Chemical and Petroleum Engineering, Vol. 42, Nos.

56, 2006

RESEARCH, DESIGN, CALCULATIONS,

AND OPERATING EXPERIENCE
CHEMICAL AND PETROLEUM-GAS
EQUIPMENT
PROCESSES FOR SULFUR RECOVERY,
REGENERATION OF SPENT ACID,
AND REDUCTION OF NOx EMISSIONS

J. Kr. Laursen1 and A. N. Karavanov2

The different sulfur sources at oil refineries are treated by different processes dedicated to each specific effluent;
however, with the WSA (wet gas sulfuric acid) process in its various versions one can convert effluents containing sulfur
in any form into sulfuric acid. In some cases, e.g., when recovering alkylation acid, the sulfuric acid is recycled within the
refinery, whereas in other cases the acid will be sold on the open market.
Haldor Topsoe A/S elaborates and supplies to oil refineries WSA plants of various capacities (Fig. 1).
This paper will focus on the application of the WSA process in oil refineries for:
treatment of H2S from amine regenerators of sour water strippers (SWS);
regeneration of spent sulfuric acid from alkylation;
treatment of Claus plant tail gases;
cleaning of flue gases with high sulfur content;
cleaning of flue and other gases against nitrogen oxides.
WSA Process for H2S Gas. The WSA process for H2S gas (Fig. 2) applies conversion to SO2 by incineration,
heating/cooling of the gas to the reactor temperature, conversion of SO2 to SO3, hydration of the SO3 to H2SO4, and condensation to liquid H2SO4 in the WSA condenser.
This process version is an attractive alternative to the Claus process. Overall, the WSA process will have a lower
investment than a Claus plant with tail gas treatment and have a much better heat economy.
Furthermore, the WSA process is more versatile as it even accepts a feed gas with quite high amounts of hydrocarbons, and it is also able to accommodate significant changes in feed gas composition. It will also be possible to include other
vent gases such as sour water stripper gas.
Chemical Reactions in a WSA/SNOX Plant
Combustion
Decomposition
1
2

H2S + 3/2 O2 H2O + SO2 + 518 kJ/mole;

H2SO4 (liq) + HC + O2 + q SO2 + xCO2 + yH2O;

Haldor Topsoe A/S, Denmark.

Haldor Topsoe A/S, Moscow Representative Office.
Published in Khimicheskoe i Neftegazovoe Mashinostroenie, No. 5, pp. 36, May, 2006.

0009-2355/06/0506-0229 2006 Springer Science+Business Media, Inc.

229

Fig. 1. Topsoe WSA plant 220 MTPD sulfuric acid from H2S.

Oxidation
Hydration
Condensation
SCR DENOX

SO2 + 1/2 O2 SO3 + 99 kJ/mole;

SO3 + H2O H2SO4 (gas) + 101 kJ/mole;
H2SO4 (gas) + 0.17 H2O (gas) H2SO4 (liq) + 69 kJ/mole;
NO + NH3 + 1/4 O2 N2 + 3/2 H2O + 410 kJ/mole (SCR selective catalytic reduction).

H2S gas is incinerated to SO2 in a burner followed by a waste heat boiler. The gas typically contains 56% SO2 plus
all the water from the combustion of the H2S and other combustibles. The gas leaving the waste heat boiler has a temperature of ~400C. The gas then enters the reactor, which contains one, two, or three catalyst beds, depending on the SO2 content and the desired degree of conversion. The catalyst is a vanadium pentoxide based catalyst (Topse VK series) selected
for optimal performance for the given requirements. Since reaction in the reactor is exothermal, the gas is cooled between the
stages in order to favor the SO2/SO3 equilibrium. After the last conversion stage, the gas is cooled below 300C, whereby
SO3 reacts with the water vapor to form gas phase sulfuric acid, and then the process gas goes to the WSA condenser which
has a vertical shell with tubes made of boron silicate acid and shock resistant glass. The process gas flows upwards inside the
tubes, which are cooled on the outside by ambient air. Sulfuric acid condenses in the tubes and flows down the inside tube
surface while being concentrated in countercurrent flow with the hot process gas. The sulfuric acid is collected in the brick
lined condenser bottom and is cooled to 3040C in a plate heat exchanger and pumped to storage. The process gas leaves
the condenser at ~100C and can be sent directly to stack. It is a distinct feature of the WSA condenser that the gas contains
only a low amount of acid mist.
The cooling air leaves the WSA condenser at ~200C. Part of the hot air is used as combustion air in the incinerator and the remaining part can be mixed into the stack for increased buoyancy or it can be used for boiler feed water
preheating.
If necessary, NOx in the incinerator off-gas may be reduced by introducing a SCR reactor upstream the SO2 reactor.
In such a case, ammonia in stoichiometric amount to the NOx content is injected before the SCR reactor to reduce the NOx
to elemental nitrogen.
The heat of reaction is recovered in the form of steam. By the very nature of the process the process, gas is wet and
also contains SO3 in increasing amounts through the process scheme. Therefore, in order to avoid corrosion, all surface temperatures must be above the acid dew point. Therefore, the steam recovery system works typically at 6 MPa (g). Saturated
steam will be generated in the waste heat boiler and in the gas cooler below the SO2-converter. The interbed coolers will
cool the process gas by superheating the steam and all steam for export will be exported as superheated steam, typically at
6 MPa (g), 300350C.
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H2S gas

Incinerator

Stack gas

Blower

Combustion air
SO2
converter

WHB

Blower
Air
Interbed
cooler

WSA
condenser

Interbed
cooler
Gas
cooler
Steam
system

Acid
pump
Acid
cooler

Superheated
steam

Product acid

Fig. 2. WSA process for H2S gas.

In certain cases, it will be advantageous to cool by using a heat transfer medium in the form of molten salt, a commercial product consisting of an eutectic mixture of potassium nitrate and sodium nitrate/nitrite. This is especially advantageous where a fast response to changes is required, such as in Claus tail gas plants (shown later). The salt heat displacement
system will generate medium pressure export steam, saturated, with a possibility for superheating if required.
Material of construction is generally carbon steel except where design temperatures necessitate heat resistant steel.
The combustion chamber and the waste heat boiler inlet is protected by refractory lining. The parts of the condenser in contact
with condensing acid are protected with a fluorinated polymer lining; the bottom part is lined with acid resistant bricks. The acid
cooler is typically made of Hastelloy C. The piping in the acid cooling circuit is carbon steel protected with a Teflon liner.
Claus Plant Tail Gas Processing. Claus plant tail gases containing SO2, H2S, and COS can also be converted to
sulfuric acid by the WSA process installed as a tail gas unit (TGU) (Fig. 3).
The tail gas itself has a very low heating value, and the process gas temperature must be increased by means of a
support burner using refinery gas. The process gas coming from the Claus plant contains no oxygen. The necessary oxygen
is provided by addition of hot air from the WSA condenser being further heated by the burner. The amount of support fuel is
relatively low, as the temperature only needs to be increased to the H2S ignition temperature (250300C). In the reactor, H2S
will be oxidized to SO2 in the first catalyst bed over an oxidation catalyst (Topse series CK) and the temperature will rise
to the SO2 conversion temperature of 400C. The following catalytic stages will contain SO2 oxidation catalyst (Topse
series VK).
For a WSA plant operating as Claus plant TGU, it is recommended to use indirect cooling by means of salt in order
to better follow the fluctuations of the Claus plant, as there is no waste heat boiler to provide a heat buffer capacity.
The WSA process is an attractive alternative to sulfur producing tail gas processes, and it will be an obvious choice
for refineries wishing to upgrade an older Claus plant without TGU. The acid production will be limited and the process will
be ideal for refineries having a captive use for acid or having an acid consumer nearby.
WSA Process for Spent Acid Recovery. The WSA process is increasingly used for recovery of spent sulfuric acid
from alkylation processes (Fig. 4). Today (2006), five WSA plants (Fig. 5) are in operation for spent alkylation acid in oil
refineries with capacities ranging from 50 MTPD to 270 MTPD.
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Hot air

Fuel gas
Support
burner

Flue gas

Stack gas

Blower

SO2
converter Gas
heater

Combustion
SO2 oxidation

Interbed
cooler

SO2 oxidation

Gas
cooler

Steam

Blower
Air
WSA
condenser

Salt
circ.

Acid
pump
Acid
cooler
Product acid

Fig. 3. WSA process for Claus tail gas.

Spent sulfuric acid is decomposed thermally in a furnace and the flue gas is cooled in a waste heat boiler (WHB).
Solid impurities (mainly iron oxide and alkali compounds) are separated in an electrostatic precipitator (ESP). In order to
limit the size of the furnace and the WHB, the decomposition takes place using minimum excess air, and the amount of air
necessary for the subsequent SO2 conversion is added as preheated air from the WSA condenser. The SO2-containing gas is
converted in the SO2 converter. This and the rest of the process scheme is as discussed previously. The sulfuric acid product
will have a concentration of min. 98% and can be directly returned to the alkylation process.
The thermal decomposition process needs support fuel. If H2S is available, the necessary heat can be supplied by
burning H2S. This will typically result in a surplus production of acid, which is available for sale. If surplus sulfuric acid
production is not desired, fuel gas can be used and make up for the inevitable loss in the alkylation/regeneration cycle can
be added as a minor amount of H2S or elemental sulfur.
When compared with the conventional dry sulfuric acid process, the WSA process for spent sulfuric acid has the
advantage that the process gas is not scrubbed and dried after the decomposition furnace. This has these major implications:
The SO3 generated in the incinerator along with the SO2 is not lost with the effluent from a scrubber. This will
increase the acid yield and also eliminate the need for waste water treatment.
For the same reason, the SO3 content after the furnace is not critical. It is therefore possible to operate the furnace at lower temperatures (800900C instead of 10001100C), which will, among other benefits, reduce fuel
consumption.
The operating economy is also better as there will be no need for process gas re-heating, and the pressure drop is low.
The process scheme is simpler and uses less equipment than the conventional process, resulting in lower investment and maintenance costs.
Case Stories
Hydrogen Sulfide and Spent Acid. The Ryazan Oil Refinery revamped their two wet catalysis plants for conversion of H2S to sulfuric acid. WSA condensers replaced the acid absorbers, while the H2S burners, waste heat boilers, and
converters were maintained. The plants were completed in 1993/94 and have been in successful operation since then.
232

Superheated
steam

Stack gas
Blower

Combustion air

Air preheater
Incinerator
Spent acid

WHB

Blower

Dust
filter

Air
SO2
converter

WSA
condenser

H2S gas/fuel gas

Gas
cooler
Steam
system
Superheated
steam

Acid pump
Acid cooler
Product acid

Fig. 4. WSA process for spent acid recovery.

Main design data are (two trains):

Process gas flow, Nm3/h
2 31000
Acid production (as 98%wt), MTPD
2 154
Steam production, tons/h
2 5.2
In the late 1990s, the Ryazan Refinery decided to install the WSA process for two new sulfuric acid regeneration
and recovery units. The first of them has been put into operation. The two new WSA units will each treat 50% of the H2S
from the new HDS unit amine regenerators and one of them spent acid from sulfuric acid alkylation, and another SWS
gas. In order to reduce NOx emission caused by the NH3 in the SWS gas a DENOX reactor is installed. The two units will
produce a total of 70 tons/h steam at 4.1 MPa. Separate gas-fired heaters will superheat the steam to 420C. SO2 emission to
the stack will be below 250 ppm.
Claus Tail Gas, Hydrogen Sulfide, and Spent Acid. In 2001 at Irving Oil Limited in New Brunswick, Canada,
Topse participated in modernization of the refinery with two WSA plants: one for treatment of Claus tail gas, another for
regeneration of spent sulfuric acid.
The WSA tail gas unit is installed downstream the existing Claus plant. The WSA plant is simpler and less costly
than a sulfur-generating TGU. A total of 20000 Nm3/h tail gas is treated and 30 MTPD acid (94%) is produced. This acid is
blended with the excess 98% acid from the spent acid plant and diluted with water to reach the market specification of 93%
concentration. The installation of the WSA TGU increases the overall Claus plant recovery rate to above 99.9%.
In the summer of 2002, a 50 MTPD WSA plant for spent acid regeneration was started up at Slavnefts Yaroslavl
Refinery, Russia (see Fig. 5). Spent acid feed is 30 MTPD and the balance of acid is produced by the H2S used as auxiliary
fuel. The WSA plant has been in successful operation since the start up, producing an acid product of >98% concentration.
SO2 emission to the stack is 200 ppmv.
A large plant for conversion of H2S is installed at Lukoils Perm Oil Refinery, Russia, and has been in operation
since the start up in 1999. The plant treats a 8090% H2S gas coming from the HDS amine regenerator.
The reactor system is designed for cooling by 62 barg steam (sat.), which subsequently is reduced to 1.5 MPa (g).
The thermal efficiency of the plant is increased by recovery of heat from the WSA condenser cooling air. Part of the air is
used for combustion air in the incinerator and the balance of hot air is used for preheating of demineralized process water.
233

Fig. 5. WSA plant for spent acid regeneration.

The sulfuric acid is produced at a concentration of 98% w/w. A dilution unit is installed for dilution of the acid to
GOST specification of 93% when required. The plant has an SO2 conversion of min. 99%.
In 2004, a plant for processing of H2S gas from amine wash from hydrotreaters was put into operation at Naftan AO
(Novopolotsk, Belarus). Plant capacity is 220 MTPD acid.
DENOX Process. In the early 1980s, Haldor Topsoe A/S elaborated the SCR DENOX process. The first full-scale
industrial SCR DENOX Unit was put into operation in 1990. In the past years, the company has applied knowhow, equipment, and catalyst for removal of NOx in more than 225 units. One of new WSA Plants at the Ryazan Oil Refinery will be
supplemented with a unit for removal of NOx.
In the SCR DENOX process, ammonia reacts with nitrogen oxides with formation of nitrogen and water. Normally,
the reactions take place over the catalyst at 250450C. The minimal temperature becomes higher if there is some sulfur in
flue gas. Cleaning efficiency may be in the range from 60 to 95% depending on the requirement of the client; ammonia slip
is below 210 ppm. Noncatalytic reduction of NOx does not provide efficiencies higher than 60%, and it is difficult to keep
ammonia slip at the desirable level.
Haldor Topsoe A/S were the first to implement the corrugated fiber-reinforced catalyst. Due to the unique manufacturing process, the catalyst gets such properties as flexibility, thermal resistance, mechanical stability, and low SO2 oxidation
activity. The company has elaborated more than 50 various compositions of DENOX catalyst supplied as standard elements.
The results of operation of about 50 industrial WSA units with capacity from 4 to 1100 MTPD in various branches
of industry indicate their high energy efficiency. High commercial grade of product acid is achieved due to a simple and reliable layout of the process without side products and liquid wastes.

234