SICHUAN PROVINCIAL CHEMICAL ENGINEERING DESIGN INSTITUTE

OKI PULP AND PAPER

18T/D SO2 SOLUTION PLANT TRAINING MANUAL

SCEDI/You Hoa

2015.12

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

 SICHUAN PROVINCIAL CHEMICAL ENGINEERING DESIGN INSTITUTE

Catalogue

1. General

2. Sulfur treatment

3. Production of SO2

4. Cooling of SO2

5 .Absorption of SO2

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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1. General
The Manual is prepared to help operators understand fundamental
principles, raw materials, knowledge of environmental friendliness and safety
and process flow of sulfur dioxide production as well as related equipment
and their operation.
Sulfur dioxide (chemical formula: SO2) is the most common sulfur oxide.
It is a colorless gas with a pungent odor．It is mainly used in the production of
sulfuric acid, and also has the following important applications: for production
of pulp in papermaking industry; for production of sulfite, bisulfite, and
thiosulfate; for production of organic compounds, such as polyamide (nylon 6)
monomer, and synthetic detergent; for production in the pharmaceutical
industry. It can also be used as bleach for textile and leather, and fumigant in
agriculture, and Antiseptic sand disinfectants in food industry. Liquid sulfur
dioxide is an effective solvent for some organics, and therefore is used for
refining of mineral oil.
There are a great many of raw materials used for production of sulfur
dioxide, such as sulfur, pyrite, and non-ferrous metals. Among them, sulfur is
the cleanest for this purpose.
The process flow is described as follows:
The raw solid sulfur is fed into sulfur hopper by a telpher and then
transmitted to sulfur melting tank through a circular disc feeder and a belt
conveyor. Calcined lime is added into the sulfur hopper to neutralize acidic
substance possibly contained in raw sulfur.
Melted sulfur overspills to the pre-processing tank from the sulfur melting
tank, and then is pumped by preprocessing pump to preprocessing and
filtering.
A filter is used. Pre-processing pump preprocesses melt sulfur and
diatomite suspension on the vertical blades of filter in a circulation manner,
and then pumps melted sulfur for circulated filtering. The filtered liquid sulfur

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goes to purified sulfur tank for storage.

Liquid sulfur is pumped by the fluid-flow pump to the melted sulfur ejector
attached to the sulfur incinerator, which ejects melted sulfur into sulfur
incinerator for burning in the sulfur incinerator with SO 2 generated. The high-
temperature furnace gas containing SO 2 after burning is cooled by two-stage
gas cooler and then goes to two stage cooler for scrubbing and cooling and
further to two-stage absorber to absorb SO 2. The tail gas is scrubbed with
10％ NaOH and demisted by fiber demister before discharged through stack.
Air is blown into the sulfur incinerator by an air blower. The filtered melt
sulfur burns in the air.
Sulfur incinerator is installed with HP atomizing nozzle and two retaining
walls. The design clearance will enable air to reach necessary mixed turbulent
without causing two much pressure drop. Sulfur incinerator is fixed with
additional fuel gas burner, which is used to increase temperature during
startup. Therefore, there is no need to provide startup preheater separately.
HT furnace gas containing SO 2 is cooled in jacket air cooler and shell air
cooler to 400℃ before going to venturi tube.
The furnace gas in venturi tube and furnace gas cooler is cooled and
dehumidified with sprayed water, and calefactive circulating fluid is cooled by
plate heat exchanger before reuse. The furnace gas is cooled to 38℃ before
going to 1＃and 2# SO2 absorbers to absorb SO2.
2# SO2 absorber absorbs SO2 with conditioning water, and then the
absorption liquid goes into liquid SO2 circulating tank and is pumped to 1# SO 2
absorber by liquid SO2 circulating pump, and finally liquid SO 2 product flows to
liquid SO2 tank and pumped to SO2 storage tank.
2 Sulfur treatment
(a) Nature of sulfur
Sulfur is active chemically and generates a small amount of SO 2 and
sulfuric acid in the air, which is particularly obvious in sublimed sulfur.
Sublimed sulfur is generally acidulous. Sulfur will burn spontaneously when it

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reaches 250 C°. Powder sulfur will explode when it reaches a certain
concentration in the air. At high temperature, sulfur reacts with hydrogen,
carbon and chlorine to generate H 2S, CS2 and S2Cl2. It can react with all
metals but Au and Pt to generate sulfide.
Inhale of powder sulfur for a long time will cause the diseases of
respiratory system, and frequent contact may cause dermatitis.
The freezing point of sulfur is 115 C°, and 95.5 C° is the transition point of
the two allotropic substances of rhombic sulfur (α sulfur) and monoclinic sulfur
(β sulfur).
When heating solid sulfur, it starts melting from 119 C° to become light
yellow flowing liquid. With increasing of temperature, sulfur presents different
states: becoming liquid sulfur (λ sulfur) with highest fluidity at around 153C°
and rather sticky sulfur (μ sulfur) over 157 C°. This is the result of sulfur
molecules starting to aggregate. If the temperature increases further, the
generated polymeride depolymerizes, resulting in reduced molecular weight
and viscosity and boiling at 444.6℃ (see Tab1，Tab. 2 and Tab. 3). The liquid
sulfur also has allotropic substance S λ and Sμ. Sλ→Sμ is often balanced.
Viscosity varying with the increase of temperature is a result of changes in
number Sμ.
Table 1 Density of Liquid Sulfur
T/℃ Density g/ml T/℃ Density g/ml T/℃ Density g/ml
121.1 1.8037 146.1 1.7818 178.3 1.7671
123.9 1.8007 178.9 1.7795 184.0 1.7644
126.7 1.7981 151.7 1.7773 210.0 1.7509
129.4 1.7957 154.4 1.7752 239.5 1.7329
132.2 1.7935 156.9 1.7739 278.5 1.7096
135.0 1.7912 158.5 1.7729 357.0 1.6583
137.8 1.7888 161.0 1.7723 445.0 1.6060
140.6 1.7864 165.0 1.7714
143.3 1.7842 171.3 1.7705

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Table 2 Sulfur Melting Heat

T/℃ Melting Heat cal/g
S(Orthorhombic)→Sλ(Liquid) 112.8 11.9
S(Monoclinic)→Sλ(Liquid) 118.9 9.2
S(Monoclinic)→S(Liquid) 115.21 12.80

Table 3 Sulfur Melting Point（1）

State Change Melting Point/℃
Sα（Orthorhombic Crystal System）→Sλ（S8）and
110.1
Sπ（S4）of equilibrium concentration
Sα→Pure Sλ 112.8
Sβ（Monoclinic Crystal System）→Sλ and Sπ of 114.5（Generally refers to the
equilibrium concentration freezing point）
118.9（Generally refers to melting
Sβ→Pure Sλ
point）

λ sulfur is solidified to become α sulfur or β sulfur, and μ sulfur is solidified

to become plastic amorphous sulfur. Hot sulfur is chilled to become black
brown elastic blocks. Such state is determined by original temperature
balance. Both λ sulfur and μ sulfur are high polymers. This sulfur polymer
depolymerizes with the elapse of time and finally become rhombic sulfur.
(b) Solid sulfur
Color: bright yellow, yellow, orange, brown, brown, and gray etc., varying
with hydrocarbon content and type Commercial sulfurs can be categorized
into Bright Sulphur and Dark Sulphur.
Volume-weight: 1.1~1.4
Angle of repose: 40 °
Ignition temperature of powder sulfur in atmosphere
Suspending powder sulfur 190 °
Unevenly-distributed powder sulfur 220 °
Explosion of suspending power sulfur in atmosphere
Lower limit 35g/m3 Upper limit： 1.4kg/ m3
Maximum explosion pressure: 2.8 ata

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Average pressure increase rate: 48 ata/s

Max. pressure increase rate: 133 ata/s
Min. O2 concentration: 11%
As far as sulfur shape concerned, there are powder agglomerates from
crushed sulfur blocks, coarse brushed regular or irregular solid sulfur plate,
and dried granulate sulfur from melt sulfur ejected into water for granulating.
OKI Sulfur Dioxide Factory employs granulate sulfur.
Solid sulfur is generally stored indoors, specifically in fireproof buildings
or storage bin. Smoking and flames shall be prohibited in such enclosed area
to avoid explosion. Good ventilation is also necessary; and when feeding the
storage bin, ton packaged sulfur shall be placed as close to the storage bin as
possible to minimize concentration of powder sulfur.
In selection of conveying machinery, those generating no sparks shall be
selected, for example belt conveyor. Solid sulfur burns slowly and will not
cause big fire in short time. However, friction heat and sparks from the
devices may cause fire. For example, friction of poorly installed belt conveyor
or tire sliding friction of shovel loader may cause fire. In addition, sheet iron or
gravels mixed in sulfur are also causes for fire during device transportation.
Water spraying is rather effective to put out sulfur fire. In case of presence of
SO2, firefighting must be performed upwind.
Solid sulfur shall be protected against rainwater and moistening when
storing and handling. If getting wet, sulfur will be oxidized to generate dilute
acid. At such circumstance, sulfur will immerse into concrete and asphalt
ground and cause corrosion of steel device such as coils of melting unit,
bringing about big operation troubles.
(c) Sulfur melting unit
Sulfur melting units are of tank type and upright type. The former is
designed for large units into which the solid sulfur is added and melted with
heated melted sulfur in the tank. Sulfur melting tank is installed with heating
coil and agitator. Normally, saturated steam of 3.5~7kg/cm 2 is generally used

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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for heating and then solid sulfur is added to keep sulfur in tank at around
130℃. The upright type melts sulfur on heated metal surface, and is used by
OKI Sulfur Dioxide Factory.
(i) Upright sulfur melting tank
It is an SS vertical storage tank with cone bottom and agitator provided in
the middle. Heat transmission area depends on water content in the sulfur
and is generally 0.1~0.2 m 2/t·d. The sulfur melting tank in OKI Sulfur Dioxide
Factory is sized Φ3.6m×H2.5 and installed with 4 groups of concentric steam
coils, with heat transmission area of 45m 2, agitator in the middle, rotation
speed of 67rpm/min, and the melting capacity of 10t/h for sulfur with 2.5%
moisture. Each group of coil can be taken out separately for repair.
The steam pressure for the coils of sulfur melting tank is below 7kg/cm 2,
and that for preprocessing tank and purified sulfur tank is 3.5kg/cm 2. Over-
heating steam is not allowed. Steam consumption depends on moisture
content in sulfur and climate conditions, and is generally around 80~116kg/t.
For prevention of device corrosion, air and steam is generally not used for
agitating. Steam leaking from coils is also allowed. Adding an appropriate
amount of lime in sulfur containing much vitriolic acid may prevent corrosion,
however this necessitates in more cleaning of sulfur melting tank and filter.
The sulfur melting equipment to be out of operation for a long time must
be emptied and dried. When clearing out sediments, pump out sulfur as far as
possible first, stir the hot sediments while adding a small amount of water for
softening purpose, and remove it with a shovel. The softening sediment, if not
being removed, will be solidified to be as hard as concrete when clearing out
will be very troublesome.
(ii) Filter
Leaf filter is usually used in China as great achievements are made in
sulfur filtering. See maintenance manual for the filter provided.
The generally used filter is pressure leaf filter, which has a structure of

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filter leaves side by side in steel horizontal or vertical cylinder and the
cylinder insulated with steam jacket to keep sulfur temperature at 130~140℃.
The filter leave is made of SS wires. Add a certain amount of filter aid to melt
sulfur in the preprocessing tank for mixing with sulfur. The filter leaves are
covered with filter aid when pre-filtering. When sulfur in the pre-filtering tank
gets clear, pre-filtering is completed when switching over to sulfur to be
filtered. Ordinary diatomite and similar substance is usually used as filter aid
to filter medium. Filter cycle varies with filtering area and contamination of raw
sulfur. The end of filtering is judged on the basis of the extent of pump
pressure rise and the flow of filtered sulfur reducing. Severely contaminated
sulfur may shorten filtering cycle.
To peel filter cake from filter leaf, discharge sulfur in the leaf filter body
and pull out the filter leaf while it is hot. Shake the filter cake off without
damaging wire cloth, and clean the residues with a wooden shovel. In
addition, the filter cloth will be blocked after long use. At this time, it may be
soaked in 10 ~ 20% hot caustic soda solution for hours and then washed with
sufficient water.
(d) Melt sulfur
Operators of melt sulfur shall have full understanding of the following and
take corresponding measures: Firstly, keep the temperature of relevant
equipment at 130~145℃; secondly, take sufficient precaution measures
against fire; thirdly, melt sulfur contains hydrogen sulfide which can diffuse
throughout storage tank. With these taken into consideration during transport
and storage of melt sulfur, it is as easy to operate as ordinary liquid. Sulfur is
hardly corrosive at 130~145℃ when carbon steel is recommended.
(i) Storage tank
The storage tank is mostly of vertical cylindrical shape with a cone cap.
For insulation purpose, heating device is used and insulation measures are
taken. Steam is mostly used for heating, and temperature is controlled

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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through adding or reduction of coils or regulating steam amount. For the

perspective of design, the method of pressure regulation is more desirable.
There is variety of storage tank coils, and generally row tube or fin tube heater
is provided at the bottom of storage tank.
The viscosity of melt sulfur is equivalent to that of A-heavy oil. Convection
may keep temperature in the storage tank even, and therefore there is no
need to heat the ground below the storage tank with coils. The heater is
installed close to bottom plate. It shall be taken out before sulfur is solidified
when the storage tank needs to be emptied for detection purpose.
To prevent piping at the melt sulfur inlet from being electrostatic, melt
sulfur is fed through piping from tank cap straight to tank wall, or through
piping at the bottom of tank wall to avoid melt sulfur straight flowing into
storage tank.
The size of vent varies with source of sulfur. However, the concentration
of hydrogen sulfide in storage tank is around 1000~3000ppm. The explosion
limit of hydrogen sulfide is 4.3~46% at normal temperature (27.6℃) and 3.3%
at 144℃. Therefore, the concentration of hydrogen sulfide is not the important
indicator for venting. The exhaust pipe shall have steam tube tracing.
The extinguishing device shall be provided tubing so that such tubing can
be sent into the steam inlet. Valves shall be provided at safe places. Water is
also efficient for putting out fire, however, steam generated from large amount
of water will increase internal pressure greatly, bringing about risk of
explosion.
During the daily management of sulfur storage tank, it is important to
keep the temperature of the storage tank above 115℃ and confirm the
concentration of sulfur of different sources. If below 115℃, sulfur steam will
attach onto such locations as cap increase weight.
(ii) Piping, valve and pump
Melt sulfur piping is generally heated with steam. For this purpose,

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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saturated vapor with pressure of around 3kg/cm2 is maintained to keep the

sulfur conveyed at 130~140℃. Insulation is applied at the outer. There is no
essential difference in structures between the valve for sulfur and the valve
commonly used for liquid, except for clamps or tracing pipe.
In case that the pump is heated in the same way as that the valve is
heated, the pump can be operated as if it was used for general liquid.
(iii) Safe operation
Melt sulfur is flammable and may reach 130~140℃ during operations so
fireworks is prohibited. It will also burn the skin, therefore, operators must
protect their face and keep their skin from exposure by wearing clothes with
long sleeves and trousers and wearing anticorrosion gloves, etc. In case of
contact with skin, the sufferer could apply sufficient cold water to relieve
inflammation, and must not peel off the coagulated sulfur before the injury is
confirmed. In case of contact with large area skin, the sufferer could use clean
cloth to cover the wound and ask a doctor for help after the aforesaid
treatments are applied.
Operators should displace the air and determine its compositions before
the operation is carried out in the storage tank, sulfur melting tank, etc. No
operation is carried out until it is safe. Attention shall be paid to hot work.
Operators should wear hydrogen sulfide protection mask when they are
working at where the storage tank vent is arranged, and they should operate
in upwind position.
Though it will not result in a severe fire disaster once the storage tank or
sulfur melting tank is on fire, it will be too dangerous if SO 2 is released from
the vent.
3 Production of SO2
Molecular formula of SO2: SO2
Molecular weight: 64.0638
SO2 is colorless, pungent and toxic at normal temperature, of which the
density is heavier than that of air, easily liquefied and soluble in water.

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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Melting point: -72.4℃ (200.75K)

Boiling point: -10℃ (263K)
Relative density (water=1): 1.43
Relative vapor density (air=1) 2.26
Saturated vapor pressure(kPa): 338.42 (21.1℃)
Relative density (water=1): 1.43
Relative vapor density (air=1) 2.26
Saturated vapor pressure (kPa): 338.42 (21.1℃)
If SO2 is inhaled, most SO2 will stay in the upper respiratory tract due to
its solubility in water. Corrosive sulfurous acid will be generated on the moist
mucosa, some of them will be further oxidized into sulfuric acid, intensifying
the irritation. If SO2 of 100 ppm is inhaled each day, bronchus and lungs will
present obvious irritative symptoms 8 hours later, thus the lung tissue will be
injured.
SO2 can also be absorbed into human blood and thus toxic effect will be
produced to the whole body. SO2 can destroy the activity of enzyme, effect
metabolism of human body and cause certain damages to liver. Chronic
toxicity test shows that SO2 has systemic toxicity. A rabbits that inhales SO 2
with a concentration of 18~22 mg/ m3 for 2 hours each day will have an
obviously reduced immune response of typhoid fever. A mouse that inhales
SO2 with a low concentration of 5124 mg/ m3 for six months will have a
restrained immune response. Therefore, people who have been exposed to
SO2 for a long period may suffer increased morbidity of respiratory disease or
the respiratory disease will not be recovered easily, which may be associated
with restrained immune response in addition to the direct irritation of SO 2.
Long-term exposure to SO2 at an average concentration of 50 mg/m3
results in a higher prevalence of chronic rhinitis with main symptoms including
nasal mucosahypertrophy or atrophy, turbinate hypertrophy, or baryodmia,
and dental erosion also may be presented. In addition, the brain ventilation
function is significantly impaired, and mean of time vital capacityandMVV is

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reduced.
In case of SO2 leak, occupants in polluted areas shall be evacuated as
soon as possible to the windward side, and emergency personnel should
wear positive pressure self-contained breathing apparatus and protective
clothing, and access the site from the windward side. sulfur feeding shall be
suspended while keeping adequate ventilation to facilitate the spreading when
handling the leakage.
(a) Combustion of sulfur
Combustion of sulfur will be very quick at certain temperature. Sulfur
and air at certain rate fed into the incinerator burn to produce SO 2 at a certain
concentration.
Combustion reaction is generally represented by S+O2=SO 2, various
theories have been proposed, even if it appears to be a complex reaction,
which is not figured out till now. Some representative theories believe that
basic reactions are as follows:
(1) Initial reactions and side reactions:
S8→S7+S
S+O2→SO+O
S8+O→SO+S+S6
(2) Formation reactions:
SO+O→SO2*+hv(* means activated molecular)
SO+O2→SO2+O
SO2+O2→SO3+O
SO2+O→SO3
The combustion intermediate product is generally considered as sulfur
monoxide. Equilibrium of the following reaction will shift to the right at lower
temperatures
1/2 S2+1/2O2→SO
But it is difficult to identify this reaction due to the short life of SO groups.
Since reactions in the following formulas have considerable amount of SO 2 at

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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the temperature of 1250~1500℃,

SO2+1/2S2→2SO
SO2→SO+1/2O2
SO generated from above formulas can be considered as being
eliminated in accordance with the following formulas:
SO+SO→(SO)2
(SO)2+SO→S2O+SO2
(SO)2+2S→2S2O
SO2+3/2S2→2S2O
SO+O→SO2+hv
Although a series of reactions are not definitely figured out, the existence
of S2O molecules in SO determination has been confirmed.
There is also SO3 in sulfur combustion gases, whose amount is
equivalent to about 1~5% of SO3. SO3 is generated mainly due to the
combination of SO2 and oxygen atoms in the high-temperature regions above
1200 ℃. At the temperature of 900 ~ 1050 ℃, the following reaction
mechanisms are proposed:
SO2+M→SO2*+M
SO2+SO2→SO3+SO
SO2*+O2→SO3+O
SO2+O2→SO2+O
SO2+O→SO3
(M=SO, O or other active groups)
As another important reason, SO3 is considered to be generated due to
catalytic actions of nitrogen oxides :
NO+O→NO2*
NO2*+SO2→SO3+NO
NO3+SO2→SO3+NO2
Since the above catalytic reactions are slower than reactions of SO 2 and
oxygen atoms, SO2 oxidation based on atomic oxygen reaction is dominant in

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the high-temperature regions where the thermal dissociation of molecular

oxygen is rather obvious. The catalytic reaction of nitrogen oxides seems to
act when the amount of SO3 is smaller compared with the situation when SO 2
and SO3 are in equilibrium.
The formation of nitrogen oxides increases with the increase of the flame
temperature. It is related to temperature, and molecular oxygen and NO are in
equilibrium, thus the higher the temperature is, the heavier the concentration
of NO is. But the amount of nitrogen oxide in sulfur nozzle is much smaller
compared with that in heavy oil burners. When heavy oil burns at the
temperature of 1100 ℃ under the circumstance that O2 concentration is 10%,
NO concentration may reach 900ppm, while when the sulfur burns under the
same condition, NO3 in finished acid is around 1ppm and NO concentration in
the exhaust gas is 15 ~ 20ppm. When using high-purity sulfur as the raw
material, the amount of nitrogen oxide and hydrocarbon content are increased
in proportion with the increase of NO3 in the finished products.
When the sulfuric acid with less nitrogen oxide content is required, the
furnace temperature shall be reduced, and materials containing much carbon
not used.
(b) Structure of sulfur incinerator
Since the sulfur burns fast, structure of the incinerator is simple and
horizontal sulfur incinerator is employed in most cases.
As for the structure of sulfur incinerator, insulating bricks and firebricks
are laid in the inner wall of steel cylinder. Semicircular retaining walls are
made of firebricks in 2-3 places for good contact between sulfur and air. Sulfur
spray is required to generate particles easy for gasification, have large spray
angle and achieve better homodisperse. SUS316 or equivalent materials are
employed in spray gun and head of the nozzle. The spray gun shall be
provided with steam jacket in order to avoid damage from high temp in the
incinerator and growth of sulfur viscosity due to the heat. Such steam is

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adjusted with valves and emitted directly into the air.

The incinerator body shall be installed with canopy to prevent such body
from directly getting wet with rainwater, and thus escapes from the corrosion
of SO3. If such canopy is replaced with insulation material, the temp of steel
plate in the incinerator wall must be paid attention to. Although the part near
the nozzle inside the incinerator is gasified by sulfur spray, sulfur of imperfect
combustion will be still mixed in the incinerator gas. Such gas will penetrate
into bricks and steel shell, and gas or sulfur will always leak through manhole
or areas of bad welding. If the temp of inner wall of steel shell reaches 400℃
or above, sulfur will react with iron on such temp to form iron sulfide, which
accounts for the corrosion of the such shell. Therefore, enough attention shall
be paid to such problem when the thickness of refractory material is
determined as well as in case of use of insulation material.
(c) Operation of sulfur incinerator
Operation on furnace gas is related to SO 2 concentration. The Chart 1
reflects theoretical relation between such operation and SO 2. However, the
actual temp of furnace gas is different from its theoretical one due to causes
such as difference of air temp and heat loss of the incinerator body. The
difference between SO2 concentrations from furnace gas analysis and from
theoretical temp facilitates the operation and management of the incinerator.

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Chart 1 Furnace Temperature and SO2 Concentration of relationship

Operating temp of the incinerator generally is about 700~1150℃, SO2

concentration may arrive at 18% merely taking sulfur combustion into
consideration. In case of high-temp operation, enough measures shall be
taken on the refractory materials inside the incinerator. The limit temp of
firebrick which is wildly used and has more aluminum content is around
1200℃. The temp difference between the front side of retaining wall and its
back side is huge due to the structure of the incinerator, so the back side of
high temp will shrink because of high-temp combustion, as a result, even with
the use of such firebrick, the retaining wall usually gets to incline and collapse.
Sulfur flow can be measured with meter. Temp inside the incinerator, air
flow and sulfur flow can be indicated with meter and adjusted as per certain
conditions easily, which is quite similar with the operation of burning heavy oil.
See the Table 4 for the relation between air amount for sulfur combustion and
SO2 concentration.

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Table 4 The amount of air required for the 1T/d Sulfur burning
SO2 % Amount of Air Nm3/min SO2 % Amount of Air Nm3/min
6 8.08 14 3.46
7 6.94 15 3.23
8 6.06 16 3.03
9 5.39 17 2.86
10 4.85 18 2.70
11 4.40 19 2.55
12 4.04 20 2.43
13 3.73
SO2 % Amount of Air Nm3/min SO2 % Amount of Air Nm3/min
6 8.08 14 3.46
7 6.94 15 3.23
8 6.06 16 3.03
9 5.39 17 2.86
10 4.85 18 2.70
11 4.40 19 2.55
12 4.04 20 2.43
13 3.73

Sulfur flow can be adjusted with frequency converter.

(d) Preheating of device
Before its operation, the incinerator shall be preheated with natural gas
nozzle or heavy oil nozzle to the temp of spontaneous combustion temp of
sulfur (natural gas is employed for heating in OKI Sulfur Dioxide Factory). The
incinerator and device shall be preheated at the same time in sulfur acid
plants unless in special cases.
Temp of the incinerator shall be increased slowly in order to protect the
refractory material from falling off when natural gas nozzle is installed in the
incinerator. Heating shall be stopped when the temp of sulfur incinerator outlet
increases to 800℃ or so, natural gas burner shall be removed and sulfur
nozzle shall start to work. For more detail information, please see the
document of incinerator drying.

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4 Cooling of SO2
Temp of gas from sulfur incinerator shall be lowered as possible to
produce better SO2 solution. Boiler is employed in most cooling of furnace
gas, because 1) it may recycle the heat generated from sulfur combustion,
produce medium pressure steam, and reduce energy consumption during
production; 2) the technology of boiler equipment used for heat exchange of
gas from sulfur combustion is mature.
Since the air from sulfur combustion whose heat is recycled by boiler has
been dried with sulfur acid, dew point of the furnace gas is much lower than
that of without drying treatment. If boiler is employed in OKI Sulfur Dioxide
Factory, boiler tube is likely to be corroded. In addition, according to SO 2
production experience of HaiNan JinHai Pulp & Paper Co., Ltd., SO 2 devices
provided by OKI may be shutdown frequently to meet the slurrying
requirements. In the above case, condensation acid may be more likely to
damage the boiler.
SO2 cooling process employed in OKI Sulfur Dioxide Factory:
a) Jacket-type heat exchanger: It has simple structure, may bear quite
high temp and is convenient for repair. However, it has low heat
transfer coefficient, small heat transfer area and high cost. According
to operating experience of JinHai, when the tube-shell heat exchanger
is used for high-temp furnace gas, its tube sheet is easy to crack due
to heat expansion and its tube is easy to suffer from high-temp
corrosion.However, jacket-type heat exchanger may improve such
situation a lot.
b) Tube-shell heat exchanger is employed. The temp of furnace gas is
reduced to 700-750 C° when it arrives at such exchanger, and such temp
shall be reduced to 350-400C° when it goes across such exchanger.
However, the temp of furnace gas at such exchanger’s outlet shall be ＞
350C° in order to protect boiler tube from low-temp corrosion. Tube-shell heat

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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exchanger is the most common type of heat exchange, which may provide
quite large heat exchange area in consideration of the ratio of weight and
volume. Its mechanical strength is enough to bear any force during the
production, including internal and external forces encountered in
transportation, installation and normal operation. Wearing parts can be
replaced and cleaned easily, which may be applied to nearly all occasions.
c) Venturi tube (referred to as Venturi), which is made from 904L, with
good corrosion resistance, is used to reduce the temp of furnace gas to
70-80C° or so. Venturi is featured with:
1) Simple equipment and convenient repair;
2) Easy operation and no need for guardian;
3) No need for high-pressure pump and ability to cool with little
circulating fluid;
4) Small installation area.
However, the pressure drop of Venturi is quite huge with about 2000-
2500Pa.
Generally, at the throat part of Venturi where the gas speed is 30-
120m/s and the liquid-gas ratio is 0.2-1.0 l/m 3, the spray with
circulating fluid which will collide fiercely with high-speed gas and form
drop of 50μ or above, and such drop will disperse and make a full
contact with the gas. As a result, particles in the gas will gather
around the drop surface, which will then be eliminated easily by
furnace gas cooler. Due to the turbulence at the throat part of Venturi,
mass transfer coefficient between the gas side and liquid side is huge,
which may reduce the gas temp excellently and eliminate some dust,
sublimed sulfur and SO3 in the gas.
Since the pressure drop of Venturi is quite huge, increase of gas-liquid
ratio will enlarge such pressure drop and shall be operated as
required in operation manual.
d) Furnace gas cooler is a vertical tower made from FRP, with Pall ring of

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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PP installed inside. The tower may continue to reduce the temp of furnace gas
in order to absorb SO2.
Operation in packed tower is differential contact counter-current
operation, and gas-liquid two-phase inside such tower can meet the contact
status as good mass transfer required. The packed tower is featured with
strengths such as simple structure, easy manufacture out of anticorrosive
material, application to tower of small dia. and low pressure drop.
FRP is a kind of composite with glass fiber & its fabric as reinforcing
material, synthetic resin as adhesive, and through certain forming techniques,
which is featured with excellent corrosion resistance, easy machining and
forming, and good thermal properties. Its density is 1.6-1.9 g/cm 3, about 1/5-
1/4 of that of steel, its coefficient of thermal expansion is equivalent to that of
steel, and its coefficient of heat conduction is 0.5% of that of steel, which
make it an excellent heat and electrical insulator. However, heat-resistance
temp of FRP is generally low, and differs from different kinds of resin (usually
not more than the FRP operating temp of 200C° in OKI Sulfur Dioxide
Factory), while in JinHai, such temp is not less than 100 C°. Protection system
is set in circulating fluid system of Venturi tube to protect FRP equipment:
Ⅰ) Control of inlet temp of Venturi.
Ⅱ) Control of circulating fluid flow of Venturi. When the circulating fluid
flow is low or none at the inlet of Venturi, the outlet valve at safe water
tank can be open quickly to reduce the temp of furnace gas at Venturi
outlet.
5 Absorption of SO2
Absorption of SO2 is carried out with 2 packed towers of FRP. The feature
of easy absorption of SO2 has been explained before, so the reason for using
2 towers is to reduce the SO 2 concentration in off-gas absorber as possible,
and further to reduce sulfur consumption on the one hand, and to reduce
NaOH consumption on the other hand.The solubility of SO 2 in water is related

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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to the temp of water and the partial pressure of SO 2 in the furnace gas. See
Table 5,6,7 for Solubility in water of sulfur dioxide gas. See the Chart 2 for
such relation.
Table 5 Solubility in water of sulfur dioxide gas（1）
0℃ 25℃ 50℃
SO2 SO2 SO2
Pso2mmHg g/100cc Pso2mmHg g/100cc Pso2mmHg g/100cc
solution solution solution
0.4 0.0537 1.4 0.0534 4.9 0.0525
3.5 0.237 11.75 0.234 30.5 0.2276
29.4 1.227 87.9 1.212 204.5 1.181
109.4 3.804 313 3.750 696 3.628

Table 6 Solubility in water of sulfur dioxide gas（2）

0℃ 20℃ 40℃ 60℃

Pso2m SO2 Pso2m SO2 Pso2m SO2 Pso2m SO2

mHg g/100ccH2O mHg g/100ccH2O mHg g/100ccH2O mHg g/100ccH2O

474.8 11.55 198.6 2.97 306.4 2.21 175.7 0.84

224.4 3.34 373.8 2.68
366.6 5.22
1107.8 15.01

Table 7 Solubility in water of sulfur dioxide gas（3）

T/℃ Solubility l(N.T.P)/l concentration of saturated aqueous solution %
0 79.789 22.83
5 67.485 19.31
10 56.647 16.21
15 47.276 13.54
20 39.374 11.29
25 32.786 9.40
30 27.161 7.80
35 22.489 6.47
40 18.766 5.41
50 — 4.5

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Chart 2 SO2 solubility curve

Ripple packing which is a kind of stacked packing by means of folding
many ripple sheet together, vertically and reversely, to form a disc, is adopted
in SO2 absorber. Due to the stacked structure, its resistance is much lower
than that of random packing, and thus the speed of gas or liquid can be
improved. Due to its compact structure, the packing has large specific
surface, which provides high efficiency, high operating flexibility and
advantage to contact between gas and liquid.
However, it is not applicable to materials that are easy to get scabbed,
with solid precipitation or polymerization, or with high liquid viscosity. In
addition, the operation of filling is not so convenient as that of random
stacking since the filling is difficult to be cleaned.
6) Off-gas treatment: Gas from the absorber is mixed with a small amount of
SO2 which will pollute the environment without treatment. Methods of SO 2
treatment is numerous, and can be generally classified into dry and wet

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT

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method. Dry method includes active carbon adsorption, activated manganese

oxide method, etc.; wet method mainly includes lime plaster method, alkaline
method, sodium sulfite method and ammonia absorption.
Since OKI has caustic soda liquid and equipment for alkaline method,
that the process of alkaline method is simple and that its absorption liquid can
be reused for slurring, alkaline method is adopted in OKI Sulfur Dioxide
Factory.
Reactions for alkaline method are as follows:
2NaOH+SO2 → Na2SO3+H2O PH≈8.9
Na2SO3+SO2+H2O → NaHSO3 PH=4-4.5
Actually Reaction 2 is the main reaction in SO 2 plants. Therefore, the
circulating fluid is the mixture of Na 2SO3 and NaHSO3, between which the
amount of Na2SO3 shall be controlled by adding NaOH solution continuously.
The content of Na2SO3 can be guaranteed by controlling the PH of the
circulating fluid, and such PH can be controlled at around 6-6.5 to reduce the
consumption of NaOH solution.
FRP material is employed in the absorber and Pall ring is installed inside
the tower to strengthen mass transfer.
Mesh demister is provided at the absorber outlet, and can eliminate
fogdrop effectively. Operating principle of demister is as follows:
To completely remove ultrafine fog droplets with a particle size of smaller
than 2μm, the I.C.I developed the non-wet fiber demister (also called
cylindrical demister or candle shaped demister), whose action mechanism is
as follows. For liquid particle with a particle size of larger than 1 ~ 2μm,
impact mechanism will be employed for removal. If the particle size is smaller,
when diffusion caused by Brownian movement is dominated (namely gas
passing through filter bed layer), the surrounding gas molecule will impact the
fine mist particle, causing the irregular diffusion of particle on fiber surface.
Although the efficiency of single fiber is low, the filter bed layer is composed of
tens of thousands of fibers, having considerably total efficiency.

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To avoid the hindering of diffusion caused by Brownian movement, the

filtration velocity shall be low. Designers finally determined the fiber material
through which highest efficiency would be obtained and proper packing
density after tests with glass fibers with different surface nature, diameter, and
density. The filter bed layer produced in this way has good demisting
efficiency within allowable range of pressure drop; moreover, it has been
discovered that if hydrophobic fiber material is selected, when the mist passes
through the bed layer, the trapped liquid will not be collected together, the
liquid particle trapped by fiber on fiber surface is in the form of drop not film,
and the fiber is dry. This is the so called “non-wet fiber”.
In actual production, the air flow is large and the flow rate is high, but the
filtering rate of filter bed shall be low. Such conflict shall be resolved by the
new design of demister structure. For this purpose, cylindrical demister (also
called candle shaped demister) is designed, with the structure as follows.
It is composed of two concentric cylinders made of anticorrosive screen
frame, with a space of 20cm. The filter bed is in the center of the space. The
candle shaped demister is installed vertically, and gas is filtered horizontally,
with the trapped liquid particle being aggregated and exhausted. The gas can
pass through the filter bed outwards or inwards, and the entire structure is
completely modularized. Meanwhile, the filter material can be replaced on
site, and it is no needed to carry back the filter to the manufacturer to replace
the packing or other parts.

OKI PULP AND PAPER 18T/D SO2 SOLUTION PLANT