
pH of the raw effluent is >11.5. The reaction with the
waters Ca(HCO3)2, forming CaCO3 according to the equilibrium in Eq. (12), adjusts the pH upon mixing of the
wastewater with natural water.
(2) Brine purification sludge
Due to the natural alkaline earth metal-impurities of the
crude brine (see Table 2 for a typical composition of crude
brine), purification of the brine is essential to avoid scaling
of the production units (mainly the carbonization units and
heat exchangers) and contamination of the final product
with insoluble basic and neutral carbonates of Ca2+ and
Mg2+, as well as the triple salt northupite (NaCl$MgCO3$Na2CO3). Purification is performed by precipitation
of these alkaline earth metal ions. In the first step, milk
of lime is added to remove Mg2+ ions. Since the crude
brine is saturated with gypsum in many cases (especially

G. Steinhauser / Journal of Cleaner Production 16 (2008) 833e841


Table 2
Composition (in kg/m3) of crude sodium chloride brine (density 1.202 kg/l)
and mother liquor (density 1.264 kg/l)

Na
K
Mg2
Ca2
Sr2
Cl
Br
SO2
4
HCO
3
CO2
3

Mixed crude
brine from three
Austrian salt mines

Mother liquor,
Ebensee, Austria

117.82
2.487
1.500
0.809
0.025
183.24
0.065
8.69
0.102
n.d.

120.85
46.26
n.d.
n.d.
n.d.
189.97
n.d.
50.24
n.d.
1.02

sterreich GmbH, Ebensee, Austria, 2002;


Data were provided by Solvay O
personal communication.

in brine from alpine salt deposits), the addition of Ca2+


ions leads to the precipitation of CaSO4$2H2O in this
step, too:
Mg2 CaOH2 SO2
4 2H2 O / MgOH2 Y
CaSO4 $2H2 OY
14
In a second step, soda ash is added to precipitate the brines
residual Ca2+ ions in the form of CaCO3:
Ca2 Na2 CO3 / CaCO3 Y 2Na

15

The precipitates are separated from the purified brine by


decantation and/or filtration and form the brine purification
mud (containing Mg(OH)2, CaSO4$2H2O, CaCO3). Although this mud is sometimes used as a fertilizer (see the
Section 3 of this paper), many soda ash producers regard
it as a waste product and therefore suspend it in water
and dispose of it in the waterways (or in abandoned caverns
of a salt mine).
In some cases (as it was the case in the factory of Solvay
sterreich GmbH in Ebensee, Austria), a waste product
O
of the production of evaporated salt e the so-called
mother liquor e can be made use of for the purification
of the crude brine: due to the fact that sulfate is not removed in conventional brine purification, evaporation of
brine has to be stopped prior to the crystallization of solid
Na2SO4. The residual mother liquor contains NaCl, Na2SO4,
a little Na2CO3 (due to the excess of Na2CO3 addition in
the second step of brine purification, see Eq. (15)) and potassium compounds (see Table 2). Although it is generally
regarded as a waste product, it can be utilized as a source of
Na+ in the Solvay Process, because, like NaCl, Na2SO4 is
better soluble than NaHCO3, which is the only precondition
for the Na+-source that has to be fulfilled for the production
of soda ash in the Solvay Process. In Ebensee, milk of lime
was added to a mixture of 10% mother liquor and 90%
crude brine in the first step of the purification of brine.
This method has the advantage that mother liquor is a cheap
raw material and that it saves valuable soda ash in the

835

second step of brine purification, because more of the


Ca2+ is precipitated in the form of gypsum. Unfortunately,
the high sulfate content such brine causes problems during
the NH3 distillation, because of the onset of waste-gypsum
and scaling of the DS-units.
Although the only obvious by-product of the Solvay Process is CaCl2 (see Eq. (10)), the onset of solid wastes (sludge)
may not be neglected. In the Austrian Solvay factory in Ebensee (producing an annual amount of 164 000 tons of Na2CO3),
approximately 40 000 tons (dry mass equivalent) of solids
were annually disposed to the lake Traunsee; the ratio of brine
purification mud to solid distiller waste was approximately
1:3. The composition of both types of waste from the factory
in Ebensee is shown in Table 1. After decantation and filtration, the brine purification sludge contained approximately
40% moisture in Ebensee. For easier disposal, it was suspended in water again and pumped to the disposal site. The
solid DS waste was disposed of in the form of a thin aqueous
suspension (solids in CaCl2/NaCl-solution), forming a sludge
not until sedimentation on the bottom of lake Traunsee.
2. Samples and methods
2.1. Experimental aims
In addition to a general discussion, aim of this study was to
experimentally show the impact of the purity of the raw materials to the onset of wastes and to investigate the regeneration
of lake Traunsee, where the wastewaters of the Solvay Factory
in Ebensee had been drained to until its shutdown. For this
purpose, chloride titration and Neutron Activation Analysis
(NAA) were used.
2.2. Chloride titration
The chloride content of water from the river Traun and the
lake Traunsee (see Fig. 1) was determined by Volhards chloride titration. Although less known than Mohrs chloride titration (using AgNO3 and K2CrO4 as an indicator), in the
authors opinion, the indicator in Volhards titration shows
a clearer change of color. Water samples were taken in the
summer of 2002, when the Solvay factory was still producing
164 kt soda ash per year, as well as in the summer of 2006 e 1
year after this soda ash factory was shut down (after 120 years
of soda ash production). All samples were taken on the places
shown in Fig. 1. To an aliquot of 25 ml of water, 1 ml of 0.1 M
AgNO3 solution was added, leading to the precipitation of
AgCl. Residual Ag
aq. ions were titrated using a 0.1 M
NH4SCN solution. A few drops of an acidic solution of
NH4Fe(SO4)2$12H2O were used as an indicator. Each titration
was repeated: n 3 (2002) and n 6 (2006).
2.3. Instrumental neutron activation analysis
Short time Instrumental neutron activation analysis (INAA)
was applied primarily to determine the Al content of the solid

836

G. Steinhauser / Journal of Cleaner Production 16 (2008) 833e841

preconcentration of the non-carbonaceous and thus insoluble


matter. After washing with H2O and drying to constant weight
at 100  C, homogenization of the residual sandy matter was
performed in an agate mortar. The brine purification mud is
very homogeneous and had to be dried only.
The samples were weighed into polyethylene vials and irradiated sequentially for 2 min using the pneumatic transfer system of the TRIGA Mark II research reactor of the Atominstitut
(Vienna University of Technology) at a thermal neutron flux
density of approximately 3  1012 cm2 s1 together with
a set of reference materials, namely CANMET reference soil
SO1, NIST SRM 1633b Coal fly ash, light sandy soil BCR
No. 142, and MC rhyolite GBW 07113. After a cooling time
of 5 min, a first g(gamma)-photon-spectrum was measured
to obtain the activities of the short-lived activation products
28
Al (half-life T1/2 2.24 min), 51Ti (T1/2 5.8 min), and
52
V (T1/2 3.74 min). Four hours later, a second measurement
was started to detect the longer-lived activation products 56Mn
(T1/2 2.6 h) and 76As (T1/2 25.9 h). The measuring times
were 600 s and 1800 s, respectively. All samples were
measured in a fixed measurement position at a distance of
4 cm from the detector. The whole analysis was performed
with a 151 cm3 HPGe-detector (1.8 keV resolution at the
1332 keV 60Co peak; 50.1% relative efficiency), connected
to a PC-based multi-channel analyzer with preloaded filter
and Loss-Free Counting system.

3. Results and discussion


Fig. 1. Location of the Solvay factory in Ebensee (Austria) and its limestonequarry as well as locations of the sampling sites of water from the river Traun
and lake Traunsee: A e River Traun near Plankau; B e Bridge over the river
Traun in Ebensee; C e Rindbach, Ebensee (lake Traunsee); D e Ebensee,
location of the disposal of Solvays wastewaters to the lake Traunsee; E e
Traunkirchen; F e Altmunster; G e Gmunden; and H e mouth of the lake
Traunsee to the Traun river.

wastes, which is a good indicator for the content of clayey


minerals. Additionally, the content of some other elements
could be determined. INAA is an excellent tool for the simultaneous bulk analysis of a set of elements and it is the method
of choice for the analysis of geological samples [5].
All samples investigated with INAA were offered by Solvay
sterreich GmbH in 2002: brine purification mud and samples
O
of the limestone (iron oxide-rich Hierlatz limestone used until
the 1990s and white Upper Jurassic Tressenstein limestone,
used since then) that was used for the production of milk of
lime. Both types of limestone are found and open-cut mined
in Solvays quarry in Karbach on the eastern side of lake
Traunsee. The solid wastes of the DS are finely suspended particles in the distillation waste solution, which complicates
sampling. The insolubles of limestone were regarded to be
a sample as good as the solid distiller waste on the bottom
of lake Traunsee, since all insoluble compounds of the limestone finally form a part of the DS waste. Three kilogram of
each type of limestone was dissolved in diluted HNO3 for

Acidic dissolution of the two types of limestone led to


the production of 8.5 g/kg fine-grained insoluble material
(Tressenstein limestone) and 9.5 g/kg (Hierlatz limestone),
respectively. Thus the use of the cleaner raw material e limestone e was a significant step towards the ecologization of the
Solvay Process in Austria. The SiO2/Al2O3/Fe2O3 effluents
could be reduced by more than 10%.
The results of the INAA of solid wastes of the Solvay Process are presented in Table 3. They show that the content of
clay (for which Al is a good indicator) and heavy metals in
the insolubles of Tressenstein limestone is significantly
reduced in comparison to the insolubles of the Hierlatz limestone. Obviously, the insolubles of Tressenstein limestone consist mostly of quartz. In literature, one can find purity limits
for the limestone used in the Solvay Process, e.g. >90%
CaCO3, <6% SiO2, <1.5% Al2O3 Fe2O3 [6], which should
be regarded as unsustainable. Limestone just about complying
Table 3
Results of the INAA

Brine purification mud


Insolubles of Hierlatz limestone
Insolubles of Tressenstein limestone

Al

Ti

Mn

As

860
58 000
3800

<300
<300
1000

<2
130
10

212
396
88

2.2a
56
<40

All values given in mg/kg. Errors due to counting statistics are <10% for As
and Ti, and <5% for all other elements.
a
This value is taken from Steinhauser et al. [27] (a study using long-time
activation INAA).

G. Steinhauser / Journal of Cleaner Production 16 (2008) 833e841

with these limits should not be used any longer for ecological
reason, since its tailings will result in an unnecessarily high
content of suspended solids in the liquid effluents. Because
of its low carbonate content, the utilization of impure limestone also causes increased transportation costs: in such
a case, a larger volume of rocks has to be delivered to the factory to obtain the same amount of reactive CaCO3 compared
with high purity limestone. Moreover, in many industrialized
countries, the extent of production of soda ash is limited by
environmental regulations. In this case, the use of impure
limestone causes the decrease of production or environment
pollution fines. Modern soda ash plants should use limestone
with a purity grade of 95e99% CaCO3.
The results of the chloride analyses (shown in Table 4, see
also Fig. 1 for explanatory notes) evidence that, concerning
soluble chloride wastes, the capability for regeneration is
very high, even for an inland water like lake Traunsee.
One year after the production of soda ash had stopped in
Ebensee, the chloride values decreased by approximately
75%. This is in good agreement with Schmidt [7], who found
a retention rate of Traunsee water of 1.1 years. The residual
chloride content in the water of lake Traunsee found in 2006
is mostly due to the activity of the salt work in Ebensee,
caused by draining the mother liquor into this water (approximately 70 t/d).
One of the most important drawbacks of the Solvay Process
is the high energy consumption of 10e13 GJ/t soda ash, compared to the production of soda ash from natural minerals
(approximately 5.25 GJ/t Na2CO3 in case of Trona processing). In the latter case, neither energy extensive steam for
the NH3 distillation nor calcination of limestone is needed.
The lime kilns of a Solvay plant need 2.2e2.8 GJ/t Na2CO3,
the other process steps need 7.5e10.8 GJ/t Na2CO3. As a consequence of the combustion of fossil fuel (primarily coal), the
production of 1 ton of soda ash causes the emission of 200e
400 kg CO2. The other gaseous/aerosol emissions are 4e
20 kg CO, <1.5 kg NH3, and <0.2 kg dust per ton of soda
ash. Gas compressors used in the process can be driven by
electrical motors or steam turbines, leading to an electrical
consumption of 50e130 kWh/t Na2CO3 [2].
The experimental results of this study explain why solid
and sparingly soluble compounds, in general, are regarded
as more troublesome than liquid solutions: because sludgeand slurry-like wastes accumulate on the bottom of the
waterways into which they are discharged, whereas the salt
solutions dilute in water. A simple method (property of Solvay
S.A.) for the reduction of the amount of insoluble solids in
brine purification mud has been presented by the author

837

[8,9]. This process called Split-Precipitation shows that the


reduction of solids can be easily achieved by re-arrangement
of the order of reactions: instead of substituting Mg2 by
Ca2 ions, in this case the first step is adding soda ash to the
crude brine:
Mg2 Ca2 2Na2 CO3 / MgCO3 Y CaCO3 Y
4Na

16

In this equation, MgCO3 is the simplified notation for


basic magnesium carbonate (magnesia alba). Approximately
10% of the Mg2 ions are removed in the form of basic
MgCO3 in this reaction and need not be precipitated with
Ca(OH)2. This helps to save milk of lime, and furthermore
reduces the input of Ca2 and consequently the amount of
sludge. However, Mg2 cannot be removed quantitatively
due to the solubility of the magnesia alba in concentrated
brine.
In the next reaction, therefore, Ca(OH)2 and mother liquor
(here abbreviated as SO2
4 ) are added to the brine to remove
the remaining Mg2 ions:
Mg2 SO2
4 CaOH2 / MgOH2 Y CaSO4 Y

17

Of course, CaCO3 is precipitated in this reaction as well,


because of the residual CO2
3 ions dissolved in the brine, as
a consequence of reaction (16). In the final reaction, residual
Ca2 ions are precipitated like in the traditional process, using
soda ash (see reaction 15).
The precipitates are removed from the brine by sedimentation and/or filtration after each purification step. Before the
sludge is disposed of into the waters, it is suspended in water
and thoroughly stirred. Two solids, namely basic MgCO3,
coming from reaction (16), and CaSO4 from reaction (17),
react within a short time and reduce the amount of sludge
once more by formation of solid CaCO3 and water-soluble
MgSO4:
MgCO3 CaSO4 / MgSO4aq: CaCO3 Y

18

The overall reduction of solids in this proposed process is


approximately 30% per weight. It requires an increased
Na2CO3 consumption of approximately 11% (5.0 g/l instead
of 4.5 g/l crude brine) and one additional filtration step.
In the U.S.A., environmental regulations have forced the
shutdown of all synthetic soda ash plants already decades
ago. This was, of course, only possible because of the
existence of large trona deposits in the Green River basin
(Wyoming), which are used since 1953 for the production of
the essential industrial commodity soda ash, as well as the

Table 4
sterreich GmbH stopped the
Chloride concentrations (mg/l) in the water of the Traun river and lake Traunsee in summer 2002 and summer 2006 (Solvay O
production of soda ash in summer 2005)
Cl concentration (mg/l)

2002
2006

3.2  0.3
0.5  0.2

4.3  0.3
1.2  0.3

50  8
13  2

57  9
13  1

55  4
12  3

49  4
14  2

59  5
13  2

36  4
12  2

See captions of Fig. 1 for the explanation of the symbols AeH.

G. Steinhauser / Journal of Cleaner Production 16 (2008) 833e841

838

processing of natural Na2CO3-rich brines in California and of


nahcolite-deposits in Colorado [1]. Compared to the Solvay
Process, the solid and liquid effluents from the processing of
soda minerals are negligible. However, in Europe, there are
no comparable soda mineral deposits. The European industry
is thus dependent either on the production of synthetic soda
ash or its importation. As a consequence of increasing environmental regulations, European soda ash producers might be
forced to transfer their factories to the coast. The dissolved
compounds of the distillation wastewater (mainly CaCl2 and
NaCl) lose most of their ecological significance when discharged to the sea [4]. The fate of the Solvay S.A. plant in
Ebensee (Austria), which stopped soda ash production in
2005, showed that probably only soda ash plants on the coast
will succeed in the future. Already now, the largest European
soda ash plants of the leading soda ash producer, Solvay S.A.,
are located on the coast1.
In the literature, there are hundreds or thousands of reports
about modifications of the Solvay Process. Many of them aim
at a cleaner production by production of a valuable by-product
from the wastes of the Solvay Process. From the vast of propositions existent, the following will be shortly discussed.
3.1. The production of magnesium chloride instead of
calcium chloride
During the Second World War, the Diamond Alkali Company [10] modified the Solvay Process to obtain MgCl2, which
was used for the production of Mg as a raw material for the
construction of airplanes. They used dolomite instead of limestone as a source of CO2 and for the DS:
Calcination:
MgCO3 $CaCO3 / MgO$CaO 2CO2

19

Slaking of burnt dolomite:


MgO$CaO 2H2 O / MgOH2 $CaOH2

20

Ammonia distillation:
MgOH2 $CaOH2 2NH4 Cl / CaCl2 aq: MgOH2 Y
2NH3 [ 2H2 O 21

could not meet the requirements, but it was stopped soon after
the war.
3.2. The production of ammonium chloride as rice paddy
fertilizers
In Japan, where NaCl is imported as a solid, a modification of
the Solvay Process was developed [11,12] that yields higher
Na conversion rates (90%) and leads to the crystallization solid
NH4Cl by cooling and the addition of solid NaCl to the process
solution after NaHCO3 precipitation. The resulting mother
liquor is then saturated with NaCl again and recycled e there
are no liquid DS effluents, because the process water is recycled.
The solid NH4Cl is used as a rice paddy fertilizer, because rice is
a chloride tolerating plant. This modification of the Solvay
Process has been used in Japan only, because of the very special
regional necessities there. A few years ago, the last factory
using this process modification was shut down because of the
decreasing demand for NH4Cl fertilizers and the importation
of cheaper soda ash from the U.S.A.
3.3. The production of hydrochloric acid
Lynn and Forrester [13] developed a process modification,
using magnesite instead of limestone, in which the MgCl2containing DS-solution is decomposed by pyrohydrolysis:
MgCl2 $H2 O / MgOHCl HCl approx: 200  C

23

MgOHCl / MgO HCl above 500  C

24

The MgO is recycled for the ammonia distillation. The


process had never been applied for two main reasons.
Firstly, the additional energy consumption of this process
thwarts its implementation: the distillation wastewater had
to be evaporated completely before pyrohydrolysis (more
than 20 GJ/t Na2CO3 just for the evaporation of the water)
and the DS with the weak base Mg(OH)2 requires much
more steam than with Ca(OH)2. Secondly, the HCl-market
is more than saturated with HCl as a by-product from the
production of organic chlorides and from chlor-alkali electrolysis. Thus it is uneconomic and has never been adopted
industrially.

Production of MgCl2:
3.4. The use of amines instead of ammonia
CaCl2aq: MgOH2 CO2 / CaCO3 Y MgCl2 aq:
H2 O

22

This process modification was only profitable because of


a temporal necessity, when conventional sources of MgCl2

The largest European soda ash factories with a capacity of production of


approximately 1 Mt/a each are: Devnya (Bulgaria), Rosignano (Italy), Torrelavega (Spain, all Solvay), and Northwich (UK, Brunner Mond).

Some processes have been developed to increase the Na


conversion rates with the help of tertiary or primary amines
instead of NH3 e.g. see Refs. [14e21]. The regeneration of
the amines should be performed with Ca(OH)2 or Mg(OH)2.
This proposed process has been successful on a pilot plant
stage, but it was never implemented on the large industrial
scale so far because of technical problems, like the additional
efforts to avoid any environmental contamination with amines
or organic solvents.

G. Steinhauser / Journal of Cleaner Production 16 (2008) 833e841

3.5. The production of vinyl chloride


Hutchings and Joffe [22] proposed the regeneration of a tertiary amine hydrochloride as discussed above, using acetylene
and producing vinyl chloride using a gold catalyst:
NR3 $HCl C2 H2 / C2 H3 Cl NR3

25

Vinyl chloride would then be separated from the amine by


distillation. To the authors knowledge, this process has never
been adopted industrially, either. This is probably due to the
same technological and environmental reasons like described
above.
3.6. The production of cosmetic chalk
Kasikowski et al. [4] recently proposed the production of
CaCO3 from the wastewater of the Solvay Process. They propose the reverse reaction of the Solvay Process itself (Eq.
(10)), by precipitation of the Ca2 ions of the DS wastewater
with a defective Na2CO3 assortment e a product, which
fails to meet the quality standards for light (bulk density
0.5e0.6 kg/l) or dense (1.0e1.1 kg/l) soda ash:
CaCl2 Na2 CO3 / CaCO3 Y 2NaCl

26

Cosmetic chalk or precipitated calcium carbonate (PCC; or


calcium carbonicum praecipitatum, CCP) is a widely used
functional filler material or whiting agent. CCP is characterized by several factors, such as purity, particle size, porosity,
brightness, stiffness, rheology, and the right crystallographic
modification (calcite or aragonite), which can be influenced
by various factors like the temperature during precipitation.
It is state-of-the-art to produce CCP by precipitation of
highest-purity-Ca(OH)2 with CO2:
CaOH2 aq: CO2 / CaCO3 Y H2 O

27

Precipitation from milk of lime is preferred over the precipitation from Ca2 salt solutions in order to avoid salt inclusions, which would contaminate the final product. When
using DS wastewater, all suspended particles had to be
removed completely prior to the reaction. Moreover, the dissolved Mg2 ions of the DS waste would partly precipitate
in the form of basic MgCO3 (approx. 4MgCO3$Mg(OH)2$4
or 5H2O) upon the addition of soda ash. The final contaminated precipitate would therefore, contain crystal water in
the form of magnesia alba. This is certainly not desired for
some applications. From these points of view, the strategy proposed by Kasikowski et al., should be reconsidered before
applying such functional fillers in delicate technological fields
like pharmaceuticals, plastics or printing inks.
In Solvays factory in Ebensee, there had been attempts to
obtain high quality CCP in the second step of brine purification, when soda ash is added to precipitate Ca2 ions (Eq.
(15)). Because of the salt inclusions mentioned above, these
experiments were stopped (see Ref. [2], p. 64), and Solvay
S.A. now exclusively embarks the other strategy using
Ca(OH)2 and CO2. The problem of salt inclusions in a precipitate

839

is, by the way, an inherent technical problem of the Solvay


Process itself: chloride inclusions in the NaHCO3-precipitate
lead to a much higher NaCl content in synthetic Na2CO3
(namely 0.15%) than compared to soda ash from trona
(0.035%) [21]. The chloride content of Solvay-Na2CO3 is close
the upper limit for the production of glass, were a lower chloride
content is preferable.
3.7. The production of fertilizers from brine
purification mud
Recently, the use of brine purification sludge as a lime fertilizer has been discussed [23e25]. However, the application
of this sludge as a fertilizer is limited due to several aspects
[8]: the brine purification mud has to be washed thoroughly
to remove most of the chloride. A fertilizer should contain
1% chloride, which is equal to 1.65% NaCl. This is still
a quite high amount for chloride sensitive plants. The sludge
must have a sufficiently low water content (28 wt %), if conventional fertilizer-distributing machines are to be used. The
fundamental problem of such fertilizers is that they do
not contain significant amounts of the three major macronutrients nitrogen, phosphorus, and potassium (NPK). However,
in some cases, brine purification sludge may be applied for the
neutralization of acidic soils. The content and the bioavailability of heavy metals in a fertilizer made of brine purification
sludge should be considered prior to its utilization for such
purposes (see Table 3 and [26,27]).
The historical development of the Solvay Process shows
that only very few modifications aiming at the production
of a valuable by-product have been successful. If at all, temporal or regional conditions allowed these modifications, but
only few could succeed on a global scale. Beside technological barriers (like insufficient quality of the by-product due to
the utilization of a waste product as a raw material), the main
reason for this phenomenon is probably the high production
rate of a soda ash factory, which is necessary to obtain profit
out of the production of the low-cost commodity soda ash,
whereas the demand for the by-product is limited or the market is already saturated by competing technologies. Thus, it
is difficult to successfully adopt such a modification of the
Solvay Process on industrial scale for technical and economic reasons.
However, there is still room for ecological optimization in
this process, primarily by increasing the conversion rate of the
raw materials (especially NaCl), or new technologies for
avoidance of the onset of wastes (like selective solution
mining of the rock salt deposit without dissolving the gypsum-tailings, which helps reducing of the alkaline earth metal
sterreichiion content in the crude brine, as proposed by the O
sche Salinen AG [28]) thus the research must continue.
4. Conclusions
The experimental results of this study as well as the observations of the development of the industrial landscape of soda
ash production allow the following conclusions.

840

G. Steinhauser / Journal of Cleaner Production 16 (2008) 833e841

(1) Solid and insoluble wastes from the Solvay Process should
be regarded as the more troublesome than dissolved solutions of Ca2, Na, and Mg2 salts. The slurry-like solids
accumulate on the bottom of the waters into which they
are discharged, whereas solutions dilute in water. Of
course, salt solutions to a certain extent impact the aquatic
environment, too. A few studies (and Schmidt [7,29])
showed that the diatom flora slightly changes in lake
Traunsee with increased Cl concentrations: Cl tolerating species are subtly preferred over Cl sensitive species.
Sonntag et al. [30] investigated the pelagic protozooplankton (ciliates and flagellates) and found that there are no
differences at the community level between lake Traunsee
and two neighboring lakes without industrial influence. On
the other hand, Schmidt [7] showed that benthic organisms
are much more influenced by the reducing conditions
caused by the alkalinity of the sludges. Higher organisms
cannot survive in such alkaline environment, whereas
some microorganisms are able to accommodate to such
conditions. According to Schmidt, the influenced lake sediments can be regarded as partially sterile (and lethal for
fish eggs). However, Schmidt emphasizes that the fish
population of lake Traunsee as a whole is not or only
marginally influenced by the Solvay emissions. The phytal
environment is only slightly and locally affected.
In this study, it could be shown that even an inland
water like lake Traunsee shows an excellent capability
for regeneration with regards to the waters chloride concentration. However, the environmental influences of the
sludge, covering 19% by area of the bottom of the lake,
will last for years.
(2) Cleaner production in the Solvay Process can be achieved
most efficiently by the utilization of cleaner raw materials.
Since every impurity will cause the onset of (mostly solid)
waste, the limestone used in this process should consist of
almost 100% CaCO3. Wherever it is possible, the use of
a salt works sulfate-rich mother liquor as a Na-source
should be avoided for reduction of the amount of wastegypsum as a by-product of the NH3 distillation.
(3) At present, one main technological challenge of soda ash
producers is to increase the utilization rates of the raw
materials of the Solvay Process. Especially the loss of
30% NaCl in the course of NaHCO3 precipitation offers
a big opportunity for making improvements in the process.
(4) In most cases, avoiding wastes is a much more promising
strategy than to attempt to make use of the wastes. Any
modification of the process causes additional costs. In general, it should be ascertained how sensible it is to attempt
the production of valuable commodities from the wastes of
a process focusing upon the production of a low-priced
industrial product like soda ash. Since the wastes of the
Solvay Process, e.g. the distillation wastewater, containing
dissolved CaCl2, MgCl2, NaCl and a huge amount of suspended particles of various chemical compounds, are not
homogeneous, the industrial efforts focusing upon the production of a high quality by-product would be enormous.
The main problem from an economic point of view is the

competition with existing technologies for the production


of the respective by-product (e.g. CCP as a filler). Since
the CCP market is saturated, a low-quality by-product
from the wastes of the Solvay Process might not compete
with high-quality products of high purity. Only in a few
occasions, has a modification of the Solvay Process that
aims at the production of a by-product been successful
in the past (e.g. the production of NH4Cl as a fertilizer
in Japan, or the production of MgCl2 in the U.S.A. during
the Second World War).
(5) Without future developments in the avoidance of wastes at
their sources and increasing raw material utilization rates,
in combination with increasing environmental protection
regulations, probably only (synthetic) soda ash plants
that can dispose of their wastes to the sea will survive in
industrialized countries, on the long run.

Acknowledgements
sterreich GmbH, in parThe author likes to thank Solvay O
ticular Gerhard Eder and Gerhard Hubweber for the good
cooperation, Matthias Kerbl for his support in laboratory
work, and Max Bichler for providing access to the analytical
facilities in his laboratory. Thanks are also due to Francis
Coustry (Director Research & Technology Alkali Products,
Solvay S.A., Brussels) for his support.
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