Catalytic
Reaction section:
2H2S
+SO2 --> 3/x Sx +2H2O
Overall
reaction:
3H2S+1.5O2
---> 3/x Sx + 3H2O
This
is a simplified interpretation of the reactions taking place.The reaction
is complicated by the existence of various species of gaseous sulfur. Fig
below shows the scheme from heat recovery viewpoint.
There
are basically 2 heat recovery systems.The reaction waste heat boiler recovers
energy from the gas stream behind the sulfur burner ;the gas contains SO2,H2S,Sx,CO,CO2,H2,CH4,N2,
and is cooled from about 2200-2400 F to about 600 F,generating 500-600
psig saturated steam. An elevated drum fire tube boiler is typically the
design used ; this design helps protect the tube sheet and tubes through
proper circulation.Ferrules are used at the inlet tube sheet to transfer
heat flux away from the tube sheet into the region where boiling occurs,thus
keeping the tube inlet and tube sheet region cool.A two-gas pass boiler
may be used,though single pass designs are also available.Provision for
sulfur recovery is made at the gas exit zone by using sulfur drains,which
are kept warm by circulating steam. Since the gas pressure is atmospheric,casing
designs are not special as in reformed gas boiler in hydrogen plants.Adequete
refractory is used ensuring the casing is hot and is near or above the
sulfur dew point of 350-370 F.Gas bypass systems are not generally used.Carbon
steel tubes are adequete.Economizers are not recommended due to low temperature
corrosion concerns.
The
second stage of heat recovery takes the form of sulfur condenser; it is
a low pressure steam generating section,where multiple low temperature
gas streams leaving the various stages of catalytic conversion ranging
from 350-500 F are cooled in the boiler generating 20-50 psig saturated
steam.Here too the drains have to be kept warm to prevent solidification
of sulfur.Carbon steel tubes are adequete. Single shell fire tube boilers
are widely used for this application if the gas flow is small,as they are
less expensive than elevated rum designs.Separate exchangers may be used
for each stage of conversion if the gas flow is large.
SULFURIC
ACID PLANTS
In
the manufacture of sulfuric acid by the contact process,raw sulfur is burned
in a combustor with air. The resulting gases containing SO2,N2,O2
at about 1800-1900 F and at a pressure of about 2 psig enter a waste heat
boiler and the gas is cooled to about 750-800 F.The boiler could be of
fire tube or water tube design,depending on the gas flow and economics.High
pressure saturated or superheated steam is generated.The exit gas temperature
is controlled as this is the optimum temperature for conversion of
SO2 to SO3 in the converter,which follows the boiler.In
the converter,catalysts convert most of the SO2 to SO3.Exothermic
reactions occur and the gas stream is again cooled using superheaters or
air heaters.After each stage of cooling,the gas stream enters the reactor
for converting more of the sulfur dioxide to trioxide.In the final stage,
an economizer is used.Finally the gas is absorbed in dilute sulfuric acid
acid to form concentrated acid.A simple scheme for this process is shown
below.
Though
the gas stream behind sulfur combustor contains little water vapor,acid
formation is likely if the air is moist and startups,shutdowns are frequent.Hence
the casing has to be preferably a hot casing. A membrane wall design for
water tube boilers is suggested as the tube walls can be kept above the
acid dew point. The feed water temperature entering the economizer has
to be above 280 F to minimize low temperature corrosion concerns.The casing
design has to handle the high gas pressure. Soot blowers are not used as
it affects the gas composition,which is critical to the process. Tube wastage
due to potential corrosion is sometimes handled in Europe,Asia by using
cast iron gilled tubes for economizers,though in the US,carbon steel finned
tube economizers are widely used.Internal as well external gas bypass systems
are used for the sulfur combustor waste heat boiler.Fire tube boilers if
used are of elevated drum design with tube sheet/tube inlet region protected
by refractory and ferrules.For more information on these designs,see my
Waste Heat Boiler Deskbook.
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