Overview of Cryogenic Air Separation

Authors: Jared Watkins, Juan Tellez

INTRODUCTION EQUATIONS
Key steps of the cryogenic air distillation process including air 1. Equilibrium Condition
compression, air cooling and purification, heat exchange, refrigeration,
internal product compression and rectification were investigated. The
2. Mass Balance

study of this process has become increasingly popular in accordance 3. Energy Balance
with the rise in demand for these components within industry such as
mining and semiconductors. Within the separation unit the air is 4. Rectifying Section Operating Line
separated via distillation at very low temperatures to take advantage of 5. Stripping Section Operating Line
the boiling point differences of the air components in a process known 6. Peng Robinson EOS
as rectification. The distillation column can be designed depending on 7. Joule-Thompson Effect Where =vapor phase
the specific products needed, with the most common design being the composition of component i, and the liquid phase, n=molar flow rate,
double column system with an adjacent argon unit. The energy needed h=enthalpy, and R=reflux ratio
for the very low temperatures constitutes most of cost of production and
so it is of interest to optimize the process and obtain maximum
efficiency. While involving a high initial capital cost air separation units
have relatively high yields and can obtain large volumes of high purity
gases or liquids.

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
compressors with an intercooler.
Figure 1: Vapor Pressure The air is compressed to an
curve for atmospheric
operational pressure of about 6
gasses, showing the dew bar.
Pressure
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
waste gas from the
Internal Compression
Heat Exchange
and Refrigeration
Further cooling of process air A refrigeration process
in heat exchangers by means provides further cooling for
of countercurrent exchange the cold temperatures
with nitrogen waste gas from required for air separation.
the rectification process. The Side streams are drawn off
air is cooled to nearly and compressed further in an
liquefaction temperature. air booster compressor and
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
pressure column, oxygen
Process Advantages Disadvantages
Rectification of Argon
A side stream enriched in Low amount of electricity per Large site space and utility
Argon and Oxygen is taken unit nitrogen requirements
from the bottom of the low Produces very high purity High capital cost
Cryogenic
pressure column and fed to nitrogen Limited scaleability in
the crude argon column. High Can generate liquid nitrogen production
for storage on site Long start-up and shutdown
purity Argon is produced at
the top and liquid oxygen at

point and bubble point rectification process. CO2, then expanded in turbo- enriched liquid forms in the the sump. The oxygen is Low to moderate capital cost
(Pa)

of air and its major
components. Retrieved
from Linde Engineering.
Temperatur
e (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
O2 product Purity economically running a column.
99.6%
Energy is the biggest cost input
Gas N2 product output, m3/h 1449 and therefore a maximum return
N2 product Purity .999 is desired. A high recovery at a
high purity is ideal. This can be
Liquid O2 product output, m3/h 30.05
accomplished by controlling the
Liquid O2 product Purity
99.75% processes different variables,
Argon product output 9.5 including the column pressure,
top composition and bottoms
Argon product purity 95.09%
composition (Amarkhail).
water vapor and expanders taking advantage column sump and pure refluxed back to the low- Cost-effective nitrogen High maintenance equipment
hydrocarbons are removed of the Joule-Thompson effect nitrogen gas at the column pressure column. PSA production of relativity high Noisy operation
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
impurities otherwise would column with pure oxygen gas
freeze and disrupt equipment. at the bottom Uneconomical for high purity
Low capital cost
requirements
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
rate
amount of electricity per unit
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 isnt as well defined 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, , from the high pressure column. Nitrogen is more as in the previous Figures. Separation is still horizontal line, q=1, at the feed composition, separation. Retrieved from http://www.linde-
which the line is plotted. volatile than oxygen, resulting in a good possible but more trays are needed. x=0.79 for Nitrogen. The desired distillate engineering.com/internet.global.lindeengineering.global/en/images/AS.B1EN
vapor-liquid separation as seen in the above purity acts as the starting point The operating %201113%20-%20%26AA_History_.layout19_4353.pdf
This diagram represents, with respect to figure. lines and equilibrium line act as the lower and 5. Roffel, B., Betlem, B., & Ruijter, J. (2000, March). First Principles dynamic
nitrogen, the amount of nitrogen vapor in upper boundary's from which subsequent modeling and multivariable control of a cryogenic distillation process.
equilibrium with the liquid nitrogen at 1.4 material and equilibrium balance lines, or Retrieved from
atm. This represents the conditions of the low steps, are used to get to the desired bottoms http://tbk.eldoc.ub.rug.nl/FILES/root/2000/CompChemEngRoffel/2000CompC
pressure column. composition. The number of steps is the hemEngRoffel.pdf
6. Zhu, Y., Liu, X., & Zhou, Z. (2006, June). Optimization of Cryogenic Air
number of theoretical stages.
Separation Distillation Columns. Dalian, China. Retrieved from
http://people.tamu.edu/~wangzhu/YuZhu_WCICA2006.pdf