Acknowledgement

Kurdistan Regional Government ‫هەرێمى كوردستانى عيراق‬
Presidency of Ministers Council ‫سەرۆكايەتى ئەنجومەنى وەزيران‬

Ministry of Higher Education And ‫وەزارەتى خوێندنى باالوتوێژينەوەى‬
Scientific Research ‫زانستى‬
KOYA University ‫سەرۆكايەتى زانكۆى كۆيە‬
Faculty of Engineering ‫فاكەلتى ئەندازيارى‬
Department: chemical engineering ‫ كيمياوى‬: ‫بەشى‬
Computer Simulation of Oxygen Production using

Cryogenic Air Separation Method by DWSIM
Software
A Project Submitted to the Chemical Engineering Department Faculty of

Engineering/ Koya University in partial Fulfillment of the Requirement
for the Degree of Bachelor in Chemical Engineering
Prepared by
Abdullah Najmaddin Tahir
Kardo Mazhar Ibraheem
Jegr Hussein Paez
Qutaiba Muhammed Hussein
Supervised by
Assist Prof. Dr. Saif T. Manji
May 2019
i
Acknowledgement
I take immense pleasure in thanking and wish to express my deep sense of gratitude
to my project supervisor Dr. Saif T. Manji, and to the Head of Chemical Eng.
Department and the staff of Department. KOYA University for his able guidance
and useful suggestions. It would not been possible for me to bring out this project
without his assistance and encouragement. I would also like to acknowledge my
colleagues at the department or the university for their wonderful collaboration. You
supported me greatly and were always willing to help me
To my family, thank you for encouraging me in all of my pursuits and inspiring me
to follow my dreams. I am especially grateful to my parents, who supported me
emotionally and financially. I always knew that you believed in me and wanted the
best for me. Thank you for teaching me that my job in life was to learn, to be happy,
and to know and understand myself; only then could I know and understand others.
Thank you to my mother, for guiding me. special thank to my sisters and brothers
for there support
ii
Abstract
It’s been a few days now, requirement of Nitrogen and Oxygen and increases day
by day. Especially for a steel industry this tow components are very essential for
their steel production like decarburization, desulphurization, hydrogen removal,
nitrogenating, argon, oxygen removal, metal cutting, welding, and cooling etc.
Cryogenic air separation has the best impact to separate the air. Study and analyses
of practical plant performance through computer aided programs has better and cost
effective. System simulation is the calculation of operating variables such as
pressure, temperature and flow rates of energy and fluids in a thermal system
operating in a steady state. The equations for performance characteristics of the
components and thermodynamic properties along with energy and mass balance
form a set of simultaneous equations relating the operating variables. The
mathematical description of system simulation is that of solving these set of
simultaneous equations which may be non-linear in nature. Cryogenics is the branch
of engineering that is applied to very low temperature refrigeration applications such
as in liquefaction of gases and in the study of physical phenomenon at temperature
of absolute zero. the liquefaction of various industrial gases as Nitrogen, Helium
etc. The following work aims to simulate the cryogenic cycles with the help of the
simulation tool DWSIM where all calculations are done at steady state and the results
hence obtained.
DWSIM software program is one of the process simulators that are widely used in
cryogenic, chemical and thermodynamic process industries today. In this work, the
simulation study of cryogenic air separation process is performed by DWSIM
software . The simulation study is based on both steady state (high pressure column
and low pressure column). The plant efficiency, , product purity and behavior of
process parameter with respect to time and feed disturbance have been discussed.
iii
Contents page
Acknowledgement……………………………………..………...…………...……………………i
Abstract…………………………………………………………….………….…………………..ii
Contents………………………………………………………….….…...……………………….iii
List of figure……………………………………………………….……………………………...v
List of tables………………………………………………………………………….………….vii
Chapter One: Introduction …………………………………………….……………………….1
1.1 Historical Background………………..………………………………………………………..1
1.2. The Occurrence of Oxygen…………………………………..……………………………..…2
1.2.1 Oxygen in the Air and Photosynthesis…………………………………………………….....3
1.3. Physical properties ……………………………………………………………………………5
1.4. methodology (method of Productions)………………………………………………….…….8
1.4.1. Methods of production………………………………………………………………..…….9
1.42. Adsorptive Air Separation……………………………………………………………….…..9
1.4.3. Membrane Air Separation …………………………………………………………………11
1.4.4. Oxygen from Cryogenic Air Separation……………………………………………….…..11
1.5. Uses……………………………………………………………………………………...…..13
1.5.1. Combustion and Metallurgy……………………………………………………………….14
1.5.2. Production of Chemicals…………………………………………………………………..18
1.5.3. Oxygen Bleaching of Wood Pulp……………………………………………………….…20
1.5.4. Wastewater Treatment…………………………………………………………………..…21
1.5.5. Medicine……………………………………………………………………………….…..22
1.6. Storage and Transportation…………………………………………………………………..23
1.6.1. Storage……………………………………………………………………………………..23
1.6.2. Material Selection for Oxygen Compatibility…………………………………..………….23
1.6.3. Transportation…………………………………….……………………………………….24
1.7. Safe storage, Handling………………………………………………………………...……..26
1.7.1. Disposal…………………………………………………………………………..………..26
1.7.2. Handling leaked and emergences…………………………………………………………..26
1.7.3. First aid…………………………………………………………………………………….26
1.7.4. Method of Shipment……………………………………………………………...………..27
1.7.5. Containers…………………………………………………………………………..……..27
1.7.6. Filling limits……………………………………………………………………………….27
1.7.7. Cylinders…………………………………………………………………………………..27
1.7.8. Tube trailers and cargo tanks on trucks or trailers……………………………….…………28
1.7.9. Small portable liquid containers…………………………………………………..……….28
1.7.9. Small portable liquid containers………………………………………………………..….28
1.7.10. Tank cars………………………………………………………………………..………..28
1.8 The Biological Role of Oxygen………………………………………………………………28
Chapter Tow: Process instrumentation……………………………………………………….29
2.1 Cryogenic Technology……………………………………………………………….………29
2.2 Air Separation………………………………………………………………………………..30
2.3 Oxygen from Cryogenic Air Separation……………………………………………..………34
iv
Contents page
2.4 Cryogenic Instrumentation……………………………………………………………….…..36
2.4.1 Pressure…………………………………………………………………………………….36
2.4.2 Liquid Level…………………………………………………………………………..……37
2.4.3 Flow……………………………………………………………..…………………………37
2.4.4 Temperature………………………………………………………………………………..37
2.5 Process Equipment……………………………………………………………………….…..38
2.5.1 Heat Exchangers………………………………………………………………….………..38
2.5.2 Heat-Transfer equipment…………………………………………………………………..39
2.5.3 Expanders……………………………………………………………………………….….41
2.5.3 Mechanical Expanders……………………………………………………………..………41
2.5.4 Joule-Thomson Valves…………………………………………………….……………….41
2.5.5 Separation and purification system……………………………………………..………….41
2.6 Air-Separation Systems……………………………………...………………………………42
Chapter Three: Process Simulation…………………………………………………………...45
3.1. Process concept……………………………………………..………………………...……..45
3.1.1. Double-column system……………………………..……..……………………....………45
3.2. process simulation by DWSIM………………………….…………………………………..46
3.3. Process description………………………………………………………………………..…46
3.3.1. Production of oxygen and nitrogen by double column……………………………..……..47
3.4. Factors influencing distillation process………………………………………………….….52
Chapter Foure : Result and discussions ……….…………………………….……………….52
4.1. Steady state separation plant air………………………………….……………….…………52
4.2. Result and discussions………………………………………………………...…………….55
4.2.1. Steady-state simulation analysis…………………………………………………………..55
4.2.2. High pressure column……………………………………………………………..………55
4.2.3. Low pressure column…………………………………………………………………...…57
4.3. Heat exchanger………………………………………………………………………..……..60
4.4. Product recovery…………………………………………………………………………….65
Chapter Five: Conclusion, Future work ……………………………..……………………….66
Chapter Six : References …………………………………...………………………………….67
v
List of figures page
Figure 1.1. Schematic illustration of photosynthesis ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 3
Figure 1.2. air compassion˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 4
Figure 1.3. Oxygen pressure swing adsorption (PSA) system ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 10
Figure 1.4. Cryogenic oxygen plant (schematic) ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 13
Figure 1.5. Effect of oxygen enrichment on flame velocity of methane ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 15
Figure 1.6. Effect of oxygen enrichment on flame temperature of methane ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 15

Figure 1.7. Oxygen-blown LD converter ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖17
Figure 1.8. Three-stage UNOX system (Union Carbide) ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 21
Figure 1.9.Oxygen production in the United States (U.S. Bureau of the Census, Current
Industrial Reports M-28C)˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖23
Figure1.10. Minimum distances between liquid-oxygen storage and exposures ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 25

Fig. 2.1. Cryogenic air separation process ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 30
Fig. 2.2. Pumped liquid oxygen process. ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 32
Fig. 2.3. UHP nitrogen process with UHP oxygen coproduction. ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 33
Figure 2.4. Cryogenic oxygen plant (schematic) ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 35
Figure 2.5 .Linde single-column air separator. ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 43
Figure 2.6 .Linde double-column air separator ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 44
Fig.3.1. Linde double column system ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 46
Fig. 3.2. Line diagram of the actual cryogenic air separation (N2.O2, AR) process. ˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 48
Fig. 3.3. Line diagram of the simulated cryogenic air separation by DWSIM program ˖˖˖˖˖˖˖˖˖˖˖ 49
Fig. 3.4.A. Line diagram of the simulated cryogenic air separation by DWSIM program ˖˖˖˖˖˖˖˖˖50
Fig. 3.4.B. Line diagram of the simulated cryogenic air separation by DWSIM program ˖˖˖˖˖˖˖ 51
Fig.4.2. High pressure column profile: (a) variation of temperature with stage from top to
bottom; (b) variation of pressure with stage ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 55
Fig.4.2. (c) variation of composition with stage; (d) variation of net molar floe with stage. ˖˖˖˖˖˖ 56
Fig.4.3.a Low pressure column profile from top to bottom ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 57
Fig.4.3. Low pressure column profile from top to bottom: (a) temperature versus stage; (b)
pressure versus stage; (c) molar fraction versus stage ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 58
Fig.4.3. (d) net molar flow versus stage ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 59
vi
List of tables Page
Table 1.1. Oxygen occurrence in different “regions” ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 2
Table 1.2. The complex photosynthesis reaction ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 4
Table 1.3. Oxygen Solubility in Water (Early, 2004) ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 5
Table 1.4. of some physical properties are as follows (Perry and Green, 2008) ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 6
Table 1.5. Physical Properties of Oxygena (Early, 2004) ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 7
Table 4.1. The Simulation parameters for the cryogenic air separation unit. ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖53
Table 4.2. Properties of each material stream in the process simulation. ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 61
Table 4.3 Energy streams in the process simulation˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖63
Table 4.4 Composition of each stream in the process simulation˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖64
vii
KOYA University 2019
CHAPTER ONE
Introduction
1.1. Historical Background
Oxygen [7782-44-7] forms acids by combining with many different substances and accordingly
derives its name from the Greek oxys “sharp acid”, and -genes “born” meaning acid former. Itis a
nonmetallic element of group 16 of the periodic table. Under standard conditions it is a colorless,
odorless, and tasteless diatomic gas, having the molecular formula O2. Oxygen is essential to life,
as we know it, and the most abundant element on the Earth’s surface. Oxygen accounts for 23.2
wt% of the atmosphere, 85.8 wt% of seawater, and 46.6 wt% of the Earth’s crust. The discovery
of oxygen is credited to the independent work of the Swedish chemist Scheele and the English
chemist Priestley.Scheele (1772) obtained oxygen by heating potassium nitrate and mercury (II)
oxide to decomposition and collecting the evolved gas. Priestley (1774) also thermally
decomposed mercury (II) oxide to obtain oxygen and further demonstrated that at a lower
temperature, mercury and oxygen could be quantitatively recombined in the reverse reaction to
reproduce the starting oxide. Neither researcher, however, recognized oxygen for what it was. The
French chemist Lavoisier (1777), who first understood the gas to be elemental, gave the new
substance its present name and, in opposition to the prevailing phlogiston theory, explained
combustion as the union of oxygen with a burning fuel. Oxygen is nonflammable but readily
supports combustion. All materials that are flammable in air burn much more vigorously in
oxygen, some with an explosive intensity. Free oxygen constitutes about one-fifth of the
atmosphere (20.99 vol%) and is the result of photosynthesis. In green plants, incident solar energy
is captured and used to convert water, carbon dioxide, and minerals into oxygen, which is released
into the atmosphere, and energy-rich organic compounds (carbohydrates, amino acids, proteins,
lipids, and pigments) required by the plants for growth and reproduction. Isotope studies with 18O
have confirmed that the source of the released oxygen is water. Oxygen combined as carbon
dioxide is retained in the organic products. (Mark J. Kirschner, 2011)
After the discovery of oxygen, Cavendish, who had been the first to make a thorough study of
hydrogen in 1766, sparked hydrogen with air and oxygen, thereby producing and proving the
nature of water (qv). Cavendish also sparked the mixture of oxygen and air to form nitric oxide
and nitrogen dioxide, which was absorbed in aqueous alkali. He also burned the excess oxygen
with sulfur, and the resultant sulfur dioxide was absorbed in alkali. For well over 100 years after
its discovery and initial preparation, oxygen was made either chemically or by the electrolysis of
water. Early in the twentieth century, Linde and Claude introduced processes for the liquefaction
and distillation of air that have since grown into a mature and highly competitive industry. In 1991,
over 13.4×109 m3 (4.7×1011 ft3) of oxygen was produced in the United States. About 70×109 m3
(24.7×1011 ft3) was produced worldwide. Oxygen in combination with hydrogen forms the waters
of the earth’s surface (89 wt% O2). In combination with metals and nonmetals oxygen is contained
in well over 98% of rocks, entering into a very large number of known minerals as well as a vast
array of organic compounds. Together, free and combined oxygen constitute 46.6% (Radetzki,
1978) of the mass of the earth’s crust, making it the most abundant element. In the Earth’s
geological beginning the atmosphere probably contained little or no oxygen. The subsequent
emergence of free molecular oxygen into the atmosphere may have arisen because of dissociation
of water by high energy rays from the sun and cosmic rays in the upper atmosphere, followed by
1|Page
differential escape of hydrogen into space (Mao et al., 1995). The detection by the Apollo16 moon
flight, in April 1972, of a massive cloud of atomic hydrogen enveloping (Early, 2004)
As gas, oxygen occupies 862 times as much space as the liquid. Oxygen is one of the most useful
elements and is marketed in steel cylinders under pressure, although most of the industrial uses are
in the form of its compounds. An important direct use is in welding and metal cutting, for which
it should be at least 99.5% pure. Oxygen-enriched air is used in a number of oxidation and
combustion processes in the steel, cement, glass, petrochemical, refining, and paper-and-pulp
industries, and it has potential economic and environmental benefits in waste combustion. Oxygen
enrichment improves overall combustion by raising oxygen partial pressure, thus increasing the
combustion temperature and waste destruction. (Vaccari, 2002)
1.2. The Occurrence of Oxygen

Oxygen is the most common element on earth and the third most abundant in the universe. Its
occurrence is described in Table 1.1. (Enghag, 2008)
Table 1.1. Oxygen occurrence in different “regions”
Region Comments
Entire universe In the whole universe, hydrogen and helium are the most common
elements. Oxygen has the third position
Whole earth 29% of the total mass of the earth is estimated to consist of oxygen
Earth’s crust 46% of the earth’s crust consists of oxygen, which makes it the most
common element in the crust. Oxygen is present in oxides, silicates,
carbonates, phosphates and so on
The hydrosphere Oxygen is of course a major component of the water of oceans, lakes
and rivers, and is also present in the water as dissolved oxygen gas
and in dissolved sulfates, carbonates, etc. The ice near the poles also
is a considerable part of the hydrosphere. The total mass of the
hydrosphere is ca. 1.5 · 1018 tonne, of which oxygen represents 86%
The atmosphere The oxygen content in the atmosphere is 21% by volume at the
surface of the sea. The total amount of oxygen in the atmosphere is
an impressive 1.2 · 1015 tonnes. However, this is only one-millionth
of the total amount of oxygen on the earth
The biosphere In living organisms, oxygen is present bound in water, phosphates,
carbohydrates and proteins. An adult is made up of 65% oxygen. The
oxygen supply occurs by breathing in daily an air volume
corresponding to 630 liters of oxygen. A further ca. 225 g is taken in
from food
2|Page
1.2.1 Oxygen in the Air and Photosynthesis
The development of microorganisms able to split the water molecule was an important, early step
in evolution. In this process carbon dioxide and water are transformed to carbohydrates, such as
for instance glucose and free oxygen. Sunlight is essential for the process (Figure 1.1.). The
photosynthesis reaction for the production of glucose C6H12O6 can be written simply as
6CO2 + 6H2O → C6H12O6 + 6O2
However, Table 1.2. is an attempt to show, more realistically, how the complicated photosynthesis
reaction actually functions. Almost all the oxygen in the atmosphere has been formed by
photosynthesis. Until conditions for this reaction were favorable, about 3 billion years ago, the
oxygen
Figure 1.1. Schematic illustration of photosynthesis
content of the earth’s atmosphere was very low. With the right conditions, the process started and
the oxygen content increased. The oxygen formed in photosynthesis gave problems. For what
purpose should it be used? The chemist can see from the photosynthesis reaction equation that
increasing the oxygen content in the atmosphere makes it more difficult for the reaction to proceed
to the right. (Enghag, 2008)
3|Page
Table 1.2. The complex photosynthesis reaction
6CO2 + 12H + light →

Carbon dioxide. Available water.
Its oxygen goes to make glucose This provides the oxygen formed in
and newly formed water photosynthesis
→ 6O2 + C6H12O6 + 6H2O

Oxygen. Glucose. Formed water
Formed from water Made with oxygen Its oxygen comes from
available at the beginning from carbon dioxide carbon dioxide
Thus from the viewpoint of the carbohydrates, the oxygen formed was a poison. The content of
oxygen, however, increased during geological epochs and became a threat to green vegetation.
But, in contrast, the increasing oxygen content created the necessary conditions for a new type of
living matter, animals. They utilized oxygen for their vital processes. A balance arose with an
atmosphere, well suited for both animals and vegetation. Photosynthesis is the basis for the
generation and maintenance of this balance. The behavior of mankind in our time may disturb the
balance, as has been treated in Chapter 39 Carbon. (Enghag, 2008)
Figure 1.2. air compassion
4|Page
1.3. Physical properties

Gaseous oxygen is colorless, odorless, and tasteless. When cooled to 90.188 K it becomes a pale
blue liquid, slightly more dense than water. On further cooling, it becomes a blue solid. The blue
color probably results from a small equilibrium concentration of associated oxygen molecules. The
liquid becomes colorless when passed through a bed of carefully activated silica gel, presumably
because the associated molecules are removed. The color returns after some hours of standing.
Oxygen is moderately soluble in water. Selected physical properties are listed in Table . The
oxygen molecule is paramagnetic, having a magnetic moment in accord with two unpaired
electrons. The gases with which oxygen is normally associated are diamagnetic. Thus the oxygen
content of a mixture of gases can be determined using simple instruments that measure the
magnetic properties of the gas some physical properties are as follows (Early, 2004)
Table 1.3. Oxygen Solubility in Water (Early, 2004)
NO. Temperature, °C Aqueous solubility of O2 at STP, L/L

0 0 0.0489
1 5 0.0429
2 10 0.0380
3 15 0.0342
4 20 0.0310
5 25 0.0283
6 30 0.0261
7 40 0.0231
8 50 0.0209
9 60 0.0195
10 70 0.0183
11 80 0.0176
12 90 0.0172
13 10 0.0170
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Table 1.4. of some physical properties are as follows (Perry and Green, 2008)
NO. Property Value Units

1 Chemical formula O2
2 Formula weight 32.00
3 Color, crystalline form col. gas or hex. solid
and refractive index
4 Specific gravity , sp gr 1.14−188°, 1.426−252.5°
5 Metaling point, mp −218.4 C°
6 Boiling point , bp −183 C°
7 Solubility in 100 parts, 4.890° cc
Cold water
8 Solubility in 100 parts, 2.630° Cc
Hot water
9 Vapor Pressure, Ps Ps = exp(C1 + C2/T + C3 ln T + C4TC5) P in Pa, T in
K
10 Density , ρ ρ= C1/C2[1 + (1−T/C3)C4] ρ in
mol/dm3 , T
is in K,
11 Critical Temperature, Tc 154.58 K
12 Critical Pressure , Pc 5.043 MPa
13 Critical Volume , Vc 0.0734 m3/kmol
14 Heat of fusion 106 cal/mol
15 Heat of vaporization , ∆Hc = C1(1 − Tr) C2+ C3Tr+ C4Tr2+ C5Tr3 J/kmol , T is
∆Hc Tr = T/Tc in K
16 Liquid Heat Capacities , CpL = C1 + C2T + C3T2 + C4T3 + C4T4 J/(kmol/K)
CpL
17 Gas heat capacity , Cp0 Cp0=C1+C2 [C3/T /sinh(c3/T) ]2 +C4 J/(kmol/K)
[C5/T/cosh(c5/T)]2
18 Ratio of specific heat at ɣ = Cp /Cv , 1.398 -
T-C°= 15, ɣ
19 Ideal gas enthalpy of 0 J/kmol ×
formation at 298.15 K, H 1E-07
20 Ideal gas Gibbs energy of 0 J/kmol ×
formation at 298.15 K 1E-07
21 Ideal gas entropy at 2.05043 J/(kmol/K)
298.15 K, S × 1E-05
22 Standard net enthalpy of 0 J/kmol ×
combustion at 298.15 K 1E-09
23 Viscosity , μ T in K° μ = exp(C1 + C2/T + C3 ln T+ C4Tc5) Pa.s
24 Vapor Viscosity, μ T in μ = C1Tc2 / 1+ C1/T + C4/T2 Pa.s
K°
25 Vapor Thermal k=C1Tc2 /1+C3/T +C4/T2 W/(m.K)
Conductivity, k , T in K°
26 Diffusivities in Liquids Glycerol*-water (106 poise) = 0.24 DL × 105 , sq
(25 °C) cm/sec
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27 Diffusivities in Liquids Sucrose*-water (125 poise) = 0.25 DL × 105 ,

(25 °C) sq cm/sec
Table 1.5. Physical Properties of Oxygen (Early, 2004)
NO. Property Value

1 temperature, K 54.359 ± 0.002
2 pressure, Pab 146.4
3 density, g/L gas 0.0108
4 density, g/L liquid 1306.5
5 density, g/L solid 1300
6 boiling point, at 101.3 kPa, K 90.188
density, g/L
gas 4.470
liquid 1141.1
7 melting point, K 54.22
8 critical point
temperature, K 154.581
pressure, MPac 5.043
density, g/L 436.1
9 heat capacity, J/(mol˖K)d
Cp, at 258°C 29.40
Cp, at 268°C 1.396
10 dielectric constant at 208°C 1.0004947
11 Viscosity at 258°C, µPa˖s(=cP×10-3) 20.639
12 thermal conductivity, at 0°C, mW/(m˖K) 2.448
13 Liquid
heat capacity, sat liq, J/(mol˖K)d 54.317
heat of vaporization, J/mold 6820
Viscosity, µPa˖s(=cP×10-3) 189.4
thermal conductivity, mW/(m˖K) 149.87
sound velocity, at 87 K, m/s 904.6
surface tension, at 87 K, N/m 13.85×10 -7
volume ratio, gas at 218°C to liquid at bp 859.9
14 Solid
heat of sublimation, J/mold 8204.1
heat capacity, J/(mol˖K)d 46.40
d
heat of fusion, J/(mol) 444.5
To convert Pa to mm Hg, multiply by 0.0075. , To convert MPa to psi, multiply by 145., To
convert joule to cal, divide by 4.184.
7|Page
Density Relative density Melting point Boiling point Specif ic heat cp at

(at 273 K) (air = 1) 298 K
1.429 kg m–3 1.10 54.8 K 90.19 K 918 J K–1 kg–1
1.43 g/l –218.4 °C –182.96 °C
Thermal conductivity Wm–1K–1
73 K 173 K 273 K 373 K 1273 K
- 0.0159 0.0245 0.0323 0.086
–2
Heat capacity coeff icients in Cp = a + bT + cT (valid 298–2000 K)
a b c
29.96 4.18 · 10–3 –1.67 · 105
Ratio Cp/Cv (ideal gas = 5/3 = 1.667) O2 1.4 (278–287 K)
3 3
Solubility in water m gas at STP per m water
273 K 293 K 313 K 333 K 353 K 373 K
O2/0.0489 O2/0.0310 O2/0.023 O2/0.0195 O2/0.0176 O2/0.0170
Mass magnetic susceptibility χmass at 293 K 1355 · 10–9 m3 kg–1
Magnetic characterization Paramagnetic (as susceptibility is positive)
Critical point: Tc 154.8 K
Pc 5.08 MPa
(Enghag, 2008)
1.4. methodology (method of Productions )

Commercial oxygen, both gaseous and liquid, at about 99.5% purity is produced by cryogenic
distillation in air separation plants. In these plants the air is cleaned, dried, compressed, and
refrigerated until it partially liquefies at about 80 K . The air is then distilled into its components .
Commercial gaseous oxygen at about 90–93% purity is produced from air by vacuum swing
adsorption (VSA) processes . The VSA method is the fastest growth portion of oxygen production.
Air was first liquefied and oxygen subsequently separated about 1900. Technologies introduced
after World War II substantially improved the air separation process for high purity oxygen
production. In the 1960s the production of high volume, low cost oxygen for the manufacture of
chemicals and petrochemicals, and especially for the basic oxygen process (BOP) for the
manufacture of steel (qv), provided a distinct advantage. Since about 1980 a number of further
improvements have occurred in the cryogenic air separation process resulting in significant
efficiency, productivity, and reliability gains. The most modern cryogenic plants operate at
thermodynamic efficiencies in the vicinity of 35%, a number significantly higher than for other
industrial processes, such as petroleum refining. Process improvements include (1) improved
energy transfer in heat exchangers via improved thermal design of the main heat exchangers; (2)
more complex heat integration yielding more optimal distillation column performance; (3)
improved expander–compressor efficiencies; (4) reduced pressure drops within distillation
columns via improved distillation tray design and the use of packing in place of trays; (5) use of
down-flow reboilers; (6) use of high (up to ca 3100 kPa (450 psi)) pressure operating cycles; and
(7) improved front-end purification equipment requiring less energy to reactivate. Process
8|Page
improvements have been combined into a number of operating cycles. The choice of which cycle
to use depends on a number of factors, including the ratio of oxygen:nitrogen produced; the ratio
of liquid oxygen:nitrogen vs gaseous oxygen:nitrogen produced; and the final pressure required of
the gaseous oxygen and nitrogen. Improvements in instrumentation and automatic controls,
especially the introduction of digital, ie, computerized, control systems, have provided significant
gains in personnel productivity as well as in the ability to optimize process parameters to maintain
peak efficiencies. The standardization of (especially) smaller cryogenic air separation plants has
further reduced design and construction costs. These types of plants often operate unattended. Even
moderately large plants may be unattended during certain periods of operation. The principal
impurity in 99.5% oxygen is argon because of the closeness of the boiling points. There was a high
demand for argon in the 1990s so that the oxygen is further refined (via distillation) to recover the
argon. As a result, oxygen purity often rises to 99.8%. This additional refining has also influenced
the selection of operating cycles. (Suslick, 1998)
1.4.1. Methods of production
Commercial oxygen is produced at air separation plants by liquefaction of atmospheric air and
separation of the oxygen by fractionation. Very small quantities are produced by the electrolysis
of water. Oxygen ranging in purity between 90 percent and 97 percent is produced by pressure
swing absorption (PSA) techniques. PSA oxygen is used chiefly in steel making, but there are also
many small units in homes producing therapeutic oxygen. Recent innovations in membrane
technology are also being used for production of oxygen from the air.(Suslick, 1998)
1.4.2. Adsorptive Air Separation
Various forms of molecular sieves exhibit a greater capacity for nitrogen than for oxygen, in a
ratio of ca. 2: 1. When used in an isothermal fractionator (pressure-swing adsorption) with
compressed air feed, the nitrogen is preferentially adsorbed, leaving a product gas rich in oxygen
and argon. Because the actual nitrogen capacity is relatively small, the phenomenon is basically a
transient one, with nitrogen breaking through after one to two volume changes with feed. The
principle of oxygen enrichment from air by pressure-swing adsorption (PSA) is relatively simple.
Compressed air enters the adsorption bed at high pressure. Typical adsorbents are usually based
on zeolites. Because zeolite has a higher selectivity for nitrogen, and oxygen is at a lower partial
pressure, nitrogen is adsorbed to an appreciably greater extent and oxygen-enriched air is obtained
at the outlet. The bed is then blown down to a lower pressure to desorb nitrogen. A purge step may
sometimes be used to sweep nitrogen out of the bed before a new cycle begins (Skarstrom, 2018).
Oxygen PSA had its beginnings in the late 1960s as an extension of hydrogen production by
synthetic zeolites. The driving force for this development was linear capacity turndown and low
operating costs for wastewater treatment. The high power consumption and relatively high capital
cost, compared to cryogenic systems, were characteristic of a design that was advantageous to the
federal government-funded wastewater treatment market. The government supported capital but
not operating expenses for these wastewater treatment facilities. These same factors, however,
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initially limited success in the traditional industrial sector, but this has now changed. Advances in
adsorptive materials and process design in recent years have improved the process economics of
oxygen PSA. A simple PSA plant, as illustrated in Figure 1.3, consists of two vessels containing
beds of zeolite, a feed of clean compressed air, waste gas discharge, and a control system that
switches valves according to the adsorption – desorption sequence of operation. Bed 1 is shown in
the adsorption mode: its feed air and product valves are open, and the waste gas valve is closed.
Nitrogen in the feed air is adsorbed onto the zeolite, permitting the product gas, which is enriched
in oxygen, to pass through to whatever process is being served. Bed 2 is in the regeneration or
desorption mode: its feed air and product valves are closed, and the waste gas valve is open,
thereby allowing the vessel to depressurize and venting desorbed nitrogen to the atmosphere. After
some time, normally several minutes, valve positions are switched. Bed 2 goes into the adsorption
mode while bed 1 is regenerated. Thus, by periodic bed switching, a continuous supply of oxygen
is generated.(Mark J. Kirschner, 2011)
Figure 1.3. Oxygen pressure swing adsorption (PSA) system
10 | P a g e
Sometimes more than two vessels are used, with a more complicated valve switching sequence. In
this way, the batch PSA process can better approximate a continuous process. Another product
smoothing technique is to insert a surge vessel in the product gas line, downstream of the
adsorption beds, to dampen pressure pulses caused by bed switching. Other variations have been
engineered, including vacuum-swing adsorption and a combined vacuum – pressure-swing
adsorption process. By careful selection of the molecular sieve and creative process engineering,
oxygen concentrations up to 93.5% can be achieved. Because most oxygen applications do not
require the highest purity available, lower purities are generally provided, with an attendant
decrease in specific capital and power charges. Air enrichment makes a product of ca. 75% oxygen,
which is subsequently diluted with air to the required enrichment level; this procedure is more
economical than direct production of a product containing a lower level of oxygen.(Mark J.
Kirschner, 2011)
1.4.3. Membrane Air Separation
Membrane separation of oxygen is accomplished by a thin polymeric film that allows selective
transport of oxygen through it as a result of a driving force, such as differential partial pressure.
Permeation of oxygen through a membrane can be expressed in terms of the permeability
coefficient of the membrane.
Oxygen dissolves into the membrane at its upstream surface and diffuses across the membrane to
the downstream surface, where it volatilizes into the adjacent gas phase. Other gases in air also
dissolve into the membrane and diffuse along with oxygen; the most important of these is nitrogen.
Thus, selectivity of a membrane material for oxygen becomes an important design parameter. The
preferred membrane material must have both a high permeability and a high selectivity for oxygen.
Unfortunately, achieving a high permeability rate concurrent with a high selectivity for oxygen –
nitrogen separation in a single material has been elusive. Polymers derived from silicone rubber
offer the best performance , but even these are not competitive with alternative oxygen supply
means, except for the smallest amounts, where high purity is not required. Small membrane units,
used to supply a single patient’s medical oxygen needs, meet these criteria and have been
commercially successful. These systems deliver 30 – 40% oxygen at flow rates of 1 – 10
L/min.(Mark J. Kirschner, 2011)
1.4.4. Oxygen from Cryogenic Air Separation:
In the late 1800s, various attempts were made to separate oxygen from air on a commercial scale.
These all relied on chemical processes employing thermal cycling (Simpson, 1969). The most
successful processes involved heating barium oxide in air at 590 ◦C under pressure, so that it
accumulated oxygen to form barium peroxide. The peroxide, in turn, was heated to ca. 870 ◦C, at
which point it released half of its oxygen, which was collected at ca. 95% purity. This was
subsequently improved by maintaining the barium oxide at 600 ◦C, while oxygen was absorbed
11 | P a g e
from air supplied at 170 kPa and subsequently desorbed under vacuum. At this time, successful
experiments in air liquefaction were being conducted, which eventually led to the separation of
oxygen via distillation. Because the percentage of oxygen in the gas phase that is in equilibrium
with liquid air (containing 21% oxygen) is only 6%, separation of oxygen by distillation is
convenient. In 1901, Carl von Linde (Germany) demonstrated the first practical method for
controlling the distillation of liquid air: rectification. Early columns were inefficient, but by 1910,
Linde had introduced a double column, one above the other, with a condenser – evaporator in
between. This remains the concept employed for producing oxygen by cryogenic air separation.
Over the years, oxygen production plants have continued evolving into larger, more efficient
process systems. To date, the largest modular plant is capable of producing 2250 t/d (F. Wolf,
1979). Cryogenic air separation involves three steps:
1. Purification of the incoming air to remove particles, carbon dioxide, and water
2. Refrigeration and economization of refrigeration values contained in the product and waste
streams.
3. Separation by distillation.
Figure 1 shows a schematic of a process embodying these steps to produce oxygen. Filtered air
compressed to 600 – 700 kPa is cooled and scrubbed in a direct-contact water wash tower (a) and
then directed into a plate-fin reversing heat exchanger (b), where it is cooled further in counterflow
to product oxygen and waste nitrogen. Carbon dioxide and water are removed from the air stream
by condensation and solidification in this heat exchanger. Every few minutes, the paths of the
incoming air and the waste nitrogen streams are reversed (hence the name reversing heat
exchanger) so that deposited impurities can be purged from the exchanger. In this way, the process
is able to operate continuously on a cyclic basis. State-of-the-art plants are, however, being
constructed with molecular sieve adsorption units, in place of the reversing heat exchangers. After
carbon dioxide and water have been removed by the sieve, the incoming air is then cooled by cold
waste gas in counter flow heat exchangers. Refrigeration for this process is achieved primarily by
the Claude principle of conversion of energy into work by the expansion of a compressed gas in a
turbine. Some of the cooled air is returned through the cold end of the heat exchanger before
expansion to ca. 120 kPa in a turbine (c), and then introduced at an appropriate point in the upper,
low-pressure column of the double column rectifier (d). The remainder of the air passes into the
lower, high-pressure column (Mark J. Kirschner, 2011)
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Figure 1.4. Cryogenic oxygen plant (schematic) a) Water wash cooler; b) Reversing heat
exchanger; c) Expansion turbine; d) Double column rectifier; e) Condenser; f) Subcooler; g)
Adsorber; h) Compressor; i) Filter
at 500 – 600 kPa where it is separated into nitrogen gas at the top and oxygen-enriched liquid (38%
O2) at the bottom. Gaseous nitrogen is condensed by liquid oxygen (which is vaporized) in the
condenser – reboiler (e). Part of this liquid nitrogen is returned as reflux to the lower column, and
part is expanded into the top of the upper column as reflux liquid. The oxygen-enriched liquid (rich
liquid) from the sump of the lower column is expanded as feed into an appropriate point in the
upper column. The reflux liquids used are subcooled by returning nitrogen in the heat exchanger
(f ), to reduce the amount of liquid vaporized on expansion. In the upper column, the feed is
separated into pure oxygen (99.6%) at the bottom and waste nitrogen with 1–2% oxygen at the
top. The adsorber (g), packed with silica gel, removes trace hydrocarbon matter from liquid oxygen
in the condenser – reboiler and from the rich liquid, ensuring that unsafe hydrocarbon
concentrations do not accumulate in the process.(Mark J. Kirschner, 2011)
1.5. Uses
The major uses of oxygen stem from its life sustaining and combustion supporting properties. It is
used extensively in medicine for therapeutic purposes, for resuscitation in asphyxia, and with other
gases in anesthesia. It is also used in high-altitude flying, deep sea diving, and both as an inhalant
and a power source in the United States space program. Industrial applications include its very
wide utilization with acetylene, propane, hydrogen, and other fuel gases for such purposes as metal
cutting, welding, hardening, and scarfing. In the steel industry, oxygen helps increase the capacity
and efficiency of production in steel and iron furnaces. One of its major uses is in the production
of synthesis gas (a hydrogen-carbon monoxide mixture) from coal, natural gas or liquid fuels;
synthesis gas is in tum used to make gasoline, methanol, and ammonia. Oxygen is similarly used
13 | P a g e
in manufacturing some acetylene through partial oxidation of the hydrocarbons in methane-rich

feedstocks such as natural gas. It is also used in the production of nitric acid, ethylene, and other
compounds. (Association, 2012)
In many applications, the choice is to operate with ambient air as the source of oxygen or to obtain
the oxygen in concentrated form, otherwise known as commercial oxygen. The choice is always
dictated by the relative process economics, and experience shows that most of the oxygen
consumed in industrial and biological processes is introduced in the form of air. Sometimes oxygen
is used to assist an air-based process to increase production without significant capital
expenditures, or to overcome a mass-transfer limitation when dissolved oxygen is required. At
other times, pure oxygen-based systems are employed that fully exploit the chemical and physical
properties of oxygen by eliminating nitrogen, the attendant diluent that is always present in air-
based systems. The first significant industrial use of oxygen began in the early 1900s, when
gaseous oxygen became available relatively cheaply and in quantity from air liquefaction. The
oxyacetylene flame was improved, modified, and developed into a cutting tool and welding torch.
During this time, hospitals began using oxygen to treat patients suffering from respiratory ailments.
(Mark J. Kirschner, 2011)
1.5.1. Combustion and Metallurgy
The source of oxygen for the combustion of carbonaceous fuel is usually air. The kinetic theory of
gases (Barrow, 1973) predicts that the number of binary collisions in a unit volume per unit time
is proportional to the square of the pressure of the gas. Thus, increasing the partial pressure of
oxygen in a combustion process exponentially increases the number of oxygen – fuel interactions
per unit volume per unit time. The result of increasing the oxygen concentration in an air – fuel
flame is a higher rate of flame propagation, or flame velocity, due to more frequent molecular
collisions, and a higher flame temperature due to the higher rate of heat release within a given
combustion volume. Figures 1.5 and 1.6 demonstrate the effect of oxygen enrichment on the
velocity and temperature of a methane flame. A radiative flame transfers heat more readily at a
higher temperature, and a higher velocity flame allows more heat to be released from a given fuel
within a limited combustion space. Both of these attributes are exploited in various industrial
operations that employ oxygen enrichment to increase production capacity.
14 | P a g e
Figure 1.5. Effect of oxygen enrichment on flame velocity of methane
Figure 1.6. Effect of oxygen enrichment on flame temperature of methane
15 | P a g e
Oxygen enrichment also displaces nitrogen from the system. The presence of nitrogen in
combustion has a number of effects, one of which is to chill the flame. Nitrogen is heated by the
flame, thereby decreasing the overall thermal efficiency of the process. Because the release of 1GJ
requires the addition of ca. 280m3 of air and only ca. 55m3 of oxygen, the combustion space
required for pure oxygen is much less. Because nitrogen does not have to be expanded, the space
requirement for a given thermal demand becomes minimal, adding to the effect of increased flame
velocity. Although the combustion products, water and carbon dioxide are heated initially to a
higher temperature, their rate of thermal decay over the cold charge is much more rapid than that
of nitrogen, and they leave the furnace at a temperature that is the same or lower than with air
combustion. Pure oxygen combustion on an exclusive basis, however, is not an industrial practice
because of economic and material properties limitations. To overcome these restrictions, the
industrial gas industry has developed methods for oxygen enrichment and supplementary oxygen
– fuel burners to aid many of the pyroprocess industries. The most common approach is the use of
oxygen to enrich the air – fuel burner combustion air. A diffuser in the air main introduces
commercial oxygen so that the oxygen content of air reaching the burner is elevated above its
normal 21 %. As oxygen is added to the air, the flow of air is reduced to maintain the desired
combustion stoichiometry. In practice, the final oxygen concentration is held to
23 – 25% because of refractory temperature limitations.With oxygen enrichment of air, the
radiative heat-transfer mode is most affected.
The advantage of this method, besides simplicity, is that it affects the entire combustion system
and helps overcome many deficiencies of existing air – fuel burners. Postmix burners (diffusion
flames) usually lend themselves to these moderate enrichment levels without modification, but
premix burners are severely limited because the increase in flame speed, imparted by additional
oxygen, can result in flashback into the mixer. Some of the constraints imposed on general oxygen
enrichment by furnace design can be overcome by more selective techniques. Depending on the
burner type used, oxygen may be introduced into the primary or atomizing air where liquid fuels
are used. This more closely approaches the characteristics of pure oxygen combustion. Oxygen –
fuel mixing is improved, and the oxygen is subject to less dilution by the secondary air and
combustion products.
In some cases, pure oxygen is lanced into an air – fuel flame to obtain selective enrichment of the
flame in the lower section adjacent to the furnace charge. The unaffected upper portion of the
flame protects the furnace refractory by providing a shielding area against the intense radiation of
the lower section. This procedure is frequently used in steel mill open hearths, glass melting
furnaces, and rotary kilns. Another variation in oxygen use is the impingement of an oxygen – fuel
flame against the air – fuel flame. This is especially effective in stabilizing flames fired with hard-
to-burn fuels such as coal or hogged wood. The air – fuel stream is selectively preheated and a
portion of the fuel is volatilized. Selective preheating in this case means that the air – fuel stream
receives an enthalpy increase from the highly directional oxygen – fuel burner, and since the
oxygen – fuel flame is not radiative, the refractory and furnace contents are not directly heated by
this flame. This technique is particularly suitable for rotary kilns (Kirschner, 1979). A very
effective method of oxygen use is to add supplementary oxygen – fuel burners to obtain all the
advantages of pure oxygen combustion. These include accelerated melting, reduced fuel
consumption, and reduced oxidation losses by virtue of shorter melt cycles. By adding
25%additional fuel through oxygen – fuel burners, melt rates can be doubled while fuel
consumption is reduced by about 30 %. The rapid heat transfer of the highly directional convective
oxygen – fuel flame allows the placement of burners to add heat directly to the charge without
16 | P a g e
heating the refractory. In most cases, the refractory temperature is lower than normal, and the flue
gas temperature is unchanged despite the higher thermal input. This technique has found
widespread acceptance in steel, copper, lead, and aluminum melting operations. In 1856, Sir Henry
Bessemer invented his process for the conversion of low sulfur and phosphorus hematite iron into
steel. He produced malleable steel by blowing air through liquid metal; this resulted in the
exothermic oxidation of carbon, silicon, and manganese. The later development of the basic
Bessemer or Thomas Converter allowed the phosphoric limonite ore fields of France and Germany
to be exploited. This process was the major steelproducing method employed in Europe until it
was superseded in the 1960s by top-blown oxygen
converter processes (Moore and Marshall, 1980). An over-simplification of the chemistry, but a
nevertheless useful way to understand the role of oxygen in steel production, is illustrated by the
following equation:
Fe (l) +C(s) + 1/2 O2 (g) −→ Fe (l) +CO(g) + Heat
Carbon is removed from solution in the iron by conversion to carbon monoxide.

Increased demand for steel during the 1940s and 1950s stimulated research into rapid steelmaking
processes, which utilized tonnage oxygen being made available for the first time in economic
quantities during the immediate postwar period. A number of novel oxygen-blown converter
processes were developed, the most successful of whichwas the AustrianLDprocess (Linz and
Donawitz). This process accounts for more than 80% of the world’s steelmaking capacity, but
outside Europe it is usually referred to as BOS (basic oxygen steelmaking) or BOP (basic oxygen
process).
Figure 1.7. Oxygen-blown LD converter a) Oxygen lance; b) Charging mouth; c) Tap hole
17 | P a g e
The LD converter (Fig. 1.7) is mounted on trunnions so that it can be tilted for loading and pouring.
The process begins when the vessel is tilted downward for loading, then charged with hot iron
from a blast furnace and up to 30 wt % scrap metal. After the vessel is turned upright, the oxygen
lance is lowered and delivers 50 –55m3 of oxygen per tonne of steel into the vessel, which contains
about 250 t of charge. Initially, soft blowing, from2–4mabove the metal level, is required to
produce foaming slags for phosphorus removal. Later, the lance is lowered to within 1mof the
molten metal surface, and hard blowing follows, which results in greater penetration of oxygen
into the bath (Moore and Marshall, 1980). The oxygen lance is water cooled with three or four exit
nozzles at the tip. With oxygen pressure up to 1.5MPa, supersonic exit velocities are achieved that
provide the necessary penetration into the bath. At the end of the blowing period, which may be
as short as 15 min, the lance is withdrawn and the vessel tilted again to tap off first the slag and
then the molten steel.(Mark J. Kirschner, 2011)
1.5.2. Production of Chemicals

The trade-offs between air and commercial oxygen for the synthesis of chemicals via partial
oxidation must consider capital investment, operating cost, reaction selectivity, environmental
impact, safety, and the vent losses of product or raw materials associated with the discharge of
large quantities of nitrogen after passage through the chemical reaction process. Where large
volumes of air must be compressed and contained in process equipment, oxygen may be the
oxidizing medium of choice. On an energy basis, an operating pressure of more than 690 kPa
favors the use of oxygen. This choice is favored further if conversion rates per reactor pass are
low, necessitating heavy recycle of the feed material. Oxygen and feed material are never charged
to a reactor without a diluent (ballast), which is required to adsorb and desorb the reactant onto
and from the catalyst surface. It also discharges free radicals, whose unchecked propagation
produces nonselective reactions. Its main function, however, is to act as a heat-transfer medium,
cooling the catalyst by rejecting reaction heat to the surface of the externally cooled reaction tubes.
With air, the ballast must be nitrogen, but nitrogen is a poor thermal transfer fluid as well as a poor
quencher of free radicals. With oxygen, a wider choice of ballast is available. Methane, ethane,
and carbon dioxide have all been used successfully, as have mixtures. From an environmental
point of view, the significant difference between using air and commercial oxygen is the volume
of process effluent. In the production of vinyl chloride monomer, the volume of the vent stream
from an air-based process is about 100 times larger than that from an oxygen-based process
(Wimer and Feathers, 1976) because of the high nitrogen content (>90 %). With oxygen, nitrogen
diluent in the vent stream is eliminated, thereby making pollution abatement more manageable and
economical, such as when the waste stream is either scrubbed or incinerated to remove or destroy
contaminants. Acetaldehyde is useful primarily as an intermediate for other chemicals, such as
acetic acid, acetic anhydride, and butanol. Of the various precursors available, ethylene appears to
be the least expensive (Austin, 1974):
This is known as the Wacker process. Commercial oxygen allows it to be conducted at lower
pressure and in a single step, as opposed to a two-step process when air is used to regenerate the
18 | P a g e
catalyst (BLAU and GRIMM, 1976). Acetaldehyde may be oxidized further to form acetic
anhydride by contact with oxygen in the presence of cobalt or manganese acetate. The oxidation
of o xylene to phthalic anhydride is performed in the gas phase, with a large excess of air:
In contrast, the oxidation of p-xylene to 1,4- benzenedicarboxylic acid (terephthalic acid) is carried
out with air oxidation in a solvent (acetic acid) in the presence of a cobalt catalyst. Oxygen
enrichment of the air feed has been used successfully on a commercial scale to expand production
capacity in this process. In the production of maleic anhydride from benzene (Eq. 13) and
formaldehyde from methanol (Eq. 14), air is favored as the source of oxygen. High-purity oxygen
does not offer any particular process benefit that can offset its higher cost, and the vapor-phase
oxidations are conducted with a mixture that is above the upper flammability limit in air (Maux,
1976). Switching to oxygen would require an even greater excess of reactant for a given production
per unit volume of catalyst in order to operate safely.
Ethylene oxide is an important petrochemical intermediate made from the direct oxidation of
ethylene (Gans and Ozero, 1976) over a silver-based catalyst in either fixed or fluid beds (Eq. 15).
About 60% of the ethylene feedstock is converted to the desired product. Approximately 40% of
the feed is converted to carbon dioxide (Gans and Ozero, 1976) and must be removed. Although
feed losses to carbon dioxide are undesirable, with a pure oxygen process the carbon dioxide
evolves in concentrated form and may be liquefied and sold as a coproduct, rather than vented to
the atmosphere as in air-based processes. Acrylonitrile from propene ammoxidation is the primary
raw material for nylon 66. Commercial oxygen is used in this process.
Poly(vinyl chloride) plastics have created enormous demand for the monomer vinyl chloride. The
usual route (Austin, 1974) is by oxychlorination of ethylene via the 1,2-dichloroethane
intermediate.
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By operating with pure oxygen instead of air, vent volumes from this process have been greatly
reduced (Moore and Marshall, 1980). Moreover, the stripping loss of ethylene from the process is
greatly diminished, which further improves process economics. The production of acetone and
phenol from isopropylbenzene ( cumene) involves the formation of cumene hydroperoxide via
liquid phase oxidation (commercial oxygen is used) and subsequent decomposition with acid to
the two coproducts (Eq. 18). This process not only is the main source of phenol but also has become
one of the most competitive processes for acetone production (Pujado, Salazar and Berger, 1976).
1.5.3. Oxygen Bleaching of Wood Pulp

The entry of oxygen into the pulp mill was prompted by efforts to find the best practical answer
towater pollution problems associated with conventional bleaching methods: color and chlorinated
organic compounds. In the face of ever increasing restraints on effluent loading, oxygen bleaching
(and oxygen-derived compounds such as ozone and hydrogen peroxide) appears to present the
most satisfactory solution. If “zero discharge” ever becomes law, bleach plant effluents will have
to be recycled within the mill. This is not practicable with chlorine or chloride containing effluent
streams. The feasibility of absorbing the oxygen stage effluent in a con conventional kraft chemical
recovery system was originally demonstrated in the Republic of South Africa (Coetzee, 1974) and
has since been implemented in every major pulp-producing country. Lignin comprises about 25%
of the wood that is converted into papermaking pulp and, for high-grade paper, must be removed
from the cellulosic portion of the fibers. Oxygen delignification (removal of lignin with oxygen)
proceeds with the hydroperoxide anion as the most active species. It may be formed initially by
oxygen abstracting hydrogen atoms and producing organic radicals (Eq. 19 and 20)
8RH+O2 −→ R• +HOO• (19)

RH+HOO• −→ R• +H2O2 (20)
that may subsequently form organic peroxides or terminate by any of the classical methods. The
result is that side chains containing α-carbonyl and α-carbinol structures are eliminated by
conversion into free acids and aldehydes, respectively, and ring opening with attendant formation
of dicarboxylic acid groups (Eckert, 1973) renders the larger lignin fragments soluble in the
aqueous alkaline medium. These organic reaction products are subsequently washed from the
cellulose fibers and, because they are chloride free, are ultimately reclaimed as fuel in the pulp
mill’s chemical recovery system. Oxygen delignification of wood pulp is carried
out at either high (30 %) or medium (12 %) pulp consistency. High-consistency pulp is relatively
dry in appearance and presents a large fibrous network surface area to the oxygen atmosphere
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inside a continuous, fluffed-bed, downflow reactor. At medium consistency, the reaction rate is
controlled by oxygen diffusion through the alkaline solution surrounding the pulp. Prior to entering
the upflow reactor, oxygen is mixed with the pulp slurry under high shear, to fully disperse the
oxygen within the fibrous network and aid the diffusion process by increasing the interfacial
surface area. In either case, ca. 25 kg of oxygen and 25 kg of sodium hydroxide per tonne of pulp
are applied.(Mark J. Kirschner, 2011)
1.5.4. Wastewater Treatment

The use of relatively high purity oxygen gas in the activated sludge process was established
Figure 1.8. Three-stage UNOX system (Union Carbide) a) Motor; b) Surface aerator
commercially in the mid-1960s with the successful introduction of the UNOX system (Union
Carbide). Today, this process and subsequent variations are used worldwide to treat municipal
sewage and industrial wastewater from diverse manufacturing operations (McWhirter, 1978). The
principle involved is not the increased level of dissolved oxygen that can be obtained with the use
of oxygen; rather, it is the rate at which oxygen can be transferred into the mixed liquor. With
higher oxygenation rates, the organic loading on the system can be increased substantially. By
simultaneously increasing the organic loading and the mixed-liquor volatile suspended solid
levels, a high degree of treatment efficiency can be obtained at the higher loading and higher
oxygen transfer rate conditions. The UNOX system is illustrated schematically in Figure 1.8 . The
system uses a covered, multistage oxygenation and reaction system in which the wastewater and
activated sludge are contacted in a series of cocurrent, gas – liquid mixing stages. The system is
operated at essentially atmospheric pressure, with relatively high purity oxygen gas, wastewater,
and recycle sludge being introduced in the first stage and flowing cocurrently through successive
contacting stages. Exhaust gas is vented from the last stage, and the mixed-liquor is settled in a
conventional gravity clarifier. The oxygen feed-gas rate can be controlled automatically in direct
proportion to the actual oxygen uptake rate in the system by means of a simple pressure controller
in the first stage. As the oxygen uptake rate diminishes, the pressure in the first stage tends to
increase and the oxygen feed rate is reduced. Alternatively, as the oxygen demand increases, the
pressure in the first stage tends to decrease and the oxygen feed rate is increased. The number of
stages employed, overall reactor geometrical configuration, tank depth, and specific type of gas –
liquid contacting devices or aerators used in the stages can be economically optimized for each
specific installation and process requirement. Standard surface aerators are typically used in most
installations. Oxygen is often used to augment air-based wastewater systems that have become
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masstransfer limited. This condition often results years after a facility is commissioned because of
increasing load on the plant.(Mark J. Kirschner, 2011)
1.5.5. Medicine
Oxygen is used extensively in medicine for therapeutic purposes, for resuscitation in asphyxia, and
with other gases in anesthesia. Adequate respiration consists of the uptake of sufficient amounts
of oxygen and the elimination of adequate amounts of carbon dioxide to maintain their partial
pressures, pO2 and pCO2 , in arterial blood at normal values. Respiratory failure is associated with
disturbances in the exchange of oxygen and carbon dioxide between gas in alveoli and blood in
pulmonary capillaries. Respiratory failure is not a disease but a disorder of function that can be
caused by a variety of conditions that affect the lungs; in some instances the lungs are completely
normal, as with an overdose of sedative drugs. When respiratory failure is severe, death results
from the central nervous system or cardiovascular consequences of hypoxia (oxygen deficiency).
During emergencies, supplementary oxygen is given without worry about the concentration being
used; in general, the higher the concentration, the better. After the patient’s condition has
stabilized, attention is directed to administering oxygen in the lowest possible concentration
required to correct the hypoxia. Any more oxygen than that required to increase the arterial pO2 to
a safe level exposes the patient to the direct toxicity of oxygen on the lung lining
(Wyngaarden and PI, 1992). Supplementary oxygen can be administered to a patient in several
ways. An oxygen tent provides the lowest inspired oxygen concentration per liter of oxygen flow.
Its inefficiency is only in part related to the difficulties encountered in proper draping of the tent
about the upper part of a bed, because rapid loss of oxygen tends to occur by diffusion through the
canopy. Poor economy and bulk, together with increased nursing problems and fire hazard, limit
its use to certain postoperative treatments. Plastic, dome-shaped hoods enclose the head and neck
of the patient, and are used with a recirculating carbon dioxide-absorbing and air conditioning
system, such as those employed with oxygen tents. The smaller volume, better seal, and non
permeability of the materials used combine to provide the hood with a higher ratio of inspired
oxygen concentration to oxygen flow. The concentration of oxygen in inspired air can be enriched
by nasal cannulas, catheters, or prongs. These devices work well even when patients breath through
their mouths. If more than 3 – 5 L/min is needed to achieve satisfactory arterial oxygenation, other
methods of administration are advisable. At this rate, unhumidified oxygen has a drying effect on
the nasal mucous membranes. Venturi masks work on the principle of entrainment of a fixed
proportion of air that mixes with the oxygen supplied and results in a constant inspired
concentration (24, 28, 35, or 40% O2). The mask is somewhat uncomfortable and must be removed
for eating and drinking. When high concentrations of oxygen (40 – 80%) are necessary for patients
who are not intubated, reservoir masks are used. To ensure optimal efficiency of operation, the
masks must be tight fitting to avoid leaks; because this often causes discomfort, delivering high
concentrations of oxygen for long periods is difficult. Mechanical ventilators have regulators that
can be set to deliver an inspired oxygen concentration that ranges from 21 to 100 %. One of the
best ways of ensuring that patients actually receive high concentrations of oxygen (60 – 100 %) is
to use a mechanical ventilator connected to an endotracheal or tracheostomy tube. For home
therapy, three types of oxygen delivery are available. Large tanks of compressed oxygen (H or K
cylinders) are easily obtainable but bulky. Smaller D and E cylinders are used for portability. The
large tanks may be used with long nasal cannulas (20 m) to allow limited ambulation in the home.
Liquid-oxygen reservoirs are more expensive but allow filling of relatively lightweight portable
units that may be carried with a shoulder strap. This is the most convenient system for ambulation.
Oxygen concentrators are probably the least expensive system in the long run. They require electric
22 | P a g e
power and utilize either a molecular sieve or a membrane to produce oxygen-enriched air. The
former systems are capable of delivering 85 – 90% oxygen at 0.3–1m3/min; the latter, 30 – 40%
oxygen at 0.3–3m3/min. A backup cylinder is recommended in case of power or mechanical
failure, and a small portable tank is useful for ambulation(Cunha, 2010).(Mark J. Kirschner, 2011)
Figure 1.9. Oxygen production in the United States (U.S. Bureau of the Census, Current
Industrial Reports M-28-C)
1.6. Storage and Transportation
1.6.1. Storage
Compressed oxygen is frequently stored in high pressure cylinders or tube trailers, depending on
the frequency and rate of consumption. For larger needs, liquid oxygen is more economically
stored at the user’s site and vaporized as required. This is replenished by cryogenic tank trailers.
At consumer sites, liquid-oxygen stations must comply with NFP 50, Standard for Bulk Oxygen
Systems at Consumer Sites (Shear and Greenberg, 1998). Although oxygen is nonflammable, it
vigorously accelerates combustion. The distances between an oxygen station and various
exposures, illustrated in Figure 1.10 , have been established to minimize the possibility of liquid
oxygen, or an oxygen-rich air mixture, interacting with persons or flammable substances.(Mark J.
Kirschner, 2011)
1.6.2. Material Selection for Oxygen Compatibility

At liquid-oxygen temperature, ordinary carbon steels and many alloy steels lose their ductility and
are therefore considered unsuitable for liquid-oxygen service. Satisfactory metals and alloys
include austenitic stainless steels (i.e., 304 and 316), nickel – chromium alloys, nickel, Monel 400,
copper, brasses, bronzes, and aluminum alloys. Many materials have been evaluated for oxygen
compatibility with respect to their ease of ignition and their combustion intensity with oxygen
(Lowrie, 1987). Careful selection of nonmetallic components for oxygen service is especially
important, because, if they are ignited, the metallic portion of the system may also be ignited.
Oxygen equipment and systems must be cleaned adequately to remove harmful contamination
prior to the introduction of oxygen. Harmful contamination includes both organic and inorganic
23 | P a g e
materials such as oil, grease, fibers, sawdust, solvents, welding slag, rust, and dirt. Organic
materials are combustible, and inorganic particles impacting at high speed, particularly at elbows
in the distribution piping, can be an ignition source. The cleaning of oxygen systems is described
in (C. G. Association, 1990b). (Mark J. Kirschner, 2011)
1.6.3. Transportation
Under controlling regulations, oxygen may be shipped as either a compressed gas (13 790 kPa or
above) or a cryogenic liquid (below 1379 kPa and −146.5 ◦C) as follows(Association, 1999): By
Rail: In cylinders and tube tank cars, for both gaseous and liquid oxygen. Special insulated
cylinders and tank cars for liquid oxygen are not subject to U.S. Department of Transportation
(DOT) regulations below 172 kPa, except in Canada where oxygen is regulated regardless of
pressure. By Road: Compressed in cylinders on trucks and in tube trailers. Liquid oxygen in
insulated cylinders and cargo tanks. By Water: Compressed in cylinders on cargo and passenger
vessels and on ferry and railroad car ferry vessels, both passenger and cargo. In authorized tank
cars on cargo vessels only. Liquefied oxygen in insulated containers on cargo and passenger
vessels and on ferry and railroad car ferry vessels, both passenger and cargo. By Air: A maximum
net weight of compressed oxygen per cylinder of 68 kg aboard passenger aircraft and 136kg aboard
cargo aircraft. Liquid oxygen is not accepted for air shipment under present regulations. The
shipment of compressed or liquid oxygen is under the jurisdiction of DOT and must be in
containers that meet regulatory specifications (WATERS and SCOPE, 2000). Cylinders meeting
DOT specifications 3A,3AA, or 3AL are the types usually employed to ship gaseous oxygen, but
oxygen is authorized for shipment in any cylinders designated for non liquefied compressed gases.
These include cylinders that comply with DOT specifications 3A, 3AA, 3AX, 3AAX, 3AL, 3B,
3E, 3T, 4B, 4BA, 4BW, and 39. Some new, higher strength steel cylinders and fiber-wrapped
aluminum cylinders are authorized under DOT exemptions (Association, 1999). Liquid oxygen is
authorized for shipment in cylinders that meet DOT specification 4L. However, when it is
packaged in dewars – small vacuum-isolated containers holding from 4 to 90 L at atmospheric
pressure –DOT cylinder regulations do not apply. Most of these cylinders must be requalified for
use by hydrostatic testing every 5 or 10 years. Specifications for filling limits (WATERS and
SCOPE, 2000), pressure relief devices (C. G. Association, 1990a), and valve outlet connections
(CGA, no date) are also regulated.(Mark J. Kirschner, 2011)
24 | P a g e
Figure1.10. Minimum distances between liquid-oxygen storage and exposures Note: These distances do not apply
where protective structures, having a minimum fire rating of 2 h, interrupt the line of sight between uninsulated
portions of the bulk oxygen storage installation and the exposure. The protective structures protect uninsulated oxygen
storage containers or supports, control equipment, and system piping (or parts thereof ) from external fire exposure.
Liquid-oxygen storage containers are insulated; such containers may provide line-of-sight protection for uninsulated
system components (Willard et al., 1988).
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1.7. Safe storage, Handling

General precautions for safe handling of gaseous oxygen are contained in CGA G-4, Oxygen
(CGA, no date). For liquid oxygen, a thorough discussion of necessary precautions can be found
in CGA P-12, When liquid oxygen is held in any closed container or space, there must be an
appropriate pressure relief device because of the very large pressure increases that can occur as the
liquid oxygen is vaporized by heat flowing into the container. Liquid oxygen must also be handled
with all the precautions required for safety with any cryogenic fluid. In addition, liquid oxygen
exhibits strong oxidizing properties. Contact between the skin and liquid oxygen, or uninsulated
piping or vessels containing it, can cause severe burnlike injuries. The ability of oxygen to react
with most materials is a hazard. All easily combustible materials, especially hydrocarbon oils and
greases, must be kept from contact with high oxygen concentrations. Sources of ignition should
be eliminated to the extent possible. Sudden opening of valves, and particles carried by oxygen
flowing at high velocity are to be avoided since these actions can result in ignition. Valves,
therefore, should be opened slowly. When this cannot be done, precautions must be taken to
prevent severe damage or injury to personnel should an ignition occur. Such safety measures
include isolation and the provision of barriers as discussed in ASTM G-88, Guide for Designing
Systems for Oxygen Service (Beeson, Stewart and Woods, 2000). High pressure cylinders, tube
trailers, and tank cars often serve as the storage supply for gaseous oxygen. Larger amounts of
oxygen are frequently stored more economically in liquid form at the user's site. Standards to
ensure safety with oxygen systems at user sites are set forth in publications ofNFPA (Swain, 1996)
(Association, 1987) (Association, 1987)(N. F. P. Association, 1990)
1.7.1. Disposal
Gaseous oxygen for which disposal becomes necessary should be vented in a manner that does not
create an oxygen-rich atmosphere in a confined space. When disposing of liquid oxygen, be sure
that the liquid and vapors do not come in contact with combustible materials, especially
hydrocarbon materials such as oil, grease, and asphalt.(Association, 2012)
1.7.2. Handling leaked and emergences

Turn off ignition sources in the general area if possible. The source of the leakage should be shut
off if possible and the area adequately ventilated. Avoid contact with liquid spills. If liquid oxygen
is spilled over asphalt or other surfaces contaminated with combustibles, such as oil-soaked
concrete or gravel, do not walk on or roll equipment over the area for at least 112 hour after the
frost has disappeared. A violent reaction may occur simply by impact or shock. Contact the
supplier for assistance.(Association, 2012)
1.7.3. First aid

In case of frostbite from contact with liquid oxygen, place the frostbitten part in warm water,
lOO°F to lO5°F (37.8°C to 40.6°C). If warm water is not available or is impractical to use, wrap
the affected part gently in blankets. Let the circulation re-establish itself naturally. Encourage the
victim to exercise the affected part while it is being warmed. Consult a physician (Association,
2012)
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1.7.4. Method of Shipment

Under the appropriate DOT and TC regulations, oxygen is authorized for shipment as follows
(Bates, Bibler and Blackmar, 1990) By Rail: In DOTITC approved cylinders, portable tanks, and
tank cars as a compressed gas; and in cylinders as a cryogenic liquid. By Highway: In OOT/TC
approved cylinders, portable tanks, and cargo tanks as a compressed gas; and in cylinders and
cargo tanks as a cryogenic liquid. By Water: In the United States, in DOT approved cylinders,
portable tanks, and cargo tanks on cargo vessels and passenger vessels within Stowage category
"A" limitations for compressed gas and category "0" for cryogenic liquid. In Canada, cylinders,
portable tanks, and cargo tanks must be stowed according to the requirements of the IMOG Code
(Nauke and Holland, 1992). By Air: In the United States and Canada, in cylinders, as a compressed
gas with a maximum net weight per cylinder of 165 lb (75 kg) aboard a passenger aircraft and up
to 330 lb (150 kg) aboard a cargo aircraft. Cryogenic liquid is forbidden on all aircraft.
(Association, 2012)
1.7.5. Containers
The shipment of liquid or pressurized gaseous oxygen is under the jurisdiction of DOT or TC and
must be done in containers meeting specifications of the applicable regulations (ofFederal
Regulations, no date). Gaseous oxygen is authorized for shipments in approved cylinders, tank
cars, and tube trailers. Oxygen is shipped as a cryogenic liquid in insulated cylinders, tank trucks,
and tank cars. Oxygen service requires certain restrictions for container design and materials, and
applicable regulations should be consulted.
1.7.6. Filling limits

The maximum filling limits authorized for gaseous oxygen in shipment are as follows: In cylinders
and tube trailers, the authorized service pressures marked on the cylinders or tube assemblies at
70°F (2 I. 1°C). In the case of cylinders of specifications 3A, 3AA, 3AX, and 3AAX that meet
special requirements, up to 10 percent in excess of their marked service pressures. See 49 CFR
173.302 (ofFederal Regulations, no date). In uninsulated tank cars of the specification 107A type,
the gas pressure at 130°F (54.4°C) must not exceed seven-tenths of the marked test pressure of the
tank. For TC/DOT 4L cylinders, filling limits for liquid oxygen as expressed in percent water
capacity by weight are given in terms of the pressure control valve start-to-discharge setting. For
TC/OOT 4L cylinders with a design service temperature of -320°F (-196°C), filling limits range
from 86 percent for a start-to-discharge setting of 625 psig (4310 kPa) to 108 percent for a start-
to-discharge setting of 45 psig (310 kPa). See 49 CFR 173.316 for further information and
requirements (ofFederal Regulations, no date). Liquid oxygen shipped in insulated truck cargo
tanks or in other insulated containers at pressures below 25.3 psig (174 kPa) is not subject to DOT
regulations except placarding, shipping papers, and incident reporting. See 49 CFR 173.320
(ofFederal Regulations, no date). In Canada, transportation of oxygen is regulated regardless of
pressure.
1.7.7. Cylinders
Cylinders meeting TC/DOT specifications 3A, 3AA, or 3AL are the types usually used to ship
gaseous oxygen, but oxygen is authorized for shipment in any cylinders designated for
nonliquefied compressed gases. These include cylinders that comply with DOT specifications
3A, 3AA,3AX, 3AAX,3A~ 3B, 3~ 3L4B, 4BA, 4BW, and 39. In addition, cylinders meeting
27 | P a g e
DOT specifications 3, 3C, 3D, 4, 4A, 4C, 7, 25, 26, 33, and 38 may be continued in gaseous
oxygen service, but new construction is not authorized. Some new higher strength steel cylinders
and fiber wrapped aluminum cylinders are authorized under DOT exemptions. Liquid oxygen is
authorized for shipment in cylinders which meet TC/DOT specification 4L. Most cylinders
authorized for gaseous oxygen service must be requalified by hydrostatic retest every 5 or, under
more restricted service requirements, 10 years. No periodic retest is required for cylinders of
specifications 3C, 3E, 4C, and 7. Cylinders of specification 4L authorized for liquid oxygen
service are also exempt from periodic retest requirements. See 49 CFR 173.34 (ofFederal
Regulations, no date).
1.7.8. Tube trailers and cargo tanks on trucks or trailers

Gaseous oxygen at pressures up to 2640 psig (18 200 kPa) is shipped in tube trailers with capacities
that may exceed 40 000 ft? (1133 m\ These trailers commonly serve as the storage supply for the
user with empty trailers being replaced periodically by the supplier. Most liquid oxygen is shipped
in bulk at pressures below 25.3 psig (174 kPa) in special insulated cargo tanks on trucks, and truck
trailers with capacities up to or in excess of 400 000 fe (11 327 m\ In Canada, a TC 341 cargo tank
must be used.(Association, 2012)
1.7.9. Small portable liquid containers

Liquid oxygen is packaged in small portable containers that hold quantities ranging from 1 gal to
more than 25 gal (3.8 L to 95 L). These containers, generally termed dewars, are encased in steel
shells and are vacuum insulated; they maintain the liquid at atmospheric pressure and are
consequently not subject to DOTITC regulations.(Association, 2012)
1.7.10. Tank cars

Gaseous oxygen is authorized for rail shipment in tank cars meeting DOT specification 107A.
Liquid oxygen is also shipped in special insulated tank cars at pressures below 25.3 psig (174 kPa)
meeting specification AAR 204W (Fields, Low and Early, 1990).
1.8 The Biological Role of Oxygen

Oxygen is critical for life on our planet and for the fate of mankind. It is the central atom for many
of the functional groups, such as hydroxyl, carboxylate and carbonyl, among others, that are
essential in nearly all the molecules involved in life. To provide the body with oxygen from the
atmosphere, specific molecules – proteins containing iron – have been developed. Myoglobin
stores oxygen in the muscle cells, and hemoglobin transports it in the blood. The reversed role of
oxygen in photosynthesis has been described above.(Enghag, 2008)
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CHAPTER TOW
Process instrumentation
2.1 Cryogenic Technology

In present day usage, the word ‘‘cryogenics’’ refers to ‘‘all phenomena, processes, techniques, or
apparatus occurring or using temperatures <120 K’’ (Ter Brake, 2000). ‘‘Refrigeration’’
technology covers the temperature range of 120–273.1 K. The choice of these temperature ranges
is somewhat arbitrary but has been accepted as an international standard. Around or below the
temperature of 120 K, the ‘ permanent’’ gases including methane, oxygen, argon, nitrogen,
hydrogen, and helium can be liquefied at ambient pressure. Cryogenic technology has contributed
greatly to scientific research and is widely used in many industrial applications. The ability to
condense a gas such that it can be stored and shipped as a cryogenic liquid rather than as a
pressurized gas has found several applications. Natural gas is stored and transported as liquified
natural gas (LNG) to many countries in the world. Liquid hydrogen is used as fuel for space
vehicles. Oxygen, nitrogen, and argon are shipped as liquids by truck and rail car to the point of
end use. Another major use of cryogenic technology has been to produce low cost, high purity
gases through fractional condensation and distillation. Cryogenic air separation is used for the
production of pure oxygen, nitrogen, and argon (Auvil, no date). These gases are used in primary
metals manufacturing (eg, steel), chemical manufacturing, glass manufacturing, electronic
industries, partial oxidation and coal gasification processes, enhanced oil recovery and many other
applications. Cryogenic methods are also used for the purification of hydrogen, helium, and carbon
monoxide. Hydrogen and carbon monoxide gases are used in chemical manufacturing and some
metal industries. Helium is used in welding, medicine, gas chromatography, and diving (Isalski,
1989). Cryogenic processes that provide low temperatures to refrigerate other materials or to alter
their properties have been used in many applications (Flynn, 2001). Liquid nitrogen is used for
freezing food such as hamburgers and shrimp. Rubber tires and scrap metal from old cars are
reclaimed using cryogenic cooling techniques to make them brittle for easier fracturing and
component separation. Biological materials such as bone marrow, blood, animal semen, tissue
cultures, tumor cells and skin are preserved by cryogenic freezing and storage. Magnetic resonance
imaging (MRI) uses cryogenics to cool high conductivity magnets for nonintrusive body
diagnostics. Low temperature infrared (ir) detectors are utilized in astronomical telescopes.
Cryogenic refrigerators have been applied industrially for cryopumping to yield high pumping
speeds and ultrahigh vacuum. With the advent of high temperature superconductivity, it is
anticipated that applications of superconductivity at near liquid nitrogen temperature will have
great potential for electric power transmission, magnetic transportation systems, and magnets for
energy generation in fusion processes.(McCabe, 1985)
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2.2 Air Separation

A considerable number of cryogenic concepts were developed near the end of the nineteenth and
beginning of the twentieth century to liquefy and separate air into its major constituents
(composition of air: 78% nitrogen, 21% oxygen, and 1% argon by volume). By 1905, Carl von
Linde’s double distillation column process to produce practically pure oxygen and nitrogen was
already known. Argon was produced industrially by 1912 (Scurlock, 1992). Trace quantities of
other rare gases such as neon, krypton, and xenon are present in air and can be recovered by proper
modifications to a cryogenic double distillation column air separation plant (Isalski, 1989). Figure
2.1 shows a cryogenic air separation process using a double distillation column of the Linde-type
with a side rectifying column to recover crude argon (Latimer, 1967). Feed air is compressed in a
multistage compressor with interstage cooling to between 550 and 650 kPa. cooling. The
compressed air is cooled in an aftercooler by cooling water and the condensed water is removed
in an aftercooler separator.
Fig. 2.1. Cryogenic air separation process
To avoid freezing of water and carbon dioxide in the cryogenic part of the plant, the feed air is
passed through an adsorbent bed of molecular sieve. Along with water and carbon dioxide, several
trace impurities in the air such as acetylene, ethylene, butane, and other heavier hydrocarbons are
also adsorbed. This alleviates some of the safety issues arising from the formation of hydrocarbon
oxygen mixtures in older plants that did not use molecular sieve adsorbers. The purified air stream
is split into two streams. One stream of _7–12% of the total air flow is boosted in pressure by _60–
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200 kPa in a booster compressor. The boosted air is cooled first by heat exchange with, typically,
cooling water and then in the main heat exchanger against the returning cold product nitrogen and
Oxygen streams. The cooled air stream is work expanded to near atmospheric pressure and fed to
the low pressure distillation column. This expander provides the needed refrigeration for the plant.
Often the work extracted from the expander drives the booster compressor so that an additional
source of energy is not required. The major portion of the air stream is cooled in the main heat
exchanger to near its dew point. Nitrogen and oxygen are separated by distillation in a two-stage
distillation process. The first stage, the high pressure column, which operates at _500–600 kPa,
separates the feed air into nitrogen and an oxygen enriched liquid (crude LOX) stream, which is
eventually fed to the low pressure column. The low pressure column, which operates at close to
ambient pressure, produces pure oxygen and nitrogen streams from its bottom and top respectively.
Nitrogen reflux for both columns is generated at the top of the high pressure column. Nitrogen
vapor at the top of the high pressure column is condensed against boiling liquid oxygen at the
bottom of the low pressure column by heat exchange between the two streams in a reboiler
condenser. The pressure difference between the two columns provides the temperature difference
between the condensing and boiling fluids. Since argon boils between oxygen and nitrogen, a peak
in the argon concentration of _7–15% occurs in the lower section of the low pressure column. A
vapor stream is drawn from the low pressure column near the location of the peak argon
concentration and is distilled in a third (argon) column. Typically, a vapor stream is drawn from
the low pressure column at a point where the concentration of nitrogen is low [10–100 parts per
million (ppm)] and the concentration of argon is 7–12%. Reflux for the argon column is provided
by heat exchange between the vapor at the top of this column and a portion of the crude LOX
stream in a crude argon condenser. The vaporized crude LOX is fed to the low pressure column
and the condensed argon-rich stream is returned as reflux to the argon column. The liquid from
the bottom of the argon column is returned to an appropriate location in the low pressure column.
A crude argon stream containing 0.5–5% O2 and 0.05–1% N2 is withdrawn from the top of the
argon column. The oxygen produced from the bottom of the low pressure column can easily have
an oxygen purity of 99.5% or greater with the remainder being mainly argon. The nitrogen product
from the top of the low pressure column can be produced with an oxygen concentration <5 ppm.
As shown in Figure 2.1, a waste stream is sometimes drawn from a couple of stages below the top
of the low pressure column. The withdrawal of this stream allows a better control of the purity of
the nitrogen product from the top of the low pressure column. Any unrecovered oxygen and argon
can now leave in this waste stream allowing the nitrogen product to have low levels of these
elements. The heat exchangers used in cryogenic air separation plants are generally brazed
aluminum plate-fin heat exchangers. Also sieve trays have been used predominantly for cryogenic
distillation. Recently, the use of structured packing, to reduce the pressure drop per theoretical
stage of separation, has become commonplace in the low pressure and argon columns. Its use in
the low pressure column decreases the power consumption by the air compressor as the pressure
of the feed air to the high pressure distillation column can be decreased by about 60 kPa. The use
of structured packing in the argon column provides more theoretical stages of separation for the
same permissible pressure drop between the bottom and top of the argon column. This allows
argon production from the argon distillation column with oxygen impurity as low as 1 ppm, thereby
either eliminating the need for, or reducing the size of, the expensive downstream processes that
have been used in the past to produce pure argon product (Agrawal, 1993). As depicted in Figure
2.1, the oxygen product is removed from the bottom of the low pressure column as a vapor then
warmed to ambient. For most applications, oxygen is needed at an elevated pressure so oxygen
31 | P a g e
product compression is required. An alternative to the approach is withdraw the oxygen product
from the low pressure column as a liquid, pump the liquid to delivery pressure, then vaporize and
warm the liquid by heat exchange with some suitable high pressure vapor stream. This approach,
which is often referred to as ‘‘pumped-LOX ’, is typically used in modern air separation plants
and is shown in Figure 2.2 .The identity of the suitable high pressure vapor stream varies
Fig. 2.2. Pumped liquid oxygen process.
but, as shown in (Figure 2.2), is usually a compressed fraction of the incoming feed air. In the field
of semiconductor device manufacturing, on-going trends toward device miniaturization and the
need for high production yield are leading to gas specifications with ultrahigh purities. This finding
requires that the concentration of all impurities in each of the nitrogen, oxygen, and argon products
be <10 parts per billion (ppb). It is widely felt that this impetus to decrease the impurity level will
continue as the devices continue to advance and gases with parts per trillion impurity
concentrations will eventually be desired. Ultrahigh purity (UHP) nitrogen is directly produced at
the end use pressures of _800–1000 kPa from the cold box . For this purpose, variants of a single
distillation column process that directly produce nitrogen at the desired pressure are generally used
(Fig. 2.3). Air typically consists of several impurities at ppm levels. Hydrogen is present in the
range of 1–5 ppm; carbon monoxide is also present at similar levels. In order to avoid the presence
of these impurities in the distilled nitrogen, both H2 and CO impurities are removed prior to feeding
the compressed feed air to the cold box. In one alternative, the compressed feed air is heated to a
temperature of _200C and passed over a noble metal catalyst such as platinum to oxidize all the
32 | P a g e
carbon monoxide and hydrogen. The resulting stream is then cooled and passed through a
molecular sieve unit (Fig. 2.3). In an alternative process, layers of adsorbent catalysts containing
noble metal are supplied within the molecular sieve unit to remove hydrogen and carbon monoxide
impurities.
Fig. 2.3. UHP nitrogen process with UHP oxygen coproduction.
The impurities-free air is then cooled in the main heat exchangers and sent to the main distillation
column of Figure 2.3 to produce UHP nitrogen from the top. A large number of separation stages
(60–100) are used in this distillation column to reduce the oxygen concentration in the nitrogen
product to a level of a few ppb. The crude liquid oxygen from the bottom of the main distillation
column is eventually fed to the top of a short column containing four to six separation stages and
operating at a pressure of _400 kPa. The boilup at the bottom of this column is provided by
condensing a portion of the UHP nitrogen from the top of the main distillation column. Not all
liquid at the bottom of the short column is vaporized and an oxygen-rich liquid is withdrawn. Its
pressure is further reduced to _200–300 kPa and it is vaporized by condensing additional UHP
nitrogen from the main distillation column. The vapor from this reboiler is partially warmed in the
main exchanger and expanded in an expander to provide the refrigeration need of the plant. The
expanded stream is discharged as a waste stream. A liquid purge stream is taken from the second
reboiler to prevent the accumulation of hydrocarbons to unsafe levels. One interesting feature of
this process is that the vapor stream leaving at the top of the short distillation column is close in
composition to that of air and therefore, is referred as ‘‘synthetic air’’. Since the synthetic air is at
_400 kPa it is recycled and mixed with the feed air stream. In Figure 2.3, it is recycled to an
intermediate stage of the feed air compressor, which reduces the cost of buying a separate booster
33 | P a g e
machine for the recycle of the synthetic air stream. The process shown in Figure 2.3 is quite
efficient and economical for UHP nitrogen production . Air contains several impurities that are
heavier than oxygen—methane and higher hydrocarbons and nitrogen oxides are all present at ppm
levels. A typical high purity oxygen produced from a process such as contains all these heavier
impurities at unacceptable levels to be considered UHP oxygen. Generally, the UHP oxygen
requirement is _1–5% of the UHP nitrogen production rate. The relatively small production rates
for UHP oxygen are met by withdrawing a heavy impurities-free but oxygen-containing liquid
stream from an intermediate location of the main distillation column in Figure 2.3 . The pressure
of this liquid stream is then reduced and fed to the top of an UHP oxygen column containing 60–
100 separation stages. Ultrahigh purity liquid oxygen product stream with concentrations of all
impurities at a few ppb is recovered from the bottom of the UHP oxygen column. The boilup at
the bottom of this column is provided by cooling crude liquid oxygen from the bottom of the main
distillation column. Once again, this process is quite economical for the production of the desired
quantities of the UHP oxygen.(Kirk-Othmer, 2007)
2.3 Oxygen from Cryogenic Air Separation

The most successful processes involved heating barium oxide in air at 590 ◦C under pressure, so
that it accumulated oxygen to form barium peroxide. The peroxide, in turn, was heated to ca. 870
◦C, at which point it released half of its oxygen, which was collected at ca. 95% purity. This was
subsequently improved by maintaining the barium oxide at 600 ◦C, while oxygen was absorbed
from air supplied at 170 kPa and subsequently desorbed under vacuum. At this time, successful
experiments in air liquefaction were being conducted, which eventually led to the separation of
oxygen via distillation. Because the percentage of oxygen in the gas phase that is in equilibrium
with liquid air (containing 21% oxygen) is only 6%, separation of oyygen by distillation is
convenient. In 1901, Carl von Linde (Germany) demonstrated the first practical method for
controlling the distillation of liquid air: rectification. Early columns were inefficient, but by 1910,
Linde had introduced a double column, one above the other, with a condenser – evaporator in
between. This remains the concept employed for producing oxygen by cryogenic air separation.
Over the years, oxygen production plants have continued evolving into larger, more efficient
process systems. To date, the largest modular plant is capable of producing 2250 t/d . Cryogenic
air separation involves three steps:
4. Purification of the incoming air to remove particles, carbon dioxide, and water
5. Refrigeration and economization of refrigeration values contained in the product and waste
streams.
6. Separation by distillation.
Figure 2.4 shows a schematic of a process embodying these steps to produce oxygen. Filtered air
compressed to 600 – 700 kPa is cooled and scrubbed in a direct-contact water wash tower (a) and
then directed into a plate-fin reversing heat exchanger (b), where it is cooled further in counterflow
to product oxygen and waste nitrogen. Carbon dioxide and water are removed from the air stream
by condensation and solidification in this heat exchanger. Every few minutes, the paths of the
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incoming air and the waste nitrogen streams are reversed (hence the name reversing heat
exchanger) so that deposited impurities can be purged from the exchanger. In this way, the process
is able to operate continuously on a cyclic basis. State-of-the-art plants are, however, being
constructed with molecular sieve adsorption units, in place of the reversing heat exchangers. After
carbon dioxide and water have been removed by the sieve, the incoming air is then cooled by cold
waste gas in counter flow heat exchangers. Refrigeration for this process is achieved primarily by
the Claude principle of conversion of energy into work by the expansion of a compressed gas in a
turbine. Some of the cooled air is returned through the cold end of the heat exchanger before
expansion to ca. 120 kPa in a turbine (c), and then introduced at an appropriate point in the upper,
low-pressure column of the double column rectifier (d). The remainder of the air passes into the
lower, high-pressure column
Figure 2.4. Cryogenic oxygen plant (schematic) a) Water wash cooler; b) Reversing heat
exchanger; c) Expansion turbine; d) Double column rectifier; e) Condenser; f) Subcooler; g)
Adsorber; h) Compressor; i) Filter
at 500 – 600 kPa where it is separated into nitrogen gas at the top and oxygen-enriched liquid (38%
O2) at the bottom. Gaseous nitrogen is condensed by liquid oxygen (which is vaporized) in the
condenser – reboiler (e). Part of this liquid nitrogen is returned as reflux to the lower column, and
part is expanded into the top of the upper column as reflux liquid. The oxygen-enriched liquid (rich
liquid) from the sump of the lower column is expanded as feed into an appropriate point in the
upper column. The reflux liquids used are subcooled by returning nitrogen in the heat exchanger
(f ), to reduce the amount of liquid vaporized on expansion. In the upper column, the feed is
separated into pure oxygen (99.6%) at the bottom and waste nitrogen with 1–2% oxygen at the
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top. The adsorber (g), packed with silica gel, removes trace hydrocarbon matter from liquid oxygen
in the condenser – reboiler and from the rich liquid, ensuring that unsafe hydrocarbon
concentrations do not accumulate in the process.(Elvers and Bellussi, 2011)
2.4 Cryogenic Instrumentation

Even though the combined production of cryogenic nitrogen and oxygen exceeds the production
of any other chemical in the United States, the cryogenic industry does not appear to warrant a
separate product line of instruments for diagnostic and control purposes. Low temperature
thermometry is the one exception. The general approach generally is that instruments developed
for the usual CPI needs must be modified or accepted as is for cryogenic use. Quite often problems
arise when instruments for normal service are subjected to low temperature use. Since some metals
become brittle at low temperatures, the instrument literally falls apart. Elastomeric gaskets and
seals contract faster with decreasing temperatures than the surrounding metal parts, and the seal
often is lost. Even hermetically sealed instruments can develop pin holes or small cracks to permit
cryogenic liquids to enter these cases with time. Warming the instrument causes the trapped liquid
to vaporize, sometimes generating excessive gas pressure and failure of the case. Therefore, the
first task in adapting normal instruments to cryogenic service is simply to give them a severe
thermal shock by immersing them in liquid nitrogen repeatedly, and checking for mechanical
integrity. This is the general issue; specific issues according to each type of measurement are
discussed below(Green and Perry, 2007)
2.4.1 Pressure
This parameter is usually measured by the flush mounted pressure transducer which consists of a
force-summing device (bellow, diaphragm, bourdon tube, etc.) that translates the
pressure into a displacement. The latter is then measured by an analog device (strain gage,
piezeoelectric crystal, variable distance between capacitor plates, and the like). Since these
elements are likely to be made of different materials (bronze diaphragm, stainless-steel case,
semiconductor strain gage), each will react to the temperature change in a different way. This is
especially serious during cool down, when the transient nature of material and construction
prohibits all of the pressure-gage elements from being at the same temperature at the same time.
Under steady-state conditions it is often possible to provide some temperature compensation
through the well-known instrument technique of common-mode-rejection. Such compensation is
generally not successful during transient temperature fluctuations. Only two courses of action are
open:
1. hand-check each type of pressure transducer for thermal noise by thermally shocking it
with immersion in liquid nitrogen
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2. simplify the pressure-transducer construction to eliminate differences between materials.

Some success has been observed in the latter area by manufacturers who make very small
pressure sensing elements from a single semiconductor chip. The miniature size of these
devices helps to reduce or eliminate temperature gradients across the device. The single-
element nature of the pressure-gage assembly reduces differences in materials of
construction(Green and Perry, 2007)
2.4.2 Liquid Level
The measurements for dense fluids such as liquid oxygen and liquid nitrogen are made in the
conventional CPI approach using floats. Sight glasses cannot be used since radiation and thermal
conduction would cause the cryogenic fluid within the sight glass to boil. The very light cryogens,
liquid helium and liquid hydrogen, cannot sustain a float. Liquid hydrogen has the density of
Styrofoam, ™ about 70 g/l, making floating devices impractical. Some electrical analog is used
for hydrogen and helium, most frequently a linear concentric-tube electrical capacitor. The
dielectric constant of cryogens is related to their density by the Clausius-Mosotti relation. As the
liquid level rises, the greater dielectric constant of the liquid between the tubes causes the overall
capacitance to vary in a linear fashion. For best accuracy, these capacitance liquid-level measuring
devices should be calibrated in place.(Green and Perry, 2007)
2.4.3 Flow
The measurement of cryogenic fluids is most troublesome. Flow rate is not a natural physical
parameter, like temperature, but is a derived quantity. A measurement of mass (or volume) must
be made over a time interval to derive the flow rate. Because of this, any flow meter is only as
good as its calibration. At this time, there is no national capability for calibrating cryogenic flow
meters. From data developed early in the nation’s space program, considerable confidence has
been developed in turbine-type flow meters and in pressure- drop-type flow meters. If all the usual
ASTM guidelines are followed for meter installation, and if adequate temperature corrections are
applied to changes in dimensions, then such meters can have an accuracy of 1 percent of their
water calibrations. For very small flow applications, the Coriolis meters are promising. Vortex
shedding flow meters appear useful for very large flow rates. Nonetheless, an actual calibration on
the cryogen of interest is the only proof of accuracy.(Green and Perry, 2007)
2.4.4 Temperature
The level of the temperature measurement (4 K, 20 K, 77 K, or higher) is the first issue to be

considered. The second issue is the range needed (e.g., a few degrees around 90 K or 1 to 400 K).
If the temperature level is that of air separation or liquefacting of natural gas (LNG), then the
favorite choice is the platinum resistance thermometer (PRT). Platinum, as with all pure metals,
has an electrical resistance that goes to zero as the absolute temperature decreases to zero.
Accordingly, the lower useful limit of platinum is about 20 K, or liquid hydrogen temperatures.
37 | P a g e
Below 20 K, semiconductor thermometers (germanium-, carbon-, or silicon-based) are preferred.

Semiconductors have just the opposite resistance temperature dependence of metals—their
resistance increases as the temperature is lowered, as fewer valence electrons can be promoted into
the conduction band at lower temperatures. Thus, semiconductors are usually chosen for
temperatures from about 1 to 20 K. If the temperature range of interest is large, say 1 to 400 K,
then diode thermometers are recommended. Diodes have other advantages compared to resistance
thermometers. By contrast, diode thermometers are very much smaller and faster. By selection of
diodes all from the same melt, they may be made interchangeable. That is, one diode has the same
calibration curve as another, which is not always the case with either semiconductor or metallic-
resistance thermometers. It is well known, however, that diode thermometers may rectify an ac
field, and thus may impose a dc noise on the diode output. Adequate shielding is required. Special
applications, such as in high-magnetic fields, require special thermometers. The carbon-glass and
strontium-titinate resistance thermometers have the least magnetoresistance effects.
Thermocouples are unsurpassed for making temperature-difference measurements. The
thermoelectric power of thermocouple materials makes them adequate for use at liquid-air
temperatures and above. At 20 K and below, the thermoelectric power drops to a few μV/K, and
their use in this range is as much art as science. A descriptive flowchart has been prepared by
Sparks (Materials at Low Temperatures, ASM, Metal Park, OH, 1983) to show the temperature
range of cryogenic thermometers in general use today. Pavese and Molinar (Modern Gas-Based
Temperature and Pressure Measurements, Plenum, New York, 1992) provide details on gas- and
vapor-pressure thermometry at these temperatures.(Green and Perry, 2007)
2.5 Process Equipment
The equipment normally associated with cryogenic systems includes heat exchangers,
compressors, expanders, throttling valves, and storage containers. Since the reciprocal or
centrifugal compressors used generally operate at ambient temperatures.
2.5.1 Heat Exchangers: Since most cryogens, with the exception of helium II behave as classical
fluids, well-established principles of mechanics and thermodynamics at ambient temperature also
apply for cryogens. Thus, similar conventional heat transfer correlations have been formulated for
simple low-temperature heat exchangers. These correlations are described in terms of well-known
dimensionless quantities such as the Nusselt, Reynolds, Prandtl, and Grashof numbers. Because of
the need to operate more efficiently at low temperatures, the simple heat exchangers have generally
been replaced with more sophisticated types. Guidance for the development of such units for low-
temperature service include the following factors:
1. Small temperature differences between inlet and exit streams to enhance efficiency
2. Large surface area-to-volume ratio to minimize heat leak
3. High heat transfer to reduce surface area.
38 | P a g e
4. Low mass to minimize start-up time

5. Multichannel capability to minimize the number of units
6. High-pressure capability to provide design flexibility
7. Minimum pressure drop to reduce compression costs
8. High reliability with minimal maintenance to reduce shutdowns
2.5.2 Heat-Transfer equipment
Problems sometimes occur in trying to minimize the temperature difference at the cold end of the
heat exchanger, particularly if the specific heat of the warm fluid decreases with decreasing
temperature as is the case with gaseous hydrogen. The selection of an exchanger for low-
temperature operation is usually determined by the process-design requirements, mechanical
design limitations, and economic considerations. Laboratory needs are generally met by concentric
tube and extended surface exchangers, while industrial needs are most often met by the coiled-
tube, plate-fin, reversing, and regenerator types of exchangers. The coiled-tube heat exchanger
offers unique advantages, especially when dealing with low-temperature design conditions where:
• simultaneous heat transfer between more than two streams is desired

• a large number of heat transfer units is required
• high operating pressures are involved
Heat transfer for single-phase flow of either gas or liquid on the tube side is generally well
represented by either the Colburn correlation or modified forms of the Dittus-Boelter relationship.
The shape of the cooling and warming curves in coiled-tube heat exchangers is affected by the
pressure drop in both the tube and shell sides of the heat exchanger. This is particularly important
for two phase flows of multicomponent systems. For example, an increase in pressure drop on the
shell side causes boiling to occur at a higher temperature, while an increase in pressure drop on
the tube side will cause condensation to occur at a lower temperature. The net result is both a
decrease in the effective temperature difference between the two streams and a requirement for
additional heat transfer area to compensate for these losses
Plate-fin heat exchangers are about nine times as compact as conventional shell-and-tube heat
exchangers with the same amount of surface area, weigh less than conventional heat exchangers,
and withstand design pressures up to 6 MPa for temperatures between 4 and 340 K. Flow instability
frequently becomes a limiting design parameter for plate-fin heat exchangers handling either
boiling or condensing two-phase flows. This results in lower optimum economic mass flow
velocities for plate-fin heat exchangers when compared with coiled tube heat exchangers. The use
of fins or extended surfaces in plate-fin or similar exchangers greatly increases the heat transfer
area There are two basic approaches to heat-exchanger design for low temperatures:
(1) the effectiveness-NTU approach

(2) the log-mean-temperature-difference (LMTD) approach. The LMTD approach is used
most frequently when all the required mass flows are known and the area of the exchanger
is to be determined. The effectiveness- NTU approach is used more often when the inlet
39 | P a g e
temperatures and the flow rates are specified for an exchanger with fixed area and the outlet
temperatures are to be determined. System performance in cryogenic liquefiers and
refrigerators is directly related to the effectiveness of the heat exchangers used in the
system. For example, the liquid yield for a simple J-T cycle as given by Eq. needs to be
modified to
if the heat exchanger is less than 100 percent effective. Likewise, the heat exchanger
ineffectiveness increases the work required for the system by an amount of
Δ ˙W = m˙ (h1 − hg)(1 − ε)
Uninterrupted operation of heat exchangers at low temperatures requires removal of essentially all
impurities present in the streams that are to be cooled. Equipment is readily available for the
satisfactory removal of these impurities by both chemical and physical methods, but at increased
operating expense. Another effective method for also accomplishing this impurity removal utilizes
reversing heat exchangers. Proper functioning of the reversing heat exchanger is dependent upon
the relationship between the pressures and temperatures of the two streams. Since the pressures
are generally fixed by other factors, the purification function of the heat exchanger is normally
controlled by selecting the right temperature difference
throughout the heat exchanger. To assure that reevaporation takes place, these differences must be
such that the vapor pressure of the impurity is greater than the partial pressure of the impurity in
the purging stream. Another type of reversing heat exchanger is the regenerator as detailed by
Ackerman (Cryogenic Regenerative Heat Exchangers, Plenum Press, New York, 1997). As with
all reversing heat exchangers, regenerators provide the simultaneous cooling and purification of
gases in low-temperature processes. As noted earlier, reversing heat exchangers usually operate
continuously. Regenerators do not operate continuously; instead, they operate by periodically
storing heat in a packing during the first half of the cycle and then giving up this stored heat to the
fluid during the second half of the cycle. Typically, a regenerator consists of two identical columns,
which are packed with a porous solid material with a high heat capacity such as metal ribbon,
through which the gases flow.
The low cost of the packing material, its large surface-area-per-unit volume, and the low-pressure
drops encountered provide compelling arguments for utilizing regenerators. However, the
intercontamination of fluid streams, caused by the periodic flow reversals, and the problems
40 | P a g e
associated with designing regenerators to handle three or more fluids, has restricted their use to
simple fluids, and favored adoption of plate-fin reversing heat exchangers.(Green and Perry, 2007)
2.5.3 Expanders: The primary function of cryogenic expansion equipment is the reduction of the
temperature of the gas being expanded to provide needed refrigeration. The expansion of a fluid
to produce refrigeration may be carried out in two distinct ways:
(1) in anexpander where mechanical work is produced

(2) in a Joule-Thomson valve where no work is produced.
2.5.3 Mechanical Expanders: Reciprocating expanders are very similar in concept and design to
reciprocating compressors. Generally these units are used with inlet pressures of 4 to 20 MPa.
These machines operate at speeds up to 500 rpm. The thermal efficiencies (actual enthalpy
difference/maximum possible enthalpy difference) range from about 75 percent for small units to
85 percent for large machines. Turbo expanders have replaced reciprocating expanders in high
power installations as well as in small helium liquefiers. Sizes range from 0.75 to 7500 kW with
flow rates up to 28 million m3/day. Today’s large-tonnage air-separation plants are a reality due
to the development of highly reliable and efficient turbo expanders. These expanders are being
selected over other cryogenic equipment because of their ability to handle condensed ethane and
heavier hydrocarbons. This type of expander usually weighs and costs less and requires less space
and operating personnel. Turbo expanders can be classified as either axial or radial. Axial flow
expanders have either impulse or reaction type blades and are suitable for multistage expanders
because they permit a much easier flow path from one stage to the next. However, radial turbo
expanders have lower stresses at a given tip speed, which permits them to run at higher speeds.
This results in higher efficiencies with correspondingly lower energy requirements. As a
consequence, most turbo expanders built today are of the radial type.(Green and Perry, 2007)
2.5.4 Joule-Thomson Valves: The principal function of a J-T valve is to obtain isenthalpic
cooling of the gas flowing through the valve. These valves generally are needle-type valves
modified for cryogenic operation. They are an important component in most refrigeration systems,
particularly in the last stage of the liquefaction process. Joule- Thomson valves also offer an
attractive alternative to turbo expanders for small-scale gas-recovery applications.
2.5.5 Separation and purification system : The energy required to reversibly separate gas
mixtures is the same as that necessary to isothermally compress each component in the mixture
from the partial pressure of the gas in the mixture to the final pressure of the mixture. This
reversible isothermal work is given by the familiar relation
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where s1 and h1 refer to conditions before the separation and s2 and h2 refer to conditions after
the separation. For a binary system, and assuming a perfect gas for both components, Eq.simplifies
to
If the mixture to be separated is essentially a binary, both the McCabe-Thiele and the Ponchon
Savarit methods .with the appropriate cryogenic properties, can be used to obtain the ideal number
of stages required. It should be noted, however, that it is not satisfactory in the separation of air to
treat it as a binary mixture of oxygen and nitrogen if high purity (99 percent or better) oxygen is
desired. The separation of oxygen from argon is a more difficult separation than oxygen from
nitrogen and would require correspondingly many more plates. In fact, if the argon is not extracted
from air, only 95 percent oxygen would be produced. The other rare gas constituents of air (helium,
neon, krypton, and xenon) are present in such small quantities and have boiling points so far
removed from those of oxygen and nitrogen that they introduce no important complications.(Green
and Perry, 2007)
2.6 Air-Separation Systems

The various separation schemes available today, the simplest is known as the Linde single-column
system shown in Fig. 2.5 .purified compressed air passes through a precooling heat exchanger (if
oxygen gas is the desired product, a three-channel exchanger for air, waste nitrogen, and oxygen
gas is used; if liquid oxygen is to be recovered from the bottom of the column, a two-channel
exchanger for air and waste nitrogen is employed), then through a coil in the boiler of the rectifying
column where it is further cooled (acting at the same time as the boiler heat source); following
this, it expands essentially to atmospheric pressure through a J-T valve and reenters the top of the
column with the liquid providing the required reflux. Rectification occurs as liquid and vapor on
each plate establish equilibrium. If oxygen gas is to be the product, purified air need only be
compressed to a pressure of 3 to 6 MPa; if the product is to be liquid oxygen, a compressor outlet
pressure of 20 MPa is necessary. Note that the Linde single-column separation system is simply a
J-T liquefaction system(Green and Perry, 2007)
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Figure 2.5 .Linde single-column air separator.
with a substitution of a rectification column for the liquid reservoir. However, any of the other
liquefaction systems discussed earlier could have been used to furnish the liquid for the column.
In a simple single-column process, although the oxygen purity is high, the nitrogen effluent stream
is impure. The equilibrium vapor concentration of the overhead nitrogen effluent for an initial
liquid mixture of 21 percent oxygen/79 percent nitrogen at 100 kPa is about 6 to 7 percent oxygen.
Thus, the nitrogen waste gas stream with such an impurity may only be usable as a purge gas for
certain conditions. The impurity problem noted in the previous paragraph was solved by the
introduction of the Linde double-column system shown in Fig. 2.6 . Two rectification columns are
placed one on top of the other (hence the name double-column system).(Green and Perry, 2007)
In this system the liquid air is introduced at an intermediate point B into the lower column, and a
condenser-evaporator at the top of the lower column makes the arrangement a complete reflux
distillation column which delivers almost pure nitrogen at E. In order for the column
simultaneously to deliver pure oxygen, the oxygen-rich liquid (about 45 percent O2) from the
bottom boiler is introduced at an intermediate level C in the upper column. The reflux and
rectification in the upper column produce pure oxygen at the bottom and pure nitrogen at the top
provided all major impurities are first removed from the column. More than enough liquid nitrogen
is produced in the lower column for the needed reflux in both columns. Since the condenser must
condense nitrogen vapor by evaporating liquid oxygen, it is necessary to operate the lower column
at a higher pressure, about 500 kPa, while the upper column is operated at approximately 110 kPa.
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This requires a reduction in the pressure of the fluids from the lower column as they are admitted
to the upper column. In the cycle shown, gaseous oxygen and nitrogen are withdrawn at room
temperature. Liquid oxygen could be withdrawn from point A and liquid nitrogen from point E,
but in this case more refrigeration would be needed. Even the best modern low-temperature air
separation plant has an efficiency only a small fraction of the theoretical optimum, that is, about
15 to 20 percent. The principal sources of inefficiency are threefold:(Green and Perry, 2007)
1. the nonideality of the refrigerating process

2. the imperfection of the heat exchangers
3. losses of refrigeration through heat leak.
Figure 2.6 .Linde double-column air separator
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Chapter Three
Process Simulation
This chapter explain the process concept of air separation technique, process description of Air
separation plant and factor influencing distillation process simulation result and graph.
3.1. Process concept

Air has a composition of nitrogen 78.08%, oxygen 20.95%, argon 0.93% and their boiling points
temperature at atmospheric pressure are -195.79 0C (77.36k),-1830C (90.15K),- 185.840C
(87.302k) respectively and they are nonreactive .so they can be separated according to their boiling
points temperature .the gas mixture which has widely boiling point difference can be separated
effectively, but it is less effective for substance which has closer boiling points. Oxygen and argon
has closer boiling points also argon has less percentage in the air so it is less effective. Air can be
separated by rectification column with repeated evaporation and condensations in counter flow.
So that the light component (vapour i.e. low boiling points component) flows upward in the column
through liquid, while the heavy component (liquid i.e. high boiling points component) flows down
ward across the vapour stream. When the vapour flows through the liquid layer, the vapour which
has higher temperature transfer heat to the liquid, results condensation of a little bit of higher
boiling point component in the vapour and evaporation of a little bit of lower boiling point
component from the liquid region. Therefore the vapour moves upward through the liquid gets
richer in low boiling component, and the liquid which moves downward gets rich in heavy
component i.e. high boiling component. Thus the top of the column is reach in light component
and bottom of the column reach in heavy component.
3.1.1. Double-column system
All chemical distillation column are condensing by cooling tower or water, but how to condense
these atmospheric gases which has boiling point very low? This problem was solved by Linde
double column system shown In Fig. 3.1. Two rectification columns are attached on top of the
other, thus its name double column system. The bottom column is operated at a pressure of 500
kPa to 600 kPa (5 atm to 6 atm), and the top column is operated at a pressure of approximately
100 kPa(1 atm). At 5 atm, the boiling point of nitrogen is 94.2 K which is higher than the boiling
point of oxygen at 1 atm i.e. 90.2 K. Therefore, the top of the bottom column get condensation by
bottom of the top column component (oxygen), at the same time bottom of the top column get boil
by top of the bottom column component (nitrogen).i.e. boiler of the upper column and condenser
of the lower column are coupled by heat exchanger. And some of liquid nitrogen produced by the
lower column feed to the upper column for reflux (Barron, 1985).
45 | P a g e
Fig.3.1. Linde double column system
3.2. process simulation by DWSIM

DWSIM is an open-source CAPE-OPEN compliant chemical process
simulator for Windows, Linux and macOS. DWSIM is built on top of the Microsoft
.NET and Mono Platforms and features a Graphical User Interface (GUI),
advanced thermodynamics calculations, reactions support and petroleum characterization
hypothetical component generation tools.
DWSIM is able to simulate steady-state, vapor–liquid, vapor–liquid-liquid, solid–liquid and
aqueous electrolyte equilibrium processes with the following Thermodynamic Models and Unit
Operations:
• Thermodynamic models: CoolProp, Peng–Robinson equation of state, Peng–Robinson-
Strÿjek-Vera (PRSV2), Soave–Redlich–Kwong, Lee-Kesler, Lee-Kesler-
Plöcker, UNIFAC(-LL), Modified UNIFAC (Dortmund), Modified UNIFAC
(NIST), UNIQUAC, NRTL, Chao-Seader, Grayson-Streed, Extended
46 | P a g e
UNIQUAC, Raoult’s Law, IAPWS-IF97 Steam Tables, IAPWS-08 Seawater, Black-Oil

and Sour Water;
• Unit operations: CAPE-OPEN Socket, Spreadsheet, Custom (IronPython Script), Mixer,
Splitter, Separator, Pump, Compressor, Expander, Heater, Cooler, Valve, Pipe Segment,
Shortcut Column, Heat exchanger, Reactors (Conversion, PFR, CSTR, Equilibrium and
Gibbs), Distillation column, Simple, Refluxed and Reboiled Absorbers, Component
Separator, Solids Separator, Continuous Cake Filter and Orifice plate;
• Utilities: Binary Data Regression, Phase Envelope, Natural Gas Hydrates, Pure Component
Properties, True Critical Point, PSV Sizing, Vessel Sizing, Spreadsheet and Petroleum
Cold Flow Properties;
• Tools: Hypothetical Component Generator, Bulk C7+/Distillation Curves Petroleum
Characterization, Petroleum Assay Manager, Reactions Manager and Compound Creator;
• Process Analysis and Optimization: Sensitivity Analysis Utility, Multivariate Optimizer
with bound constraints;
Extras: Support for Runtime Python Scripts, Plugins and CAPE-OPEN Flowsheet Monitoring
Objects. (DWSIM - Chemical Process Simulator, no date)
3.3. Process description

The cryogenic air separation technology (Agrawal, 1996). Requires a very tight optimization of
distillation columns, compressor and heat exchangers (Amin et al., 2014) to produce high purity
of component and a good plant recovery or efficiency with a minimum specific power input in the
compressor because all the energy for separation is provided by the main compression of the inlet
air of the plant. The size of the operation and the required purity of Oxygen determine the method
of separation (Smith and Klosek, 2001).
3.3.1. Production of oxygen and nitrogen by double column

Process air is filtered by a filter system and compressed to a pressure of 5 to 6 bar in main air
compressor (Fig.3.2.). Then the air is cooled in air pre-cooling system i.e. Pre cooler which is
cooled by outgoing plant west nitrogen. This pre-cooled air is passed through absorber to remove
all the traces of moisture and CO2. Generally there are two absorber parallel connected in the line
which are working alternately for 4 hours to avoid saturation. After saturation it is regenerated by
passing warm nitrogen. This air is split into two parts; one part goes to cooled by nitrogen . The
other part enters Booster Compressor where it is compressed to 750 kpa . The Booster
Compressor. Booster is also equipped with Inter-Cooler between the stages and an After-Cooler
after the delivery. Booster is also equipped with a moisture analyser in the outlet. This is a
protection against any water entering into Exchanger in case of water leakage in Inter-Cooler and
After-Cooler. For the Booster Exchanger streams are cold by product oxygen from second column
47 | P a g e
. All these t streams of air are cooled against the returning stream from the column of liquid
Oxygen, Nitrogen. The outlet expanded air is then fed to the upper column i.e. Low pressure
column. The other air stream from the Booster Compressor enters the t Exchanger and then fed to
the lower column through a JT valve. The direct air coming from absorber enters heat Exchanger
and then enter bottom of high pressure column (lower column) for the purpose of boiling. Nitrogen
rich and oxygen rich products from the high pressure column is feed to the low pressure column
at top and middle respectively throw sub cooler and JT valves for the purpose of reflux. The
product of gaseous nitrogen, liquid oxygen, gaseous oxygen, west nitrogen flows through the heat
exchangers for the purpose of pre cooling the inward flow stream. A stream from the bottom of
the high pressure column having oxygen
Fig. 3.2. Line diagram of the actual cryogenic air separation (N2.O2, AR) process.
48 | P a g e
Fig. 3.3. Line diagram of the simulated cryogenic air separation by DWSIM software program
49 | P a g e
Fig. 3.4.A. Line diagram of the simulated cryogenic air separation by DWSIM software program
50 | P a g e
Fig. 3.4.B. Line diagram of the simulated cryogenic air separation by DWSIM software program
51 | P a g e
3.4. Factors influencing distillation process

The main factors which influence the distillation process and which can potentially be changed by
the operator are the following:
• Product rate
As the withdrawal of any product stream is increased then the purity of that stream decrease.
Conversely, reducing the gaseous withdrawal increases the oxygen purity.
• Column loading
For the column to perform adequately, good contact must be maintained between the liquid and
vapor on reach tray or section of packing. At low loads there will be insufficient liquid on the trays
or liquid will pass through the tray perforations (weeping). At too high a load the space between
the trays will become full of liquid (flooding or priming). In either case the separation efficiency
will be reduced or even stopped altogether. Packed columns are less sensitive to lower flow rates
but liquid distribution may become a problem.
• Reflux ratio
The reflux ratio is the ratio of the liquid flow coming down the column to the vapour flow going
up. As with the overall loading there is a minimum and a maximum but within these limits an
increased reflux ratio results in better separation. The reflux ratio of the column may be increased
by decreasing the product liquid flow.
• Feed conditions
The feed conditions must be correct. If the feed composition is not at or near design condition then
the column will not perform as per design. In addition if the temperature of the feed (for a given
pressure) is not correct or if the liquid /vapour ratio of the feed is not as design, the column
performance will also be affected.
• Operating pressure
In general a lower operating pressure means easier separation. So if a column is operated at an
elevated pressure its performance will be reduced.
52 | P a g e
Chapter Four
Result and discussions
4.1. Steady state separation plant air
The air separation unit plant is simulated by a software DWSIM (fig 4.1). The result obtained. In
this enter simulation taken Peng-Robinson thermodynamic fluid package and components as
nitrogen, oxygen, argon. Generally the steady state air separation plants are designed according to
the pressure difference and mass flow rate (Mahapatra and Bequette, 2010). The steady-state
cryogenic air separation plant which is simulated by DWSIM software shows the major equipment
in figure 4.1. Here absorber and air filters are not shown and assuming the air composition of
nitrogen 78.12%, oxygen 20.95%, argon 0.93%. Heat duties of the reboiler of the low pressure
column and heat duties of the condenser of the high pressure column are same so they are joined
to each other and act as a condenser-reboiler. So there is no extra source of external heat required.
Power produced by the turbine is used to run the LP compressor. Table 4.1 Shows the input
Simulation parameters for the cryogenic air separation unit.
NO. Parameters Quantity

1 HP column pressure 535kpa to 549kpa
2 LP column pressure 133kpa to 140kpa
3 No. of stage in HP column 21
4 No. of stage in LP column 18
5 In put air temperature 25 oC
6 Input air pressure 101.3kPa
7 Input air molar flow rate 4600 kgmole/h
8 Input air composition Nitrogen 78.12%, oxygen 20.95%, argon 0.93%.
Table 4.1. The Simulation parameters for the cryogenic air separation unit.
53 | P a g e
Fig. 4.1. diagram of the simulated cryogenic air separation by DWSIM software program
54 | P a g e
4.2. Result and discussions

4.2.1. Steady-state simulation analysis
Fig.4.1. shows the simulation of air separation by cryogenic process for a certain input data. And
table 4.2.and 4.4 shows the material, energy and composition of all material and energy stream in
DWSIM
4.2.2. High pressure column
Stage & Temprature(K)

25
20
15
stage
10
0
94.5 95 95.5 96 96.5 97 97.5 98 98.5 99
temprature(K)
(a)
Stage & pressure

25
20
15
stage
10
0
5.34 5.35 5.36 5.37 5.38 5.39 5.4 5.41
pressure(kpa)
(b)
Fig.4.2. High pressure column profile: (a) variation of temperature with stage from top to
bottom; (b) variation of pressure with stage
55 | P a g e
Stage & mole fraction

25
20
15
Stage
N2
10 O2
AR
5
0
0 0.2 0.4 0.6 0.8 1 1.2
mole fraction
(c)
25
20
15
Stage
Vapor
10
Liquid
0
-0.2 0 0.2 0.4 0.6 0.8 1 1.2 1.4
Flow (kmol/h)
(d)
Fig.4.2. (c) variation of composition with stage; (d) variation of net molar floe with stage.
56 | P a g e
(a) Temperature profile

Fig.4.2. (a) Shows that temperature of the high pressure column reduces from bottom to top of the
column and it maintain a temperature of -174.2oC at the bottom and -178.2oC at the top of the
column. The temperature of the high pressure column slowly increases up to 10 no. Stage and after
that temperature increase rapidly from stage 10 to 21 due to boiling effect by the stream 18 at the
bottom
(b) Pressure profile
Fig.4.2. (b) shows that pressure variation across the column. The pressure increase from top of
the column to bottom of the column linearly. And the pressure at the top stage of the column is
535kpa and bottom stage is 540kpa.
(c) Composition profile
Fig.4.2. (c) shows that composition variation of the high pressure column from top stage to bottom
stage. And it observed that nitrogen mole fraction increases from bottom to top of the column
whereas oxygen mole fraction increases from top to bottom the column. And argon remains in
between them but closer to oxygen. The top of the column reach in nitrogen and has a mole fraction
of N2-0.990000 , O2-0.00867169 , and AR-0.00132831 . And bottom of the column has a
mole fraction of N2=0.624726, O2= 0.360000 and AR=0.0152740
(d) Molar flow profile
Fig.4.2 (d) shows that vapour and liquid molar flow across each of the stage throughout the
column.
4.2.3. Low pressure column
Temprature(k) & Stage

20
15
Stage
10
0
80 82 84 86 88 90 92 94
Temprature(k)
(a)
Fig.4.3. a Low pressure column profile from top to bottom
57 | P a g e
Stage & pressure(kpa)

20
18
16
14
12
Stage
10
0
1.34 1.35 1.36 1.37 1.38 1.39 1.4 1.41
pressure(kpa)
(b)
mole Fraction & Stage

20
18
16
14
12
Stage
10 N2
8 O2
6 AR
0
0 0.2 0.4 0.6 0.8 1 1.2
Mole Fraction
(c)
Fig.4.3. Low pressure column profile from top to bottom: (a) temperature versus stage; (b)
pressure versus stage; (c) molar fraction versus stage
58 | P a g e
20
18
16
14
12
Stage
10
lquid
8
vapor
6
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Mole flow (kmol/h)
(d)
Fig.4.3. (d) net molar flow versus stage
(a) Temperature profile

Fig.4.3. (a) Shows that temperature of the high pressure column reduces from bottom to top as
179.97 oC to -193.2 oC. From stage no. 8 to 18 Therese is a high gradient of temperature difference.
it should be controlled with in a certain limit to stabilize the process.
(b) Pressure profile
Fig.4.3 (b) shows that pressure variation across the column linearly. And has a pressure of 133kPa
and 140kPa at top and bottom respectively.
(c) Composition profile
Fig.4.3. (c) shows that component mole fraction (N2, O2, and AR) variation across the stage of
low pressure column. As compare to the high pressure column it has well separation of both
oxygen (0.980000) and nitrogen (0.915027) at bottom and top of the column respectively. Whereas
in high pressure column only nitrogen separation (i.e. 990000 ) at the top of the column no
oxygen purity.
59 | P a g e
(d) Molar flow profile

Fig.4.3 (d) shows that vapour and liquid molar flow across the stage throughout the column.at top
of the column high vapour flow and at the bottom of the column high liquid flow.
4.3. Heat exchanger

The energy transfer between the two streams (cold and hot) can only possible if the temperature
difference between them is above a certain minimum value. The ΔTmin between the two stream
at which heat transfer possible is called pinch point. This ΔTmin is the minimum driving force of
heat transfer. If ΔTmin increases it has high driving force of heat transfer and it required less heat
exchanger area hence less cost (Dutta et al., 2011)(Dutta et al., 2011)
60 | P a g e
Table 4.2. Properties of each material stream in the process simulation.

Table 4.2. Properties of each material stream in the process simulation
Streams 51 50 29 25 27 49 48 33
Temperature C -170 -179.913 -178 -150 -183.049 -178 -191.419 -178
Pressure kPa 300 300 130 540 130 130 130 130
Mass Flow kg/s 7.20673 7.20673 12.7498 12.7498 12.7498 17.0471 17.0471 29.7969
Molar Flow kmol/h 806.78 806.78 1635.53 1635.53 1635.53 2157.69 2157.69 3793.22
Volumetric
Flow m3/s 0.597747 0.005655 2.67852 0.80385 2.52399 3.53254 2.98711 6.21106
Streams 28 46 31 30 24 26 Nitrogen 44
Temperature C -177.521 -191.255 -176.796 -150 -175.542 -176.363 -43.3386 -17.9008
Pressure kPa 420 138 138 420 490 460 130 130
Mass Flow kg/s 17.9632 17.0471 17.9632 17.9632 17.9632 17.9632 29.7969 29.7969
Molar Flow kmol/h 2182.47 2157.69 2182.47 2182.47 2182.47 2182.47 3793.22 3793.22
Volumetric
Flow m3/s 0.056645 2.81153 3.40113 1.39673 0.032279 0.041669 15.4519 17.1758
Streams 15 41 16 17 39 18 40 37
Temperature C -30 -68.8363 -55 -80 -94.4284 -105 -68.8363 -120.17
Pressure kPa 550 130 550 550 130 550 130 130
Mass Flow kg/s 30.713 29.7969 30.713 30.713 29.7969 30.713 29.7969 29.7969
Molar Flow kmol/h 3818 3793.22 3818 3818 3793.22 3818 3793.22 3793.22
Volumetric
Flow m3/s 3.8671 13.721 3.45527 3.03993 11.9793 2.6192 13.721 10.2207
Streams 45 14 air 2 3 4 13 5
Temperature C -17.9008 -5 25 268.425 20 20 20 56.1827
Pressure kPa 130 550 101.325 550 550 550 550 750
Mass Flow kg/s 29.7969 30.713 37.0036 37.0036 37.0036 6.29061 30.713 6.29061
Molar Flow kmol/h 3793.22 3818 4600 4600 4600 782 3818 782
61 | P a g e
Volumetric
Flow m3/s 17.1758 4.27651 31.2419 10.477 5.6436 0.959411 4.68418 0.791466
Streams 6 38 42 36 19 34 20 35
-
Temperature C 20 -94.4284 -43.3386 146.161 -130 -178 -160 -146.161
Pressure kPa 750 130 130 130 550 130 550 130
Mass Flow kg/s 6.29061 29.7969 29.7969 29.7969 30.713 29.7969 30.713 29.7969
Molar Flow kmol/h 782 3793.22 3793.22 3793.22 3818 3793.22 3818 3793.22
Volumetric
Flow m3/s 0.702758 11.9793 15.4519 8.43326 2.18957 6.21106 1.65047 8.43326
O2
Streams 23 21 22 60 7 product 58 8
-
Temperature C -178.113 -160.137 -174.253 40.5578 -20 -1.40165 -79.9331 -60
Pressure kPa 540 540 540 300 750 300 300 750
Mass Flow kg/s 12.7498 30.713 17.9632 7.20673 6.29061 7.20673 7.20673 6.29061
Molar Flow kmol/h 1635.53 3818 2182.47 806.78 782 806.78 806.78 782
Volumetric
Flow m3/s 0.016071 1.68167 0.019313 1.43476 0.604029 1.68108 1.18553 0.504164
Streams 59 56 9 57 54 10 55 52
-
Temperature C -40.5578 -109.644 -90 79.9331 -139.596 -120 -109.644 -170
Pressure kPa 300 300 750 300 300 750 300 300
Mass Flow kg/s 7.20673 7.20673 6.29061 7.20673 7.20673 6.29061 7.20673 7.20673
Molar Flow kmol/h 806.78 806.78 782 806.78 806.78 782 806.78 806.78
Volumetric
Flow m3/s 1.43476 0.995683 0.427982 1.18553 0.801377 0.349785 0.995683 0.597747
Streams 11 53 32 12 47
Temperature C -150 -139.596 -178.035 -154.549 -179.974
Pressure kPa 750 300 140 380 140
Mass Flow kg/s 6.29061 7.20673 6.29061 6.29061 7.20673
Molar Flow kmol/h 782 806.78 782 782 806.78
Volumetric
Flow m3/s 0.26743 0.801377 1.18456 0.533443 0.00566
Table 4.2.Shows each material stream condition of the PFD
62 | P a g e
Table 4.3 Energy streams in the process simulation

Table 4.3. Energy streams in the plant simulation
Energy streams
ESTR-121 ESTR-118 ESTR-114 ESTR-111 ESTR-108 ESTR-104
Heat Flow Kw 1542.93 1.20745 68.9744 2603.17 382.334 242.156
ESTR-097 ESTR-094 E-1 E-2 E-3 E-4
Heat Flow Kw 420.521 3713.96 9177.51 9411.62 228.301 231.892
ESTR-081
Heat Flow Kw 132.425
Table 4.3 Shows all energy streams
63 | P a g e
Table 4.4 Composition of each stream in the process simulation
Table 4.4.Shows the composition of each material stream,
64 | P a g e
4.4. Product recovery

The performance or efficiency of an air separation unit is calculated by its main product recovery.
If oxygen is the main product, it may be define as the ratio of usable oxygen produced by the plant
divided by the oxygen in the process air intake by the plant(Kerry, 2007). To increase the oxygen-
product recovery, increase the reflux at the top of the upper column, but this depends on the
following factor:
(a) The quality and quantity of liquid nitrogen reflux sent from the lower (high pressure)
Column to upper column (low pressure column)
(b) The quantity and quality of the vapour rising to the top tray of the upper column
Kgmole
806.78 (𝑜𝑥𝑦𝑔𝑒𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑)
h
Oxygen recovery (process recovery) = 𝑘𝑔𝑚𝑜𝑙𝑒 = 0.8371
4600 𝑥 0.2095(𝑎𝑖𝑟 𝑥𝑜𝑦𝑔𝑒𝑛)
ℎ
65 | P a g e
Chapter Five
Conclusion, Future work
5.1 Conclusion
1. The air separation process is simulated using DWSIM software
2. This model produces purity of Oxygen 98.8%, Nitrogen 0.9473%, and molar flow rate of
Nitrogen 3793.22 kgmole/h, Oxygen 806.78 kgmole/h for an inlet Air flow rate of 4600 kgmole/h
at pressure of 101.3 kPa and temperature of 250C which is economically suitable for steel plant.
2. recovery of the plant is 0.8371% based on oxygen in steady state case.
3. And also observed the process parameter response with time. For a certain air flow rate this
simulation model produces molar flow and mole fraction of product up to acceptable limit.
4. For this simulation, at ±10% variation of feed molar flow the purity of the nitrogen and oxygen
are not so effected, but at ±20% variation of feed molar flow the purity of nitrogen and oxygen are
affected i.e. continuously reducing
5.2 Future work
1. The process recovery and productivity can be increased and process specific power can be
Reduced.
2. The heat exchanger performance can also be studied.
3. To obtain optimum improvement of the process is Dependent on continues progress in the

research work and advanced Process control techniques.
66 | P a g e
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Kurdistan Regional Government ‫هەرێمى كوردستانى عيراق‬

Presidency of Ministers Council ‫سەرۆكايەتى ئەنجومەنى وەزيران‬

Computer Simulation of Oxygen Production using

A Project Submitted to the Chemical Engineering Department Faculty of

Figure 1.6. Effect of oxygen enrichment on flame temperature of methane ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 15

Figure1.10. Minimum distances between liquid-oxygen storage and exposures ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 25

Fig.4.3. (d) net molar flow versus stage ˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖˖ 59

1.1. Historical Background

1.2. The Occurrence of Oxygen

Table 1.1. Oxygen occurrence in different “regions”

1.2.1 Oxygen in the Air and Photosynthesis

6CO2 + 6H2O → C6H12O6 + 6O2

Figure 1.1. Schematic illustration of photosynthesis

Table 1.2. The complex photosynthesis reaction

6CO2 + 12H + light →

→ 6O2 + C6H12O6 + 6H2O

Figure 1.2. air compassion

1.3. Physical properties

Table 1.3. Oxygen Solubility in Water (Early, 2004)

NO. Temperature, °C Aqueous solubility of O2 at STP, L/L

NO. Property Value Units

27 Diffusivities in Liquids Sucrose*-water (125 poise) = 0.25 DL × 105 ,

Table 1.5. Physical Properties of Oxygen (Early, 2004)

NO. Property Value

Density Relative density Melting point Boiling point Specif ic heat cp at

1.4. methodology (method of Productions )

1.4.1. Methods of production

1.4.2. Adsorptive Air Separation

Figure 1.3. Oxygen pressure swing adsorption (PSA) system

1.4.3. Membrane Air Separation

1.4.4. Oxygen from Cryogenic Air Separation:

in manufacturing some acetylene through partial oxidation of the hydrocarbons in methane-rich

1.5.1. Combustion and Metallurgy

Figure 1.5. Effect of oxygen enrichment on flame velocity of methane

Figure 1.6. Effect of oxygen enrichment on flame temperature of methane

Fe (l) +C(s) + 1/2 O2 (g) −→ Fe (l) +CO(g) + Heat

Carbon is removed from solution in the iron by conversion to carbon monoxide.

1.5.2. Production of Chemicals

1.5.3. Oxygen Bleaching of Wood Pulp

8RH+O2 −→ R• +HOO• (19)

1.5.4. Wastewater Treatment

1.6. Storage and Transportation

1.6.2. Material Selection for Oxygen Compatibility

1.7. Safe storage, Handling

1.7.2. Handling leaked and emergences

1.7.3. First aid

1.7.4. Method of Shipment

1.7.6. Filling limits

1.7.8. Tube trailers and cargo tanks on trucks or trailers

1.7.9. Small portable liquid containers

1.7.10. Tank cars

1.8 The Biological Role of Oxygen

2.1 Cryogenic Technology

2.2 Air Separation

Fig. 2.1. Cryogenic air separation process

Fig. 2.2. Pumped liquid oxygen process.

Fig. 2.3. UHP nitrogen process with UHP oxygen coproduction.

2.3 Oxygen from Cryogenic Air Separation

2.4 Cryogenic Instrumentation

2. simplify the pressure-transducer construction to eliminate differences between materials.

2.4.2 Liquid Level

The level of the temperature measurement (4 K, 20 K, 77 K, or higher) is the first issue to be

Below 20 K, semiconductor thermometers (germanium-, carbon-, or silicon-based) are preferred.