Chemical Technology I - Lecture 9 - 10 - 11 - Industrial Gases

Chemical Technology I (Inorganic)
Lecture 9
Manufacture of Industrial Gases
Taught By:
Sanjay Kumar Sah
M.S. [Chemical Technology, Aalto University, Finland], MBA
B.S. Chemical Engineering (BUET), Bangladesh
Outline of Today’s Lecture
• Introduction of Indstrial Gases
• Manufacture of Carbon Dioxide
• Manufacture of Acetylene Gas
Industrial Gases
• Industrial Gases have been used since last century in the developed world.
In our country also, It is used for various uses and applications.
• Nitrogen, Hydrogen, Oxygen, Carbon Dioxide and Acetylene etc are called
Industrial gases.
• Nitrogen, Hydrogen, Oxygen are used directly or indirectly for the
manufacture of other chemicals.
• Carbon dioxide is mostly used for the production of urea fertilizer, for
refrigeration (in solid form as Dry Ice) for Ice-cream, meat and other food
products. CO2 inhibits the food and meat bacteria spoilage and so in the
Coca-cola.
• CO2 is used in carbonated beverages in Soft and hard beverages.
• Gaseous CO2 is used in manufacturing of Salicylic acid in Pharmaceutical
Industry.
• CO2 is used in Oil & Gas field for pressuring Oil & Gas well when the well is
near dry out or near the end of production from oil wells.
Industrial Gases
Carbon Dioxide (CO2)
Manufacture of CO2
There are many sources of CO2, however, following four are
most important for commercial production:
I. Recovery from synthesis Gas in Ammonia Production
II. Recovery as a bi-product in the production of Synthetic
Natural Gas (SNG)
III. Recovery from production of ethanol by fermentation
IV. Recovery from natural wells
Production Process
• Oil or natural gas or Coke is burnt, giving heat (M.P. steam at 13-14 bar) for
turbine and 10-15% CO2 at 345 C.
• Flue gas containing CO, CO2, (CH4, C2H6), water vapour etc are cooled
,purified and washed by passing through two water scrubbers where ashes
and other impuries are washed away.
• CO2 is selectively absorbed in counter-current stream of Mono-ethanol amine
(MEA or DEA) and Sodium Carbonate or aquous Potassium Carbonate
Solution. Here, CO and other gas is removed from above.
• CO2 is deabsorbed in deabsorption tower by reducing pressure and heating
(by Steam H.E.) the aquous solution.
• CO2 and steam leave the top of the reactivator passing through a CO2 cooler
to condense the steam, which returns as a reflux.
• CO2 is further treated and passed through KMnO4 solution and K2Cr2O7 to
remove the traces of impurities such as H2S and amine.
• CO2 is compressed and cooled and transported (shipped as liquid) or Dry Ice.
Acetylene (C2H2)
Lecture 10
Taught By:
Sanjay Kumar Sah
• Introduction of Industrial Gases
• Manufacture of Hydrogen
• Manufacture of Oxygen
• Manufacture of Nitrogen
Industrial Gases
Industrial gases.
Coca-cola.
Industry.
Acetylene (C2H2)
Acetylene
• Acetylene(C2H2) is used with O2 to produce high welding temperature around
2700 C and in the manufacture of Industrial Chemicals such as :
 Poly Vinyl Chloride
 Acrylonitrile
 Polyvinylpyrrolidone
 Trichloroethylene
 Acetic acid.
Some of these compounds are also derived from other sources such as ethylene; Only
one chemical is made mostly from acetylene: Chloroprene and its polymer
Neoprene.
Manufacture of Acetylene
• The manufacture of acetylene (C2H2) is done through the Pyrolysis or cracking of
Natural Gas (or Liquid Hydrocarbon feeds). There are some processes which include
partial oxidation, using oxygen, thermal cracking.
• The Oxygen and Hydrocarbon (Natural Gas) feed (in a molar ratio of 0.6:1.00 for Oxygen
and methane) are preheated separately at about 650 C using fuel gas for heating in pre-
heater. These two hot gases are sent to furnace or burner having three steps: a mixing
chamber, a flame or chemical conversion zone where reaction takes place and
quenching chamber by oil or water. The chemical conversion is almost instantaneous
partial (two-thirds) combustion of methane.
• Overall reaction of the methane is around 90 to 95% whereas oxygen is 100%
converted. Residence time is 0.001 to 0.01 Second. The acetylene and gases are cooled
rapidly by quenching oil or water sprays to 38 C. The clean gas is compressed to 1.14
Mpa.
• Acetylene is removed in packed column by selective solvent, eg, Dimethylformamide.
CO2 is flashed and stripped overhead out of the rich solvent in packed column, where
the acetylene is fractionated out (distilled Out), giving 99% + product with a 30 to 36 %
yield. From the Carbon in natural gas.
• Higher acetylenes and water are stripped out under reduced pressure, and the solvent
is reused.
Hydrogen
Production Processes of Hydrogen
Hydrogen can be produced using a number of different processes. Thermo-chemical processes
use heat and chemical reactions to release hydrogen from organic materials such as fossil fuels
and biomass. Water (H2O) can 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. These are the described as followings:
A. Thermo-chemical 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.
Learn more about the following thermochemical processes:
1) Natural gas reforming (also called Steam Methane Reforming or SMR) Process
CnHm + n H2O = nCO + [(m/2) + n] H2
CO + H2O = CO2 + H2
1) Gasification of the Coal and other Hydrocarbon
2) Hydrogen from Biomass gasification (Detailed after the production process)
B. Electrolytic Processes
Electrolyzers 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.
1) Electrolysis of water
2 H2O = 2 H2 (g) + O2 (g); Enthalpy of H = + 569 kJ
1) Bi-product in Chlor-Alkali Production Plant
C. Biological Processes:
Microbes such as bacteria and microalgae can produce hydrogen through biological
reactions, using sunlight or organic matter. These technology pathways are at an early stage
of research, but in the long term have the potential for sustainable, low-carbon hydrogen
production. Learn more about the following biological processes:
1) Microbial biomass conversion
2) Photobiological.
D. High temperature Fuel Cells
E. Other Methods
Hydrogen from Biomass Gasification
• Biomass gasification is a mature technology pathway that uses a controlled process involving
heat, steam, and oxygen to convert biomass to hydrogen and other products, without
combustion. Because growing biomass removes carbon dioxide from the atmosphere, the
net carbon emissions of this method can be low, especially if coupled with carbon capture,
utilization, and storage in the long term. Gasification plants for biofuels are being built and
operated, and can provide best practices and lessons learned for hydrogen production. The
U.S. Department of Energy anticipates that biomass gasification could be deployed in the
near-term timeframe.
• What Is Biomass?
• Biomass, a renewable organic resource, includes agriculture crop residues (such as corn
stover or wheat straw), forest residues, special crops grown specifically for energy use (such
as switchgrass or willow trees), organic municipal solid waste, and animal wastes. This
renewable resource can be used to produce hydrogen, along with other byproducts, by
gasification.
• How Does Biomass Gasification Work?
• Gasification is a process that converts organic or fossil-based carbonaceous materials at high
temperatures (>700°C), without combustion, with a controlled amount of oxygen and/or
steam into carbon monoxide, hydrogen, and carbon dioxide. The carbon monoxide then
reacts with water to form carbon dioxide and more hydrogen via a water-gas shift reaction.
Adsorbers or special membranes can separate the hydrogen from this gas stream.
• Simplified example reaction
C6H12O6 + O2 + H2O → CO + CO2 + H2 + other species
• Note: The above reaction uses glucose as a surrogate for cellulose. Actual biomass
has highly variable composition and complexity with cellulose as one major
component.
• Water-gas shift reaction
CO + H2O → CO2 + H2 (+ small amount of heat)
• Pyrolysis is the gasification of biomass in the absence of oxygen. In general,
biomass does not gasify as easily as coal, and it produces other hydrocarbon
compounds in the gas mixture exiting the gasifier; this is especially true when no
oxygen is used. As a result, typically an extra step must be taken to reform these
hydrocarbons with a catalyst to yield a clean syngas mixture of hydrogen, carbon
monoxide, and carbon dioxide. Then, just as in the gasification process for
hydrogen production, a shift reaction step (with steam) converts the carbon
monoxide to carbon dioxide. The hydrogen produced is then separated and
purified.
Why Is This Pathway Being Considered?
• Biomass is an abundant domestic resource.
In the United States, there is more biomass available than is required for food and animal
feed needs. A recent report projects that with anticipated improvements in agricultural
practices and plant breeding, up to 1 billion dry tons of biomass could be available for energy
use annually.
• Biomass "recycles" carbon dioxide.
Plants consume carbon dioxide from the atmosphere as part of their natural growth process
as they make biomass, off-setting the carbon dioxide released from producing hydrogen
through biomass gasification and resulting in low net greenhouse gas emissions.
• Research Focuses on Overcoming Challenges
• Key challenges to hydrogen production via biomass gasification involve reducing costs
associated with capital equipment and biomass feedstocks.
• Research to lower capital costs:
• Replacing the cryogenic process currently used to separate oxygen from air when oxygen is
used in the gasifier with new membrane technology.
• Developing new membrane technologies to better separate and purify hydrogen from the
gas stream produced (similar to coal gasification).
• Intensifying the process (combining steps into fewer operations).
• Research to lower biomass feedstock costs:
• Improved agricultural practices and breeding efforts should result in low and stable
feedstock costs.
• As biomass gasification is a mature technology, feedstock costs and lessons learned from
commercial demonstrations will determine its potential as a viable pathway for cost-
competitive hydrogen production.
Manufacture of Hydrogen
• Steam Methane (Hydrocarbon) Reforming Process (SMR): It is thermo-chemical process.
LPG (Propane and Butane) feed is heated by steam in passing the feed in H.E. to make it in
vapour state from pressurized Liquid state. (Naphtha or other Hydro carbon can also be used
as replaced feed).
• LPG or Hydro-carbon contain some amount of Sulphur as impurities which can corrode the
metal and react with catalyst, thus, this impurities (H2S or SO2) is removed in
desulphurization chamber by contact with activated carbon to prevent deactivation of the
catalyst.
• Propane vapour is mixed with Steam in Steam Reformer where nickel catalyst is used and
temperature is maintained at 815 C in alloy tubes in a combustion furnace with alumina brick
as refractory to maintain uniform heat by thermal radiation.
CnHm + n H2O = nCO + [(m/2) + n] H2 (Endothermic Reaction)
CO + H2O = CO2 + H2
• The reaction produces H2, CO and some CO2 which are cooled to about 370 C and partial
pressure of water increased by addition of steam or condensate, and passed over an iron
oxide catalyst in 1st Stage CO converter (H.T. Shift Reactor) followed by 2nd stage L.T. Shift
reactor where 90 to 95 % of CO is converted to CO2 with more H2. This is also called Shift or
Water-Gas-conversion reaction.
• These hot gases leaving the H.T. Shift reactor is cooled by passing it through H.E. by water to
about 38 C.
• These cooled gases are scrubbed with MEA or DEA solution in the first stage Girbotol
absorber to remove almost all CO2 by absorbing CO2 first in cool MEA or DEA
followed by regeneration of CO2 from MEA or DEA solution upon heating at 90 C in
Stripping tower. This CO2 can be stored or produced Dry ice upon liquefying and
pressurizing.
• The unconverted CO (very low CO2 may exist at this stage) is mixed with excess H2 is
heated to 315 C by exchange with gases in H.E. These gases are passed to methanator
over a nickel catalyst to convert essentially all the CO to methane (CH4).
• The product H2 gas from the methanator is cooled to 38 C with water H.E. leaving
Pure H2 gas which is compressed and sent to market as Product.
Hydrogen Purification
There are following purification required for Hydrogen.
I. Carbon Monoxide Removal:
II. Carbon Dioxide and H2S removal:
III. Adsorptive Purification:
IV. Cryogenic Liquid Purification:
There are many processes commercially employed for removal of acid gases CO2and
H2S.
a. MEA or Girbotol Process: A water solution of MEA or DEA is reacted with CO2 in
absorber vessel under pressure at room temperature. The MEA solution is then
heated in a stripping tower at 90 to 120 C and near atmospheric pressure. The
CO2 leaves the top of the stripping tower while regenerative solution MEA leaves
the bottom, cooled and pumped back to absorber. The problem associated with
MEA solution is corrosive nature of the solution. Amine guard can be used or
Stainless steel metal can be used.
b. Hot Potassium Carbonate Process: This process is developed by Bureau of mines,
is particularly useful for removing large quantities of CO2. Although it can remove
CO2 down to 0.1% by volume in the gas purified and is economical at 1% or more.
The CO2 gas is absorbed into hot K2CO3 under pressure and deabsorbed at same
temperature but near atmospheric pressure. Steam consumption and H.E. are
not removed or eliminated.
c. Physical Solvent Process: These are preocesses in which CO2 is removed by
physical solution in a solvent (a Proprietary soluation and patented). Examples are
Rectisol process using cold methanol (approx. – 60 C). The Fluor solvent process
using a non-aquous organic solvent such as propylene Carbonate.
The sulfinol process uses an organic solvent , sulfonate (Tetrahydrothiophene
dioxide).
The Selexol process uses dimethyl ether of Polyethylene glycol.
Aquous ammonia solution have been used for removal of CO2 and H2S
particularly in ammonia synthesis plant where ammonia is available.
Lecture 10
Taught By:
Sanjay Kumar Sah
• Introduction of Industrial Gases
• Manufacture of Hydrogen
• Manufacture of Oxygen
• Manufacture of Nitrogen
Industrial Gases
Industrial gases.
Coca-cola.
Industry.
Acetylene (C2H2)
Acetylene
• Acetylene(C2H2) is used with O2 to produce high welding temperature around
2700 C and in the manufacture of Industrial Chemicals such as :
 Poly Vinyl Chloride
 Acrylonitrile
 Polyvinylpyrrolidone
 Trichloroethylene
 Acetic acid.
Some of these compounds are also derived from other sources such as ethylene; Only
one chemical is made mostly from acetylene: Chloroprene and its polymer
Neoprene.
Manufacture of Acetylene
• The manufacture of acetylene (C2H2) is done through the Pyrolysis or cracking of
Natural Gas (or Liquid Hydrocarbon feeds). There are some processes which include
partial oxidation, using oxygen, thermal cracking.
• The Oxygen and Hydrocarbon (Natural Gas) feed (in a molar ratio of 0.6:1.00 for Oxygen
and methane) are preheated separately at about 650 C using fuel gas for heating in pre-
heater. These two hot gases are sent to furnace or burner having three steps: a mixing
chamber, a flame or chemical conversion zone where reaction takes place and
quenching chamber by oil or water. The chemical conversion is almost instantaneous
partial (two-thirds) combustion of methane.
• Overall reaction of the methane is around 90 to 95% whereas oxygen is 100%
converted. Residence time is 0.001 to 0.01 Second. The acetylene and gases are cooled
rapidly by quenching oil or water sprays to 38 C. The clean gas is compressed to 1.14
Mpa.
• Acetylene is removed in packed column by selective solvent, eg, Dimethylformamide.
CO2 is flashed and stripped overhead out of the rich solvent in packed column, where
the acetylene is fractionated out (distilled Out), giving 99% + product with a 30 to 36 %
yield. From the Carbon in natural gas.
• Higher acetylenes and water are stripped out under reduced pressure, and the solvent
is reused.
Hydrogen
Hydrogen can be produced using a number of different processes. Thermo-chemical processes
use heat and chemical reactions to release hydrogen from organic materials such as fossil fuels
and biomass. Water (H2O) can 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. These are the described as followings:
A. Thermo-chemical 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.
Learn more about the following thermochemical processes:
1) Natural gas reforming (also called Steam Methane Reforming or SMR) Process
CnHm + n H2O = nCO + [(m/2) + n] H2
CO + H2O = CO2 + H2
1) Gasification of the Coal and other Hydrocarbon
2) Hydrogen from Biomass gasification (Detailed after the production process)
B. Electrolytic Processes
Electrolyzers 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.
1) Electrolysis of water
2 H2O = 2 H2 (g) + O2 (g); Enthalpy of H = + 569 kJ
1) Bi-product in Chlor-Alkali Production Plant
C. Biological Processes:
Microbes such as bacteria and microalgae can produce hydrogen through biological
reactions, using sunlight or organic matter. These technology pathways are at an early stage
of research, but in the long term have the potential for sustainable, low-carbon hydrogen
production. Learn more about the following biological processes:
1) Microbial biomass conversion
2) Photobiological.
D. High temperature Fuel Cells
E. Other Methods
• Biomass gasification is a mature technology pathway that uses a controlled process involving
heat, steam, and oxygen to convert biomass to hydrogen and other products, without
combustion. Because growing biomass removes carbon dioxide from the atmosphere, the
net carbon emissions of this method can be low, especially if coupled with carbon capture,
utilization, and storage in the long term. Gasification plants for biofuels are being built and
operated, and can provide best practices and lessons learned for hydrogen production. The
U.S. Department of Energy anticipates that biomass gasification could be deployed in the
near-term timeframe.
• What Is Biomass?
• Biomass, a renewable organic resource, includes agriculture crop residues (such as corn
stover or wheat straw), forest residues, special crops grown specifically for energy use (such
as switchgrass or willow trees), organic municipal solid waste, and animal wastes. This
renewable resource can be used to produce hydrogen, along with other byproducts, by
gasification.
• How Does Biomass Gasification Work?
• Gasification is a process that converts organic or fossil-based carbonaceous materials at high
temperatures (>700°C), without combustion, with a controlled amount of oxygen and/or
steam into carbon monoxide, hydrogen, and carbon dioxide. The carbon monoxide then
reacts with water to form carbon dioxide and more hydrogen via a water-gas shift reaction.
Adsorbers or special membranes can separate the hydrogen from this gas stream.
• Simplified example reaction
C6H12O6 + O2 + H2O → CO + CO2 + H2 + other species
• Note: The above reaction uses glucose as a surrogate for cellulose. Actual biomass
has highly variable composition and complexity with cellulose as one major
component.
• Water-gas shift reaction
CO + H2O → CO2 + H2 (+ small amount of heat)
• Pyrolysis is the gasification of biomass in the absence of oxygen. In general,
biomass does not gasify as easily as coal, and it produces other hydrocarbon
compounds in the gas mixture exiting the gasifier; this is especially true when no
oxygen is used. As a result, typically an extra step must be taken to reform these
hydrocarbons with a catalyst to yield a clean syngas mixture of hydrogen, carbon
monoxide, and carbon dioxide. Then, just as in the gasification process for
hydrogen production, a shift reaction step (with steam) converts the carbon
monoxide to carbon dioxide. The hydrogen produced is then separated and
purified.
Why Is This Pathway Being Considered?
• Biomass is an abundant domestic resource.
In the United States, there is more biomass available than is required for food and animal
feed needs. A recent report projects that with anticipated improvements in agricultural
practices and plant breeding, up to 1 billion dry tons of biomass could be available for energy
use annually.
• Biomass "recycles" carbon dioxide.
Plants consume carbon dioxide from the atmosphere as part of their natural growth process
as they make biomass, off-setting the carbon dioxide released from producing hydrogen
through biomass gasification and resulting in low net greenhouse gas emissions.
• Research Focuses on Overcoming Challenges
• Key challenges to hydrogen production via biomass gasification involve reducing costs
associated with capital equipment and biomass feedstocks.
• Research to lower capital costs:
• Replacing the cryogenic process currently used to separate oxygen from air when oxygen is
used in the gasifier with new membrane technology.
• Developing new membrane technologies to better separate and purify hydrogen from the
gas stream produced (similar to coal gasification).
• Intensifying the process (combining steps into fewer operations).
• Research to lower biomass feedstock costs:
• Improved agricultural practices and breeding efforts should result in low and stable
feedstock costs.
• As biomass gasification is a mature technology, feedstock costs and lessons learned from
commercial demonstrations will determine its potential as a viable pathway for cost-
competitive hydrogen production.
• Steam Methane (Hydrocarbon) Reforming Process (SMR): It is thermo-chemical process.
LPG (Propane and Butane) feed is heated by steam in passing the feed in H.E. to make it in
vapour state from pressurized Liquid state. (Naphtha or other Hydro carbon can also be used
as replaced feed).
• LPG or Hydro-carbon contain some amount of Sulphur as impurities which can corrode the
metal and react with catalyst, thus, this impurities (H2S or SO2) is removed in
desulphurization chamber by contact with activated carbon to prevent deactivation of the
catalyst.
• Propane vapour is mixed with Steam in Steam Reformer where nickel catalyst is used and
temperature is maintained at 815 C in alloy tubes in a combustion furnace with alumina brick
as refractory to maintain uniform heat by thermal radiation.
CnHm + n H2O = nCO + [(m/2) + n] H2 (Endothermic Reaction)
CO + H2O = CO2 + H2
• The reaction produces H2, CO and some CO2 which are cooled to about 370 C and partial
pressure of water increased by addition of steam or condensate, and passed over an iron
oxide catalyst in 1st Stage CO converter (H.T. Shift Reactor) followed by 2nd stage L.T. Shift
reactor where 90 to 95 % of CO is converted to CO2 with more H2. This is also called Shift or
Water-Gas-conversion reaction.
• These hot gases leaving the H.T. Shift reactor is cooled by passing it through H.E. by water to
about 38 C.
• These cooled gases are scrubbed with MEA or DEA solution in the first stage Girbotol
absorber to remove almost all CO2 by absorbing CO2 first in cool MEA or DEA
followed by regeneration of CO2 from MEA or DEA solution upon heating at 90 C in
Stripping tower. This CO2 can be stored or produced Dry ice upon liquefying and
pressurizing.
• The unconverted CO (very low CO2 may exist at this stage) is mixed with excess H2 is
heated to 315 C by exchange with gases in H.E. These gases are passed to methanator
over a nickel catalyst to convert essentially all the CO to methane (CH4).
• The product H2 gas from the methanator is cooled to 38 C with water H.E. leaving
Pure H2 gas which is compressed and sent to market as Product.
There are following purification required for Hydrogen.
I. Carbon Monoxide Removal:
II. Carbon Dioxide and H2S removal:
III. Adsorptive Purification:
IV. Cryogenic Liquid Purification:
There are many processes commercially employed for removal of acid gases CO2and
H2S.
a. MEA or Girbotol Process: A water solution of MEA or DEA is reacted with CO2 in
absorber vessel under pressure at room temperature. The MEA solution is then
heated in a stripping tower at 90 to 120 C and near atmospheric pressure. The
CO2 leaves the top of the stripping tower while regenerative solution MEA leaves
the bottom, cooled and pumped back to absorber. The problem associated with
MEA solution is corrosive nature of the solution. Amine guard can be used or
Stainless steel metal can be used.
b. Hot Potassium Carbonate Process: This process is developed by Bureau of mines,
is particularly useful for removing large quantities of CO2. Although it can remove
CO2 down to 0.1% by volume in the gas purified and is economical at 1% or more.
The CO2 gas is absorbed into hot K2CO3 under pressure and deabsorbed at same
temperature but near atmospheric pressure. Steam consumption and H.E. are
not removed or eliminated.
c. Physical Solvent Process: These are preocesses in which CO2 is removed by
physical solution in a solvent (a Proprietary soluation and patented). Examples are
Rectisol process using cold methanol (approx. – 60 C). The Fluor solvent process
using a non-aquous organic solvent such as propylene Carbonate.
The sulfinol process uses an organic solvent , sulfonate (Tetrahydrothiophene
dioxide).
The Selexol process uses dimethyl ether of Polyethylene glycol.
Aquous ammonia solution have been used for removal of CO2 and H2S
particularly in ammonia synthesis plant where ammonia is available.

Chemical Technology I - Lecture 9 - 10 - 11 - Industrial Gases

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Chemical Technology I (Inorganic)

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