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Oxidation of So To So

The document summarizes the catalytic oxidation of SO2 to SO3 using a V2O5 catalyst. It discusses using multiple fixed bed reactors in series with interstage cooling to overcome the equilibrium limitation on conversion. High conversion (>99%) is achieved through this configuration of four catalytic beds and two absorption towers to produce concentrated sulfuric acid.

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Shivansh Singh
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Download as PDF, TXT or read online on Scribd
76 views

Oxidation of So To So

The document summarizes the catalytic oxidation of SO2 to SO3 using a V2O5 catalyst. It discusses using multiple fixed bed reactors in series with interstage cooling to overcome the equilibrium limitation on conversion. High conversion (>99%) is achieved through this configuration of four catalytic beds and two absorption towers to produce concentrated sulfuric acid.

Uploaded by

Shivansh Singh
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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OXIDATION OF SO2 TO SO3

• The next step in the process is catalytic oxidation of SO2 to SO3.


• For this reaction, a catalyst is needed to enhance reaction rates; there are no side reactions.
• The catalyst is vanadium pentoxide [V2O5] on an inert carrier or support such as silica/alumina.
• The carrier materials offer high surface area on which the catalyst is dispersed and deposited.
Distributing the catalyst over the support enhances its activity by exposing its surface to the reactants.

𝑜
SO2 + 0.5 O2 (g) SO3(g) ∆𝐻298 = −98.5 𝑘𝐽/𝑚𝑜𝑙

This reaction is reversible and exothermic. Consequently, conversion


of SO2 is limited by equilibrium. The reaction has certain limitations
on temperature: it occurs at temperatures > 425 oC, below this
temperature, the rates are negligible; temperatures > 620 oC are
V2O5 catalyst on a support
detrimental to the vanadium pentoxide [V2O5] catalyst.
OXIDATION OF SO2 TO SO3
• Goal for oxidation of SO2 to SO3 is to obtain more than 99% conversion
• This high conversion ensures that SO2 is completely utilized and exceedingly low levels of unreacted SO2 are
released into the atmosphere through the vent gas. Remember: SO2 is a pollutant that can cause acid rain.
• Achieving this goal for a reversible reaction is a challenge

Effect of temperature on equilibrium conversion of SO2 to SO3

Recall Le Chatlier’s principle for reversible and exothermic reactions.


Sketch equilibrium conversion of SO2 versus temperature. What temperatures favour high equilibrium conversion
of SO2? High or low? Explain.
OXIDATION OF SO2 TO SO3
• Goal for oxidation of SO2 to SO3 is to obtain more than 99% conversion
• This high conversion ensures that SO2 is completely utilized and exceedingly low levels of unreacted SO2 are
released into the atmosphere through the vent gas. Remember: SO2 is a pollutant that can cause acid rain.
• Achieving this goal for a reversible reaction is a challenge

Effect of temperature on equilibrium conversion of SO2 to SO3

Recall Le Chatlier’s principle for reversible and exothermic reactions.


Sketch equilibrium conversion of SO2 versus temperature. What temperatures favour high equilibrium conversion
of SO2? High or low? Explain.

Sketch rate of forward reaction versus temperature


Equilibrium
conversion

temperature
OXIDATION OF SO2 TO SO3
• Goal for oxidation of SO2 to SO3 is to obtain more than 99% conversion
• This high conversion ensures that SO2 is completely utilized and exceedingly low levels of unreacted SO2 are
released into the atmosphere through the vent gas. Remember: SO2 is a pollutant that can cause acid rain.
• Achieving this goal for a reversible reaction is a challenge

Effect of temperature on equilibrium conversion of SO2 to SO3

Recall Le Chatlier’s principle for reversible and exothermic reactions.


Sketch equilibrium conversion of SO2 versus temperature. What temperatures favour high equilibrium conversion
of SO2? High or low? Explain.

Reaction rate
Sketch rate of forward reaction versus temperature
Equilibrium
conversion

temperature
temperature
OXIDATION OF SO2 TO SO3
At what pressure should the oxidation of SO2 be conducted to achieve high conversion? Choose between
10 bar and 1.5 bar pressure.
OXIDATION OF SO2 TO SO3
At what pressure should the oxidation of SO2 be conducted to achieve high conversion? Choose between
10 bar and 1.5 bar pressure.

Even though equilibrium principles suggest 10 bar for the oxidation of SO2, commercial reactors are operated at
1.5 bar, because:
• Change in number of moles is only 0.5
• Pressurizing gases is expensive; the cost of compression nullifies the benefit of high conversion

Effect of temperature on equilibrium conversion of SO2 to SO3

Let’s discuss the features of different types of reactors used for heterogeneous systems. By heterogeneous here
we mean reactants are in gaseous form that react on a solid catalyst. You might have studied these reactors in
CL 324 course. After description of the features, we wish to discuss applicability of these reactors to oxidation
of SO2 to choose the best possible reactor to achieve our goals explained earlier.
FIXED BED REACTOR
• Catalyst is dumped in reactor [cylindrical vessel] and held in place by a
supporting plate at the bottom.
• The reactor is insulated so there is no heat exchange either with
surroundings or with any coolant.
• If the reaction is exothermic, heat is released as the reactants traverse
through the reactor.
• As this heat stays with reactants and the products, their temperature rises.
• As a consequence, the reaction rates rise leading to further increase in
temperature of reactor contents.
• However, the reducing concentration of reactants lowers the rates, which
eventually plateaus to a low value.
SHELL-AND-TUBE-TYPE REACTOR
• Catalyst is filled in tubes measuring few inches in diameter.
• The reactants in the form of gas enter the tubes and react
on the catalyst particles in the tubes.
• If the reactions are exothermic, heat is released as reaction
proceeds.
• This heat is removed by circulating a coolant in the shell side,
on the outside of the tubes.
• Typical coolant is water, which is converted to steam as it
leaves the reactor.
• As heat is removed continuously, the reactor is operated under
near-isothermal conditions.
• As the reaction progresses, the rates fall as the concentration
of reaction decreases and temperature remains nearly same.
FIXED BED REACTOR CONFIGURATION FOR THE OXIDATION OF SO 2 TO SO3
• Fixed bed reactors achieve high rates by allowing the temperature of reactor contents to rise.

• However, with rising temperatures, the equilibrium conversion that can be attained decreases.
• The reactor effluents exit the reactor at a higher temperature than the temperature at which they entered and an
equilibrium conversion corresponding to this exit temperature. Clearly, this conversion is far less than 100 %.
• The equilibrium limitation on conversion of SO2 is overcome by using multiple fixed bed reactors with interstage
cooling.
• The stream emerging from the first bed is cooled and then passed through the second bed of catalyst. In the
second bed, the temperature rises again because of reaction. The effluent of second bed are cooled and then fed
to the third bed.
• As we keep using more beds of catalyst, SO2 concentration keeps dropping after every bed and lowering the
reaction rates.
• After three beds, the reaction is pushed forward by removing SO3 by dissolving it in aqueous H2SO4 to produce
concentrated H2SO4.
• The outlet stream of the absorber is passed through fourth bed to achieve an overall conversion of SO2 upwards
of 99 %.
• The effluents of this bed are passed through another absorber to mop up SO3, again in aqueous H2SO4 to produce
concentrated H2SO4.
Show the strategy on a plot of equilibrium conversion versus temperature and explain it.
Show the strategy on a plot of equilibrium conversion versus temperature and explain it.

BED 4
BED 3
Equilibrium
conversion

BED 2

BED 1

temperature
Show the strategy on a plot of equilibrium conversion versus temperature and explain it.

Draw a flowchart that achieves 99.7 % conversion of SO2


to SO3. This flowchart should have four catalytic beds and
BED 4 two absorption towers. Include cooling and heating
BED 3 operations wherever necessary.
Equilibrium
conversion

BED 2
Use the following symbols for the flowchart:
BED 1

temperature Catalyst bed Cooler Heater


Absorption
tower

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