ALTERNATIVE PROCESSES TO CRYOGENIC AIR SEPARATION

LECTURE 3
DON CHINUNGI

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 ADSORPTION PROCESS

 Pressure Swing Adsorption/Vacuum Swing Adsorption is a technology used

to separate some gas species from a mixture of gases under pressure

 The separation is achieved due to the unique molecular characteristics of

the species and their affinity to adsorbent materials.

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 VACUUM SWING ADSORPTION

 Makes use of pressure that is less than atmospheric pressure and

adsorbents to separate nitrogen, and carbon dioxide from air

 The air is separated at ambient temperature by passing it through a

column of adsorbent materials

 adsorbent material is usually inorganic crystal material.

 The adsorbent selectively adsorbs nitrogen molecules on its surface, while

the oxygen molecules pass on through the adsorbent column

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 VACUUM SWING ADSORPTION

 Oxygen product exits the adsorber column.

 The nitrogen adsorbed is released when the adsorber column is

reactivated by use of differential pressure from a vacuum.

 Once the adsorber column is reactivated, the cycle is ready to be repeated.

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 PRESSURE SWING ADSORPTION

 Pressure Swing Adsorption process produces a particular gas by passing

a pressurized gas stream through a set of adsorbent beds

 Impurities in the air stream are selectively adsorbed using molecular

sieves or other selective adsorbents

 Compressed air is passed through a column of chemical adsorbents; the

adsorbent is usually a carbon based material

 The chemical adsorbent selectively traps the oxygen molecules and

allows nitrogen molecules to pass through.

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PROCESS DIAGRAM FOR NITROGEN PSA SYSTEM

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PRODUCTION OF CARBON DIOXIDE
Sources of Carbon Dioxide

 Burning of carbonaceous material (10 -18%)

 In the production of hydrogen by steam water gas shift. About 16 % of carbon

dioxide is obtained.

 In the manufacture of ethanol by fermentation process. About 99.99% pure

carbon dioxide is obtained

 In the calcination of calcium carbonate. About 40% of carbon dioxide is obtained

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PRODUCTION OF CARBON DIOXIDE

 Raw materials

 Coke or Coal; coke is a solid fuel made by heating coal in the absence of
air in order to drive off the volatile components.

 Air

 Chemical reaction

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PRODUCTION OF CARBON DIOXIDE
 Coal/coke is burned in a boiler for the production of 200 – 250 PSI steam.

 The flue gas containing 10 – 18 % of carbon dioxide are taken from the boiler at
350oC.

 The gases are then passed through two packed towers where they are cooled
and cleaned by water in a scrubber.

 After passing through the scrubber, the cooled gases are passed through a
booster fan into the bottom of the absorption tower.

 In the absorption tower, carbon dioxide is absorbed selectively by a solution of

ethanolamine, introduced at the top of the tower
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PRODUCTION OF CARBON DIOXIDE

 Ethanolamine passes counter currently to the carbon dioxide rich gas stream.

 The carbon dioxide free flue gas are exhausted to the atmosphere while carbon
dioxide bearing solution passes out of the bottom of the adsorption tower.

 The amine solution is then sprayed from the top of the reactivation tower.

 Carbon dioxide is stripped from the amine solution by addition of heat in the
reactivation tower.

 The reactivation solution is recycled through the heat exchanger to the

absorption column.

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PRODUCTION OF CARBON DIOXIDE
 The steam condensate returns to the tower as reflux. If liquid or solid CO2 is
desired, it may be further purified for odor removal before compression

CO2 recovery by solvent absorption process

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PRODUCTION OF CARBON DIOXIDE
METHODS OF RECOVERY

 The recovery of carbon dioxide from the flue gas in the absorption tower maybe
achieved by different absorption solution and the process are therefore termed
as

 Ethanolamine process

 Sodium carbonate process

 Potassium carbonate process

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PRODUCTION OF CARBON DIOXIDE
 The choice of the suitable process depends on the individual conditions.
 In all these processes, carbon dioxide is recovered by absorption-desorption
process.
 Firstly the carbon dioxide bearing gases are passed counter currently to a
solution that absorbs carbon dioxide and retains it until desorbed by heat in a
separate piece of equipment;
 Due to relatively low water solubility of carbon dioxide, water alone cannot be
used as an absorption medium.
 Alkali carbonate and ethanolamine solutions are used due to the higher
solubility of carbon dioxide with the absorbing medium.
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PRODUCTION OF CARBON DIOXIDE

 Advantages of ethanolamine process

 Carbon dioxide is completely removed from the flue gas

 Up to 100% regeneration of ethanolamine is achieved with moderate

steam consumption

 Higher carbon dioxide absorption

 Lower operating cost

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PRODUCTION OF CARBON DIOXIDE

Uses

 It is used for pressurizing, and as a source of the bubbles and the acidic taste
in soft drinks.

 Can be filled in a type of fire extinguisher that literally depends on the

inertness of the compound.

 freezing specialty and quality foods.

 Gaseous carbon dioxide is used for pH control in water treatment and as a

growth stimulant for plant life

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HYDROGEN PRODUCTION

 Hydrogen can be produced using a number of different processes

 Thermochemical processes use heat and chemical reactions to release

hydrogen from organic materials, such as fossil fuels and biomass, or from
materials like water.

 Water (H2O) can also be split into hydrogen (H2) and oxygen (O2) using
electrolysis or solar energy.

 Microorganisms such as bacteria and algae can produce hydrogen through

biological processes.

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HYDROGEN PRODUCTION
Thermochemical Processes

 Some thermal processes use the energy in various resources, such as natural gas,
coal, or biomass, to release hydrogen from their molecular structure.

 In other processes, heat, in combination with closed-chemical cycles, produces

hydrogen from feedstocks such as water.

 Natural gas reforming (also called steam methane reforming or SMR)

 Biomass gasification

 Biomass-derived liquid reforming

 Solar thermochemical hydrogen (STCH).

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HYDROGEN PRODUCTION
 Natural gas reforming

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HYDROGEN PRODUCTION
 Biomass gasification

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HYDROGEN PRODUCTION
 Biomass-derived liquid reforming

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HYDROGEN PRODUCTION
Electrolytic Processes
 It is the process of using electricity to split water into hydrogen and oxygen. This
reaction takes place in a unit called an electrolyzer.
 Electrolyzer use electricity to split water into hydrogen and oxygen.

 This technology is well developed and available commercially, and systems that can
efficiently use intermittent renewable power are being developed.
 An electrolyzer consist of an anode and a cathode separated by an electrolyte.

 Different electrolyzers function in different ways, mainly due to the different type of
electrolyte material involved and the ionic species it conducts.
 Hydrogen produced via electrolysis can result in zero greenhouse gas emissions,
depending on the source of the electricity used.
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HYDROGEN PRODUCTION

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HYDROGEN PRODUCTION
Alkaline Electrolyzers
 Alkaline electrolyzers operate via transport of hydroxide ions (OH-) through the electrolyte from
the cathode to the anode with hydrogen being generated on the cathode side.
 Electrolyzers using a liquid alkaline solution of sodium or potassium hydroxide as the electrolyte
have been commercially available for many years.

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HYDROGEN PRODUCTION
Polymer Electrolyte Membrane Electrolyzers
 In a polymer electrolyte membrane (PEM) electrolyzer, the electrolyte is a solid specialty
plastic material.
 Water reacts at the anode to form oxygen and positively charged hydrogen ions
(protons).
 The electrons flow through an external circuit and the hydrogen ions selectively move
across the PEM to the cathode.
 At the cathode, hydrogen ions combine with electrons from the external circuit to form
hydrogen gas.
Anode Reaction: 2H2O → O2 + 4H+ + 4e-
Cathode Reaction: 4H+ + 4e- → 2H2
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HYDROGEN PRODUCTION
Solid Oxide Electrolyzers
 Solid oxide electrolyzers, which use a solid ceramic material as the electrolyte that
selectively conducts negatively charged oxygen ions (O2-) at elevated temperatures
 Steam at the cathode combines with electrons from the external circuit to form
hydrogen gas and negatively charged oxygen ions.
 The oxygen ions pass through the solid ceramic membrane and react at the anode to
form oxygen gas and generate electrons for the external circuit.
 Solid oxide electrolyzers must operate at temperatures high enough for the solid oxide
membranes to function properly (about 700°–800°C,)
 Compared to PEM electrolyzers, which operate at 70°–90°C, and commercial
alkaline electrolyzers, which typically operate at less than 100°C).
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