The Linde Solinox process: Gypsum-free

flue-gas desulphurization
J. Sporer
Linde AG, Werksgruppe Vetfahrenstechnik und Anlagenbau, 8023 Hiillriegelskreuth,
Germany

The details of a physical scrubbing process for flue-gas desulphurization are given together with a
comparison with conventional chemical absorption processes. Relative advantages of the process and
case studies of its implementation in a variety of plants are discussed.

Keywords: flue-gas desulphurization; SO2 removal; Solinox process

Principal features of the Solinox process The CaSO, formed normally requires additional oxidation
for complete conversion to gypsum, CaSO,. The volume
Over a period of more than a century. Linde has
of gypsum produced is. however. in itself a problem
accumulated comprehensive experience of physical pro-
because the quantities that can be marketed in the
cesses with over 3000 plants designed and installed for the
construction industry are limited and the remainder has
dissociation and purification of gases. Building on this
to be dumped. Moreover. the production of gypsum does
experience, a process was developed for desulphurization
not coincide with its use either locally or seasonally
of waste gases containing SO?, which similarly works
(construction is cut back in winter when power stations
with a purely physical wash. This gives the process its
are working at full loady.
principal features of:
Several studies dealing with the utilization of FGD
gypsum attest to its biological safety for construction at the
recovery of a valuable product. namely concentrated present level of knowledge4. However. it is expected that
so,: the problems entailed in the sale or disposal of mounting
stable operating conditions regardless of fluctuating volumes of FGD gypsum will steadily increase. at least in
SO? gas concentrations; the medium to long term. as public resistance to waste
simultaneous removal of hydrocarbons: products continues to grow. In addition. in those instances
almost complete absence of solid process products. where the gypsum is contaminated by heavy metals (e.g.
semi-dry processes). it must be expensively contained at
These distinctive properties of the process will be special hazardous-waste dumps. In Germany. the cost of
described in more detail while comparing it with con- hazardous-waste dumping ran as high as DM 300 t-’ in
ventional chemical absorption processes. 1990 and must be expected to increase considerably
yet”.
In accordance with these problems that could be
Production of saleable non-gypsum product foreseen. a completely different method of removing SO,
Being a medium-strength acid. SO, is capable of com- was selected in developing the Solinox process. By
bining with basic substances. which is the principle contrast with the lime washes mentioned above. the
employed in most desulphurization plants.The absorbent process uses a wash liquor that employs physical solubility
commonly used is milk of lime. a chemical that is cheap rather than chemical reaction to take up the SO?. akin to
and in ready supply. Another reason for the market dissolving CO? in mineral water. This means that the wash
dominance of the limestone-gypsum process stems from liquid and the absorbed gas enter into purely physical
the fact that it was already available as a relatively well solution, which is a relatively weak bond compared with a
developed technology at the time the boom in power- chemical compound.
station flue-gas desulphurization (FGD) plants set in and In turn. therefore. the dissolved gas can subsequently
its capital outlay is comparatively modest. be separated from the solution by simple physical means
The reactions taking place during and after absorption in a regeneration column and recovered as a reusable
are concentrated SO, product. The options for re-use are
marketing in liquid form or feeding as SO&h gas to a
Ca(OH), + SO? - CaSO, + HZ0 Claus process plant for manufacture of elemental sulphur
or feed to a sulphuric acid plant. In this way. the process
CaSO, + O> --* CaSO, complies with more recent waste-control regulations

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Gypsum-free flue-gas desulphurization: .J. Sporer

requiring extensive reutilization of residuals from FGD continuing through the hot zone of the furnace, the
plants. decomposition products are normally entrained straight
Selling prices realized in 1990h were approximately: out with the flue gas and thus escape further or complete
oxidation.
0 DM 200 t-’ for liquid SO,; Solvents used for SO, removal in the Solinox wash
l DM 200 t-’ for elemental sulphur; have been established to possess good solubility also for
l DM 70 t-’ for concentrated sulphuric acid. heavy hydrocarbons present in the raw gas. Many
constituents (e.g. benzene) can be reduced to well below
the emission levels stipulated. for instance. in Germany’s
Stable operating conditions with fluctuating SO2 TA-Luft regulations.
inlet concentrations Hydrocarbons coabsorbed in the SO, wash are stripped
from the solution togetherwith the SO, in the regeneration
From the equations given for the lime-gypsum process
stage of the process and thus pass out with the flow of SO?-
another fundamental difference to chemical absorption is
rich gas. Optimum disposal of the hydrocarbons is
apparent. Chemical reactions are stoichiometric. which
ensured by subsequent separation in a rectifying unit or
means that one mole of lime or two moles of NaOH or
by combustion when the SO,-rich gas is fed to a suitably
Na,SO, must be applied for each mole of SO, to be
hot furnace zone, as in a sulphuric acid plant.
absorbed. The higher the SO, concentration, therefore, the
larger is the volume of absorbent employed in the process
Simple and solids-avoiding process concept
and thus too of the reaction product salt, for example
gypsum. As a result, precise measurement of volumes and In principle, the only inlet flow to the Solinox process is
concentrations is necessary and suitable control devices the gas stream to be cleaned. since the solvent circulates
must be installed. being of utmost importance in main- exclusively between the absorption and regeneration
taining the desired desulphurization efficiency. especially columns and is not consumed. Only minor physical and
when the SO, inlet concentration is variable7-X. chemical losses need to be made up.
With a physical wash such as Rectisol@. a pressure Throughout the process, mass transfer is limited to two
water scrubber. or in the present instance Solinox, the rate phases: gaseous and liquid. No solid products and no
at which SO, must be removed likewise increases with its evaporation or crystallization steps are involved.
concentration in the gas, but the difference is that in Accordingly. hardly any risk of incrustation or clogging
accordance with Henry’s law the absorptive capacity of occurs in the Solinox process. For this reason. and since
the solvent also increases due to the higher partial all handling of solids (bulk stocking. solution mixing.
pressure of the SO?. evaporation. crystallization, solid product storage and
What this means is that a Solinox plant runs at stable transportation) is eliminated. the number of operating
operating conditions. the volume of circulating absorbent and maintenance staff needed is small. Moreover. no
remaining the same and the SO, concentration of the storage space has to be reserved for the considerable
cleaned exit gas being maintained virtually constant even quantities of limestone and gypsum with which other
when the SO, level of the inlet gas is subject to extreme processes are burdened.
fluctuations. incurred for example by batch operation of a
furnace.
Description of the process concept
Physical absorbents are capable of controlling the
emission of SO, also when the specified maximum SO,
Flue gas cooling and reheating
concentration is exceeded in the inlet gas. provided the
downstream systems are not limited in their capacity to A flow diagram of the process is shown in Figure I. At the
accommodate the overshoot in SO, output. absorption plant interface the flue gas is received in the
state at which it would otherwise pass to the stack when no
Example. Let a desulphurization plant be designed for a FGD unit is installed, i.e. at almost atmospheric pressure
maximum SO? inlet concentration of 15 g Nrn-j and a and a temperature between 120 and 200°C. Depending on
corresponding outlet concentration of 0.2 g Nrn-j in the the upstream process, its SO? concentration is usually
cleaned exit gas. In response to irregular conditions between 0.2 and 3%. The flue gas is first cooled in heat
causing the SO? concentration of the inlet gas to rise to exchanger El. concurrently heating the clean exit gas
20 g Nmm3, a chemical wash will allow breakthrough of from the absorber to adequate stack inlet temperature.
5.2 g Nmm3 of SOZ in the exit gas. Although sized for the If required, owing to contamination by halogenides.
same 15 g Nm-’ SO? inlet concentration, a Solinox wash dust or aerosols, the flue gas can undergo preliminary
would by contrast be able to control SO? emission in the cleaning by wet scrubbing at Dl. Make-up water for this
exit gas to less than 0.3 g Nm-j. unit is supplied by condensate from the flue gas.
Since physical gas-wash processes are more favourable
to operate the lower the absorption temperatures are, it is
Simultaneous removal of hydrocarbons advantageous to provide a second water-quench cooling
stage in which the flue gas temperature is lowered as far as
Analysis of numerous flue gases has revealed that
cooling-water conditions at the site will allow. Under
concurrent presence of unburned hydrocarbons is not
certain conditions it may be favourable to use an external
uncommon in flows containing SOI. These hydrocarbons
chilling system.
are frequently formed by pyrolysis. When charging
combustion or roasting furnaces. the coal, ore or other
SO2 wash
feed first enters a zone of comparatively low temperature
in which combustion is not complete, proceeding no The scrubbed and cooled gas leaving the water quench
further than decomposition and degasitication. Instead of enters through the bottom tray into the wash column in

134 Gas Separation Et Purification 1992 Vol 6 No 3

 Gypsum-free ftue-gas desulphurization: J. Sparer

Flue gas
i

I I D2
Clean E7

-5
9s El

Cl c2
to st' Ick

P4 ~ Cooling water

E6 &xiter Refrigerant

Tl ---PI T2

ES Al

Water

/ ( tP steam
P3
Waste Liquid
water d -
-c3 so*
product

Figure 1 Flow diagram for the Solinox process

which desulphu~zation takes place. Regenerated solvent process to still be installed conveniently when space is
is fed to the head of the packed column and absorbs the limited. With large plants it is possible for regeneration of
SO, from the rising countercurrent flow of flue gas. The the solvent from several SO, washes to be economically
saturated solvent is withdrawn via the bottom tray and centralized at any suitable location.
routed to the regeneration column. Methods of regenerating physical solvents are lowering
In keeping with the nature of a physical gas-wash. the pressure. increasing temperature or stripping with steam.
SO1 absorption system can be designed for almost any In the Solinox process, all three are combined. The
desired efficiency of removal and thus afmost any desired saturated solvent withdrawn at the bottom tray of the SO?
maximum residual concentration of SO,. Efficiencies of wash takes up enough heat from the regenerated solvent
99% and residual levels below 0.1 gNm_’ are readily in heat exchanger E3 as to be almost at regeneration
attainable. temperature when it is expanded into column 1-2, where it
With other conditions constant. absorption efficiency is regenerated by stripping. Heat required to generate the
and exit concentration are determined only by the stripping steam is supplied from reboiler E5 in the form of
number of theoretical plates. meaning the packed height low-pressure steam or cheap waste heat. Together~th the
of the column. Therefore the extra expenditure entailed in gases stripped from the solvent, the steam exits the
order to ensure constant low exit levels with very high SO: regeneration column through the top plate.
concentrations in the inlet gas is small. consisting only of
additional packed height. SO, clean-up and liquefaction
Final clean-up and liquefaction ofthe SO? is recommended
Solvent-retaining aftenwash and flue-gas compression if no provision is made for it to be processed directly, for
Although vapour pressure ofthe solvent is very low, liquid example to manufacture sulphuric acid or sulphur.
losses would rise above a neglible level due to entrainment Clean-up consists in conventional adsorption drying
with the large gas throughput. Therefore the desulphurized followed by distillative separation of inert gas in column
gas undergoes final treatment in a third column. which is T3.
again a water wash. Owing to the excellent solubility of the The high-purity SO? thus obtained is withdrawn from
solvent in water, the flue gas contains practically no the sump of column T3 in liquid form. It can be
solvent on leaving this second water wash. transported by standard tanker trucks and has a broad
Before the desulphurized gas exiting the head ofwash- variety of possible uses. The inert gases exiting the head of
column Tl can be reheated in clean gas heater El. it is the clean-up column are returned to wash-column TI.
compressed in blower C I to compensate pressure losses
occurring in the desulphurization plant. Operating experience

Solvent regeneration Proving the process

Nothing prevents regenerating the solvent at a point All physical data of the solvent important in the design of
remote from the absorption system. This allows the the process were measured at Linde’s laboratories in the

Gas Separation & Purification 1992 Vol 6 No 3 135

Gypsum-free flue-gas desulphurization: J. Sporer

entire area relating to the process. This gave sets of data

suitable for use in model computations.
So as to test long-term effects and stabilityofthe solvent
under actual flue gas conditions. a pilot plant was
constructed and operated for periods of2000 h on flue and
tail gases from various sources. This enabled the influence
of a wide variety of trace impurities and SO, inlet
concentrations (up to 2 mol%) to be recorded’. Operation
ofthe demonstration plant proved entirely successful with
all expectations fulfilled. resulting in the first contract to
design and supply a FGD plant being obtained in
December 1984.

Use at a lead and zinc mill

History. At its Arnoldstein works in KBrnten, southern

Austria, Bleiberger Bergwerksunion (BBU) has been
operating a lead mill since 1892 and a zinc mill since 195.5.
Emission of SO2 at a rate of 7000 t a-’ led to high, health-
hazard pollutant concentrations in the atmosphere of the
enclosed valley location. particularly during periods of
temperature inversion when natural ventilation is limited.
Proposals to restrict the emission of SO? by employing
lime washes were dropped on account of the unavoidable
heavy-metal content of the large volumes of sludge and
gypsum that would be produced and the attendant
hazardous waste problem. After examining all viable
methods, BBU contracted with Linde AG in 1984 to
supply a Solinox wash with a SO: recovery rate of 0 1 2
95%‘“.
SO2 concentration (vol %I
Lead-smelting flue gases. The three rotary-hearth
furnaces of the lead works incorporate BBU custom Figure 2 Typical variation of SO, concentration in the flue gas
engineering”. enabling them to smelt concentrate and from a zinc smelter
also recycled storage-battery scrap. Flue gas produced by
each furnace is IO 000 Nm3 h-‘. giving a total flow of
30 000 Nm’ h-‘. A drawback is the low SO? concentration flow from the residuals system. Integrating the solvent
of 1.4 ~01% maximum. fluctuating over a wide range. As a circuit for the two absorbers presented no difficulties in
result, its direct utilization for manufacture of sulphuric view of the relatively small piping sizes and therefore it
acid, such as is customary when roasting sulphide ores was decided to install a single system for centralized
and indeed practised by BBU at its zinc works, is not solvent regeneration and SO? liquefaction and storage.
possible. Because the dust content of the flue gases is relatively
low (under IO mg Nm-‘). it was possible to adopt more
Zinc smelting flue gases. In addition to the flue gas from advantageous heat regenerators, in place of recuperators.
the fluidized-bed zinc-roasting furnace, which is fed to a for heating the clean exit gas flows to the necessary stack
sulphuric acid plant, there is a second source of SO, in the inlet temperature of 70°C. Heat regenerators are large
zinc works. Lead, germanium, cadmium and zinc are vessels packed with heat-accumulating media, installed in
recovered from waste sludge in a residuals-processing pairs and operated alternately for absorbing and releasing
system’* of two Ddrschel furnaces operating on a 4 h heat. Compared with conventional heat exchangers they
batch cycle. This gives a flue gas flow of 50 000 Nm3 h-‘, have the advantage of a high heat-transfer capacity at low
containing a maximum of 2 ~01% SO?, which is again too pressure losses and the ceramic heat accumulators
weak for use as sulphuric-acid-plant feed. Figure 2 shows employed enable the otherwise difficult problem of
the typical variation of SO2 concentration in the Ddrschel preventing corrosion to be controlled easily. They have
furnace flue gas. the drawback of breakthrough occurring when cutting
over flow between the two units, which is why they are no
Plant concept. Photographs of the desulphurization longer adopted in plants with high SO? recovery rates.
plants for both the zinc-smelting and lead-smelting Energy to heat the reboiler is supplied by hot water at a
processes are shown in Figure 3. The layout of the Solinox low temperature level of approximately 125°C. which is
flue-gas cleaning plant generally follows the process generated at no cost when cooling the lead-smelting flue
concept as described above, but with a number of gases and was wasted before the Solinox plant was
customized features which are described here. commissioned.
Owing to the two SO1 sources being spaced far apart, Two alternative uses forthe recovered SO? are available
two wash units were installed. One wash-column cleans at the Arnoldstein site. Forone, it is liquefied and shipped
the 30 000 Nm3 h-’ flue-gas flow from the lead works and by rail tank car to customers in the pulp or other
a second tower of 50 000 Nm-’ h-’ capacity handles the industries. For the other, it is usable at the on-site

136 Gas Separation 8 Purification 1992 Vol 6 No 3

 Gypsum-free flue-gas desulphurization: J. Sporer

a b
Figure 3 Solinox desulphurization plant treating flue gas from (a) a zinc smelter and (b) a lead smelter

sulphuric-acid plant to manufacture additional quantities (2) SO2 emission level. At the time the Arnoldstein FGD
of acid. plant was commissioned. it was only possible to achieve
90% SO? removal efficiency instead ofthe guaranteed 95%.
Operating experience, problems and solutions. The The reason for this shortfall was incorrect assumptions
realization of the idea of a regenerative SO, wash has been made when scaling up from the pilot plant.
completely successful on the commercial scale. In service Improvements to the solvent inlet distributor and
for six years. the plant has been working reliably and has partial substitution of the column packings by others,
fulfilled the guaranteed emission levels and utility providing a larger surface area. enabled desulphurization
consumption figures. capacity to be increased above 95% in fact. During the
Personnel required to operate and maintain the plant guarantee run. the performance recorded was 97.7%
are small in number. as there are few mechanical actions efficiency for the lead works and 96.1% for the zinc
to be performed. One or two plant operators are normally works.
sufficient.
The concept of resource recovery in the form of a (3) S02product quality. The biggest problem that had to
marketable product has proved excellent. By virtue of the be tackled was the unexpected entry of heavy hydro-
relatively high income obtained from sale of liquid SO,. carbons into the flue-gas cleaning plant. Owing to these
the FGD plant has advanced almost to the status of a SO, being absorbed simultaneously by the solvent as previously
production facility. described. the SO? product was contaminated and thus
As was to be expected in the construction of this first unsaleable.
plant. starting difficulties were encountered and had to be In the flue gas itself. the problem-causing hydrocarbons
overcome. They are reviewed below. are not detectable by normal analytical methods except in
certain operating conditions (e.g. large volume of battery
(1) Resistance of materials. Material problems of the scrap in furnace charge). This explains why no allowance
type familiar in conventional systems necessitated some was made for hydrocarbons in the flue-gas specification
improvements in the Solinox plant as well. This particularly used as the basis for design of the plant.
concerned the solvent piping made from glass-fibre- After examining the various methods usable to separate
reinforced plastics. which had to be replaced after a few the hydrocarbons. such as thermal and catalyticcombustion
months of operation by new piping of high-alloy metal. or an upstream selective hydrocarbon wash, it was
which put an end to that problem. During general decided to install a rectification system for final clean-up
inspection of the FGD plant in September 1990. after four of the SO?. Among other things, this did not entail any
years in service. no indication of damage to the materials modifications to the roasting process or Solinox wash.
then in use was found. The long-term suitability of all the Again. this retrofit meant breaking new technological
materials of construction. namely plastics. high-alloy ground. necessitating a fresh round of laboratory and
steels, linings. etc.. had already seemed established when pilot testing.
corrosion damage occurred on the solvent reboiler in Subsequent implementation ofthis newvariant proved
December 1990. Investigation revealed the cause of successful all along the line. The hydrocarbons are
increased corrosive action to be a IOO-fold rise in the quantitatively separated and efficiently disposed of by
fluoride concentration of the flue gas above the specified routing them to the fluidized-bed furnace of the sulphuric-
level. resulting from changes in furnace operation. acid plant. No further problems have arisen in ensuring
Installation of a reboiler made from non-metallic materials the specified purity of the liquid SO? product.
brought the plant in line with the changed conditions. Accordingly, the Solinox plant makes an additional

Gas Separation Et Purification 1992 Vol 6 No 3 137

Gypsum-free flue-gas desulphurization: J. Sporer

contribution to controlling environmental pollution by physical and logistical separation of the flue gas
reducing the emission of benzenes and other heavy cleaning plant and calcium bisulphite system by two
hydrocarbons as well as SO2 to levels safely below limits discrete process steps, thereby enabling cooking liquor
prescribed by law. production to run independently of gas desulphuriza-
tion:
cleaning the exit gas to a residual SO? level of
Integration of Solinox plant in a pulp mill 200 mgNrn_j without need for additional NaOH
scrubbing or disposal of the spent liquor:
General note and history. Pulp is mostly composed of absence of need for a second wash column common to
cellulose, derived from wood or other fibrous plants. The other processes owing to the occurrence of clogging,
key function of the pulping process is acid digestion by thus eliminating need for regular purging and blow-
using various bisulphite solutions, during which the down to clean the columns;
fibrous matrix of the cellulose is broken down by production of a very small, but highly concentrated
dissolving the lignin that cements the structure. (over 80% SO?) rich gas flow, resulting in ideal
The pulping process used by Zellstoff Villach GmbH conditions for preparation of the cooking liquor
in Austria was to cook the debarked wood chips in (normal SO, concentration from sulphur burning is
digesters with calcium bisulphite, a classical pulping only 6- 18%);
liquor. The calcium bisulphite solution required for the
process was prepared at favourable cost by passing SO2 The more accurate and flexible control of cooking liquor
through absorption towers packed with limestone. The composition thereby made possible provides more favour-
raw pulp produced by this process must undergo sub- able conditions for the pulping process. accruing in
sequent treatment by washing and bleaching (e.g. chlorine economic advantages of reducing wood consumption and
or ozone bleach), while the spent cooking liquor (black uniform bleaching.
liquor) awaits disposal.
Since drainage of the spent cooking liquor containing 6 low consumption of process utilities:
lignin and sulphonic acid caused an intolerable environ- 7 by contrast with other processes, the intended later
mental nuisance, it was decided to concentrate the conversion from calcium to magnesium-base pulping,
eftluents by evaporation and incinerate them. accompanied with the added benefit of base recycling. entails no
by energy recovery. However. SO, is liberated on incinera- difficulties.
tion, which would have meant shifting the water pollution
problem to one of air pollution, therefore a decision was
made to install a Solinox plant for recovery of the SO?. The Plant concept. The flue-gas flow to be treated was
SO2 thus reclaimed from the spent cooking liquor was to 100 000 Nm’ h-’ with a SO? concentration of 0.7%. Here
be utilized in the limestone tower mentioned above to again, layout of the process generally duplicated that
prepare fresh liquor for the pulping process (Figure 4). described for lead-works FGD. but incorporated its own
special features.
Special merits of the process for cellulose production. In view of the specified sulphur removal efficiency of
The main criteria favouring selection of the Solinox 99.3%. a glass-tube heat exchanger was adopted for
process for this pulp industry application were: heating the cleaned gas instead of a heat regenerator
because of the unavoidable breakthrough occurring
1 recovery of the SO? as a resource usable in the pulping during regenerator cut-over.
process; With consideration to the special energy set-up
associated with the plant. such as utilization of waste heat
in a district-heating grid system, the reboiler was heated
by hot vapour compression for energy recovery.

Operating experience, problems and solutions. The

plant was commissioned in 1988 with successful integration
of the Solinox system into the overall concept.
Outside purchase of elemental sulphur for preparation
of the cooking liquor was no longer necessary. Only a
certain amount ofliquid SO2 had to be fed to the limestone
tower for the purpose of equalizing the sulphur balance.
Discharge of black liquor to the river Drau flowing past
the site ceased while SO, was recovered at a high rate. A
substantial amount of heat was transferred from the hot
flue gas supplied to the Solinox plant for utilization in the
city ofVillach’s district heating system. Later. gases of low
SO,concentration from other parts of the mill were routed
to the plant for disposal.
Only parts of the previous experience gathered in the
Arnoldstein project were capable of being applied to the
pulp mill plant, meaning that a number of subsequent
improvements had to be made in this instance too.
It evolved that use of the hot-vapour compressor for
Figure 4 SO, recovery plant at a pulp mill heat recovery purposes led to trace amounts of sulphuric

138 Gas Separation & Purification 1992 Vol 6 No 3

 Gypsum-free flue-gas desulphurization: J. Sporer

acid forming as a result of the high temperatures and the a zinc-barium base (lithopones, Sachtolith). Having
catalytic action of some materials of construction, causing previously introduced pollution control measures in its
corrosion damage on plates in the inlet of the following titanium oxide production by installing a weak-acid
reboiler. This problem was tackled by installing a treatment system, the company decided to upgrade the
sprinkler that rendered the impinging acid particles barium sulphide circuit of its lithopone plant as well by
harmless by immediately diluting them. incorporating resource recovery.
Material problems were also experienced with the first Lithopone is a white pigment used, like titanium
application of a glass-tube heat exchanger for clean gas dioxide, in paints, enamels and plastics. It is manufactured
heating, although of a different kind. Breakage, pre- by reacting a zinc sulphate solution with an aqueous
sumably due to thermal stresses coupled with inherent barium sulphite solution:
vibration of the exchanger, required about 5% of the total
Z&O, + BaS - ZnS + BaSO,
number of tubes to be replaced. The conditions responsible
for this damage were eliminated by modifications to The barium sulphide required for manufacture of litho-
operation. pone is produced at Sachtleben by reducing various
grades of batite with petroleum coke in three rotary
Comprehensive flue-gas cleaning in production of furnaces. The reduction process produces about
inorganic pigments 30 000 Nm’ h-’ of flue gas containing up to 0.5% SO?,
hydrochloric acid, hydrofluoric acid, dust and hydro-
Genera/ note and history. At its plant in Duisburg- carbons.
Homberg (Figure 5). Germany. Sachtleben Chemie GmbH The Solinox process was given priority mainly because
manufactures titanium oxide and also white pigments on of it being the only one among those considered that
offered complete flue-gas cleaning with removal of all
pollutants present.

Plant concept. A speciality of the Solinox process as

implemented in this project is integration of a fine dust
scrubber into the wash tower in order to reduce the dust
concentration from 0.2 g Nrn-j to 0.03 g Nm-‘. The flue
gas was to be desulphurized to a maximum SO? concen-
tration of 0.25 g Nm--‘. Halogenides and hydrocarbon
levels were to be controlled in accordance with the
emission standards of TA-Luft. The recovered SO,-rich
gas product. which also contains the coabsorbed hydro-
carbons. is delivered through a II00 m long pipeline to an
existing plant for conversion to sulphuric acid in an
approximate quantity of 5000 t a-‘.

Operating experience. Commencement of the flue-gas

cleaning plant trial run enabled the operating experience
acquired at Villach and Arnoldstein to be used for the first
time from the beginning to the end of the project. namely
for process design. selection of materials and suppliers.
installation and start-up. Indeed. no significant problems
developed during the trial run. After only three weeks in
operation, the guarantee test was completed successfully
and the plant was handed over to the owner. Actual purity
figures were in parts considerably better than the guaranteed
values. This resulted both from the reserves that had been
designed into the plant and from the cooling water supply
temperature being 1°C colder than stated in the project
specifications. Operating at 120% gas overload for example
(related to design capacity). the SO, concentration
achieved in the clean exit gas was low at 0.12 g Nm-‘.
Utility consumption figures were also well within
guarantee.
Operating irregularities in other process systems
proved of minor significance to the Solinox plant. As
expected, starting and stopping of the upstream furnaces
had no effect on operation of the desulphurization plant,
which continued running smoothly under automatic
control without need to adjust the operating parameters.
Short-term outages of the upstream electrostatic filters
also passed without incident. The fine dust scrubber
integrated in the plant was apparently capable of
Figure 5 Desulphurization plant at Duisburg-Homberg, Germany tolerating and accommodating temporary dust ingress for

Gas Separation & Purification 1992 Vol 6 No 3 139

Gypsum-free flue-gas desulphurization: J. Sporer

a certain period oftime. SO,-rich gas feed to the fluidized- As is thecase with manyotherprocesses. trace components
bed furnaces of the sulphuric-acid plant is without can particularly constitute a source of plant problems
problems and does not affect acid product quality. Failure (namely COS in MEA washes: NH+ NO and nickel
of the electronic scales used to control barite and carbonyl in Rectisol washes). Reliable design of the
petroleum coke feed to the rotary reducing furnaces process is therefore contingent on flue gas analysis being
caused uncontrolled overloading of the furnaces during as comprehensive as possible.
the guarantee run, resulting in the SO? concentration
rising to about 150% of design. Even then. the SO, level in
the exit gas was maintained below 0.4 g Nm-‘. which is Conclusion
evidence of the plant’s flexibility to absorb transients and Successful implementation of the Solinox process with
preserve stable operating conditions. flue gases of various origins under difficult and complex
Despite having recourse to the operating experience conditions such as the presence of heavy hydrocarbons.
from the Villach and Arnoldstein plants in handling this high desulphurization rate specifications. extreme fluctua-
new project, unexpected problems did arise. In normal tions of flue gas concentration and high dust concentrations
operation the SO1 and HCI concentrations in the commend the process as the optimum solution for many
incoming gas to the desulphurization plant were found to current emission problems. This has been confirmed
be appreciably higher than originally measured and anew by a contract received in December 1990 covering a
specified. This led to a higher acid concentration in the Solinox plant to be delivered to a copper mill in Poland
solvent circuit with the consequence of increased losses of for treatment of a flue gas flow of 225 000 Nm’ h-‘. A
solvent and greater expense for regeneration. The plant is power-plant off-gas stream as well as an off-gas stream
still capable of attaining the desired desulphurization from a sulphuric-acid plant will be treated and SO,
efficiency under these worse conditions. but Linde is emission will be reduced by approximately 98%. The
currently collaborating with Sachtleben Chemie on plant is now under construction and will be commissioned
devising suitable remedies to overcome the detrimental at the beginning of 1993.
effects.

References
Summary
I Peschen, N. and Plank, F.W. Bunkerung. Transport und
Contrasting with other desulphurization systems on the Dosierung von Kal k VGB Krof~,c,rkste(,/frrik (Septemher 1990)
market, the Solinox process is a regenerative physical 787-789
wash distinguished by the following principal features: 2 FGD project progresses at Drax TRIPCIXJI?II(YI/Euginwr ( I? July
1990) II-27
3 von Berg, W. Saisonprohleme hei REA-CipsElrc,rXic,(Juli 1980)
Being regenerable. the solvent can be recirculated in a R40
closed circuit. and the SO, can be recovered as a 4 Holzapfel, A. Ahsatzchancen fiir REA-Gips Umwc,/r Bd (1990)
saleable product. rather than gypsum that requires 20 (4) 158-159
5 Hammerschmid, R., Gruber, K. H., Winkler, R. and
permanent dumping.
Rentz, 0. Planung regionaler Entsorgungsalternativen fiir
Owing to the almost solids-free operation. meaning Reststoffe aus der Raucheasreinieune VGB Krufinwkvtechnik
that there are no solid end-products and no crystalliza- (Septemher 1990) C26 c c c ”
tion processes. the need for many mechanical actions 6 Sulphur No ,?//I Export Prices (September-October 1990) 6-7
and maintenance jobs is eliminated. There is hardly 7 Probst, S. MeDtechnik im Krafhverk Limwelr und Technik
(12/89)
any risk of incrustation or clogging in the system. x Probst, K. Betriehserfahrungen im Steinkohlckraftwerk
resulting in high availability. Absence of storage areas Franken II E~retgic~.In/rrgqq (1988) (7) IO-13
for limestone and gypsum makes the plant space 9 Kbhler, P., Kristof, W. and Linde, G. Enschwefelung von
requirement relatively small. Abgasen Demonstration eines neuen Verfahrens Chemieunlqen
und Veehren (1984) 12 (3) 12-14
Design of the Solinox plant remains nearly identical IO Becker, H. Die Linde Solinox-Ahgascntschwcfelungsanlagc
over a wide range of SO: inlet concentrations. meaning der Bleiherger Bergwerks Union f.i& Bc~richtc ous Twhuik untl
that the process can be used to particular advantage for Wi,r.senschqfi M/l 98R 48-59
high and fluctuating SO, concentrations. Chemical II Dlaska, H. Die Verhiittung von Bleierz und Akkumulator-
enschrott nach dem BBU-Rundherdverfahrcn Erzmndl(l977)
washes may be more appropriate for applications
28 h-12
involving low SO2 concentrations (under 0.15%). 12 M6llner, P. Die Verarheitung von Riickstlnden der Zink- und
Finally. the Solinox process is capable of simultaneously Bleihirtte der BBU im Drehtlammofen Erzmetall (1977) 30
solving hydrocarbon emission problems. 326-329

140 Gas Separation Et Purification 1992 Vol 6 No 3