Authors: Jared Watkins, Juan Tellez

INTRODUCTION EQUATIONS
Key steps of the cryogenic air distillation process including air 1. Equilibrium Condition 𝑦𝑖 = 𝑘𝑖 𝑥𝑖
compression, air cooling and purification, heat exchange, refrigeration, 2. Mass Balance 𝑛𝑓 𝑥𝑓 = 𝑛𝐷 𝑥𝐷 + 𝑛𝐵 𝑥𝐵
internal product compression and rectification were investigated. The 𝑛𝑓 = 𝑛𝐷 + 𝑛𝐵
study of this process has become increasingly popular in accordance 𝑥𝑓 −𝑥𝐵
𝑛𝐷 = 𝑛𝑓
with the rise in demand for these components within industry such as 𝑥𝐷 −𝑥𝐵

mining and semiconductors. Within the separation unit the air is 3. Energy Balance
𝑑𝐸
separated via distillation at very low temperatures to take advantage of = 𝑛𝑉𝑖𝑛 ℎ𝑉𝑖𝑛 + 𝑛𝐿𝑖𝑛 ℎ𝐿𝑖𝑛 − 𝑛𝑉𝑜𝑢𝑡 ℎ𝑉𝑜𝑢𝑡 + 𝑛𝐿𝑜𝑢𝑡 ℎ𝐿𝑜𝑢𝑡
𝑑𝑡
the boiling point differences of the air components in a process known 𝑅 𝑥
4. Rectifying Section Operating Line 𝑦= 𝑥+ 𝐷
as rectification. The distillation column can be designed depending on 𝑅+1 𝑅+1
𝑅 𝑥𝐵
the specific products needed, with the most common design being the 5. Stripping Section Operating Line 𝑦= 𝑥+
𝑅+1 𝑅+1
double column system with an adjacent argon unit. The energy needed 𝑅𝑇 𝑎 𝑇
6. Peng –Robinson EOS 𝑃= −
𝑉−𝑏 𝑉 𝑉+𝑏 +𝑏 𝑉−𝑏
for the very low temperatures constitutes most of cost of production and 𝜕𝑉
𝜕𝑉 𝑇 𝜕𝑇 −𝑉
so it is of interest to optimize the process and obtain maximum 7. Joule-Thompson Effect µ𝐽𝑇 = = 𝑃

efficiency. While involving a high initial capital cost air separation units 𝜕𝑇 𝐻 𝐶𝑃

have relatively high yields and can obtain large volumes of high purity Where 𝑦𝑖 =vapor phase composition of component i, and 𝑥𝑖 the liquid
gases or liquids. phase, n=molar flow rate, h=enthalpy, and R=reflux ratio

Figure 7: Column Tray schematic.

Retrieved from Roffel, 2000. Liquid
oxygen flows down and becomes
more concentrated as nitrogen vapor
rises. Modern plants use structured
packing's to offer maximum surface
area and a low pressure drop.

Figure 2: Process flow diagram of cryogenic air distillation. Shows the step by step procedure of this process. Retrieved from Linde Engineering.
Table 1: Air composition and thermodynamic properties of its components
at 101.1 Pa. Retrieved from Agrawal, 2000.
Air Compression
Ambient air is filtered to
remove dust particles and then
fed to a series of turbo
Figure 1: Vapor Pressure compressors with an intercooler.
curve for atmospheric The air is compressed to an
operational pressure of about 6
Pressure (Pa)
Air Cooling and
Purification
Process air is cooled with
water in a direct contact
cooler also removing soluble
air impurities. Cooling water
is prepared in an evaporation
cooler against dry nitrogen
Heat Exchange
Further cooling of process air
in heat exchangers by means
of countercurrent exchange
with nitrogen waste gas from
the rectification process. The
air is cooled to nearly
Internal Compression
and Refrigeration
A refrigeration process
provides further cooling for
the cold temperatures
required for air separation.
Side streams are drawn off
and compressed further in an
Rectification of Air
A double-column design with
a combined condenser and re-
boiler is used to obtain
oxygen and nitrogen. The
partially liquefied air enters
the bottom of the high
Process Advantages Disadvantages
Rectification of Argon
• Low amount of electricity per • Large site space and utility
A side stream enriched in
unit nitrogen requirements
Argon and Oxygen is taken
• Produces very high purity • High capital cost
from the bottom of the low Cryogenic
nitrogen • Limited scaleability in
pressure column and fed to • Can generate liquid nitrogen production
the crude argon column. High for storage on site • Long start-up and shutdown
purity Argon is produced at

gasses, showing the dew

point and bubble point
of air and its major
components. Retrieved
from Linde Engineering.
Temperature (K)
Background
Cryogenic air separation takes advantage of the differing boiling points of
its components as shown in Table 1. In order to start the separation process,
a large quantity of the incoming air needs to be liquefied. This is
accomplished by cooling the air by decreasing its temperature and
manipulating the pressure until condensation begins. Figure 1 displays a
curve delineating the range at which air condenses when approaching from
the right (decreasing temperature). The air can then be separated into its
components(Table 1), mainly Nitrogen, Oxygen and Argon. The first
process developed by Linde in 1902 separated oxygen from air , and
developed into the double column mechanism in 1910 and its Argon
constituent in 1913 as to be discussed. Figure 2 displays the general
overview of the process.
AIR SEPARATION OPTIMAL RESULTS
Table 2: Optimal air separation
Optimal results from developed
Results optimization model. Retrieved
Air total input, m3/h 3150
from Zhu, 2006.
Gas O2 product output, m3/h 516.7 Optimization plays a role in
economically running a column.
O2 product Purity 99.6%
Energy is the biggest cost input
Gas N2 product output, m3/h 1449 and therefore a maximum return
is desired. A high recovery at a
N2 product Purity .999 high purity is ideal. This can be
Liquid O2 product output, m3/h 30.05 accomplished by controlling the
processes different variables,
Liquid O2 product Purity 99.75%
including the column pressure,
Argon product output 9.5
top composition and bottoms
Argon product purity 95.09% composition (Amarkhail).
bar. waste gas from the liquefaction temperature. air booster compressor and pressure column, oxygen the top and liquid oxygen at • Low to moderate capital cost
rectification process. CO2, then expanded in turbo- enriched liquid forms in the the sump. The oxygen is • Cost-effective nitrogen • High maintenance equipment
water vapor and expanders taking advantage column sump and pure refluxed back to the low- PSA production of relativity high • Noisy operation
hydrocarbons are removed of the Joule-Thompson effect nitrogen gas at the column pressure column. purities • Limited scalability
periodically via molecular to supply the refrigeration. top. Further separation takes • Quick installation and start-up
sieve absorbers. These place in the low pressure
• Uneconomical for high purity
impurities otherwise would column with pure oxygen gas • Low capital cost
requirements
freeze and disrupt equipment. at the bottom • Production output is very
• Uneconomical for large
flexible
Membrane outputs
Table 3: Explanation of each step on process flow diagram. Retrieved from Linde Engineering. • Quick installation and start-up
• Requires relatively large
• Easy to vary purity and flow
amount of electricity per unit
rate
nitrogen
Table 4: Advantages and disadvantages of different methods of air
separation. Retrieved from Jaya, 2013.
REFERENCES
1. Agrawal, R., & Herron, D. (2000). Air Liquefaction: Distillation. Allentown,
PA, USA. Retrieved from
https://www.thevespiary.org/library/Files_Uploaded_by_Users/Sedit/Chemical
%20Analysis/Encyclopedia%20of%20Separation%20Science/Level%20III%20
-%20Practical%20Applications/AIR%20LIQUEFACTION%20-
%20DISTILLATION.pdf
2. Amarkhail, Sher shah. Air Separation Diploma project. Retrieved from
http://kchbi.chtf.stuba.sk/ODAOld/doc/Diploma%20work%20of%20Shershah
Figure 3: X-Y Diagram N2-O2 at P=1.4atm Figure 4: X-Y Diagram N2-O2 at P=5atm Figure 5: X-Y Diagram Ar-O2 at P=1.4atm Figure 6: McCabe-Thiele Analysis %20Amarkhail.pdf
(Amarkhail, 2009) (Amarkhail, 2009) (Amarkhail, 2009) (Amarkhail, 2009) 3. Jaya, A. (2013, January). Air Separation Units (Engineering Design Guideline.
Retrieved from
Using vapor-liquid equilibrium data for This Diagram is produced the same way Argon is not as volatile as Nitrogen but still The VLE diagrams can be used in column http://kolmetz.com/pdf/EDG/ENGINEERING_DESIGN_GUIDELINE_Air_Se
Oxygen and Nitrogen K values are derived as presented in Figure 3, however the pressure is more volatile than oxygen. As a result the analysis. The operating lines expressed in paration_Units_Rev01web.pdf
seen in Equation 1. The Ratio of these K now 5 atm. This represents the conditions in vapor-liquid separation isn’t as well defined as Equations 4 and 5 were plotted along with a 4. Linde Engineering. (n.d.). History and technological progress. Cryogenic air
values defines the relative volatility, α, from the high pressure column. Nitrogen is more in the previous Figures. Separation is still horizontal line, q=1, at the feed composition, separation. Retrieved from http://www.linde-
α𝑥 engineering.com/internet.global.lindeengineering.global/en/images/AS.B1EN%
which the line 𝑦 = is plotted. volatile than oxygen, resulting in a good possible but more trays are needed. x=0.79 for Nitrogen. The desired distillate
1+ α−1 𝑥 201113%20-%20%26AA_History_.layout19_4353.pdf
vapor-liquid separation as seen in the above purity acts as the starting point The operating
5. Roffel, B., Betlem, B., & Ruijter, J. (2000, March). First Principles dynamic
figure. lines and equilibrium line act as the lower and modeling and multivariable control of a cryogenic distillation process.
This diagram represents, with respect to
upper boundary's from which subsequent Retrieved from
nitrogen, the amount of nitrogen vapor in
material and equilibrium balance lines, or http://tbk.eldoc.ub.rug.nl/FILES/root/2000/CompChemEngRoffel/2000CompC
equilibrium with the liquid nitrogen at 1.4
steps, are used to get to the desired bottoms hemEngRoffel.pdf
atm. This represents the conditions of the low 6. Zhu, Y., Liu, X., & Zhou, Z. (2006, June). Optimization of Cryogenic Air
composition. The number of steps is the
pressure column. Separation Distillation Columns. Dalian, China. Retrieved from
number of theoretical stages.
http://people.tamu.edu/~wangzhu/YuZhu_WCICA2006.pdf