Contents

○ Reboilers incidents
○ Contaminants of air
SAFE OPERATION OF ○ Typical default air quality design basis
○ Adsorption of air contaminants
REBOILERS/CONDENSERS ○ Properties of air contaminants
○ Condenser／Reboiler
IN AIR SEPARATION UNITS ○ LOX Purging
○ OPERATION
Mar.13.2019 ○ Maximum contaminant levels
○ Deriming
GSC. Tech. Support Dept. ○ Internal compression type ASU

S.Yamamoto
Mar.13.2019 CONFIDENTIAL Copy right (C) TAIYO NIPPON SANSO CORPORATION Mar.13.2019 CONFIDENTIAL Copy right (C) TAIYO NIPPON SANSO CORPORATION 2

Reboilers incidents Contaminants of air

Plugging, flammable and corrosive contaminants of air

The reboiler incidents are categorized into Flammable or Reactive
three classes depending on their gravity: Plugging Contaminants
Contaminants
Corrosive Contaminants
Water H2O Methane CH4 Sulphur Dioxide SO2
Carbon Dioxide CO2 Acetylene C2H2 Sulphur Trioxide SO3
major explosions, Nitrous Oxide N2O Ethylene C2H4 Hydrogen Sulphide H2S
Ethane C2H6 Chlorine Cl2
limited explosions, and Propylene C3H6 Hydrochloric Acid HCl
Propane C3H8 Ammonia NH3
internal leaks. Other Hydrocarbons Other Sulphur Compounds
Oxides of Nitrogen NOx Other Chlorides
Ozone O3
NOTE—This table is duplicated in EIGA Doc 147 (CGA P-8):
Safe Practices Guide for Cryogenic Air Separation Plants [1]

IGC DOC 65/13/E SAFE OPERATION OF REBOILERS/CONDENSERS IN AIR SEPARATION UNITS (Appendix A)
Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 3 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 4
Typical default air quality design basis Adsorption of air contaminants
1
No Adsorption Partial Adsorption Total Adsorption
Typical default air quality design basis Alumina Methane CH4 2
Carbon dioxyde CO2 3
Ozone O3

(for adsorptive FEP system) Front End Purification Ethylene

Ethane
C2H4
C2H6
Nitrous Oxide
Acetylene
N2O
C2H2
Oxides of nitrogen NO2
N2O3
Design Air Quality Propylene C3H6 Water H2O
Component
(ppm/v) Propane
Nitric oxide
C3H8
NO
Methane CH4 5 n-butane n-C4H10
Molecular Sieve Methane CH4 Ethylene C2H4 Carbon Dioxide CO2
Ethane C2H6 0.1 Front End Purification Ethane C2H6 Propane C3H8 Acetylene C2 H2
4
Nitric Oxide NO Nitrous Oxide N2O Propylene C3 H6
Acetylene C2H2 0.3 3
Ozone O3
Ethylene C2H4 0.1 Oxides of Nitrogen NO2
N2O3
Propane C3H8 0.05 n-Butane n-C4H10
Water H2O
Propylene C3H6 0.2 Oxygenates
C4+ hydrocarbons 1 Silica Gel Methane CH4 Carbon Dioxide CO2
Chlorinated Hydrocarbons
Acetylene C2 H2
Carbon Dioxide CO2 425 Rich Liquid Adsorbers Ethane C2H6 Ethylene C2H4 Ozone O3
Vapour Phase Adsorbers Propylene C3H6 Dienes
NOx (NO+ NO2) 0.1 LOX Adsorbers Propane C3H8
(FEP: Front-end purification)
N2O 0.35 Nitrous Oxide N2O
NOTE Assumptions: Contaminant at less than 10 ppm/v; carbon dioxide at 425ppm/v Total adsorption of heavy hydrocarbons (C4+)
This table represents the maximum simultaneous concentrations in the air intake to the plant. They are 1 Degree of removal is dependent on design and operating parameters. Total removal might be possible with adequate design.
assumed for design purposes in the absence of specific data. 2 Molecular sieve is normally designed to remove carbon dioxide. Refer to Section 7 for proper operations required to prevent breakthrough.
Changes to the designs of various components may be required if these concentrations are exceeded. 3 By decomposition.
Actual data for the locality should be provided to the supplier whenever such information is available. 4 Nitric oxide is oxidized by air and subsequently trapped.

IGC DOC 65/13/E SAFE OPERATION OF REBOILERS/CONDENSERS IN AIR SEPARATION UNITS (Appendix D) IGC DOC 65/13/E SAFE OPERATION OF REBOILERS/CONDENSERS IN AIR SEPARATION UNITS (Appendix C)
Mar.13.2019 CONFIDENTIAL Copy right (C) TAIYO NIPPON SANSO CORPORATION 5 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 6

Properties of air contaminants Breakthrough curve of MS adseorber

Solubility in O2 K-value Lower Flammability Limit Adsorption

vol.ppm *1 - *2 vol.% *3 2
Carbon Dioxide CO2 4～5 10^-3 non-flammable Total
C2H4
Nitrous Oxide N 2O 140～160 5×10^-4 non-flammable Partial 1 .5
Methane CH4 Miscible 0.3 5 －
Ethane C 2H 6 128,000～250,000 2×10^-4 3 － CH4, C2H6
1

C/C0 [-]
Acetylene C 2H 2 4～6 2×10^-2 2.5 Total
Ethylene C 2H 4 13,000～30,000 2×10^-3 2.7 Partial
Propane C 3H 8 9,800 3×10^-7 2.1 Partial 0 .5
C3H8 CO2
Propylene C 3H 6 3,600 ～6,700 3×10^-6 2.1 Total C2H2, C3H6
V *1:in O2 at 90.2K,101.3kPa 0
Y *2:in O2 at 90.2K,101.3kPa
*3:in Air at 293K,101.3kPa
- 0 .5
Fin Equilibrium 0 100 200 300 400
Z t [m in ]
X Total material balance Fin=V+L
Component material balance Fin x Z=V x Y + L x X
L vapor -liquid equilibrium equation K=Y/X

Mar.13.2019 CONFIDENTIAL Copy

Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 7 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 8
Condenser／Reboiler Condenser／Reboiler

DFR vs TSCR TSCR(Thermo Syphon Condenser Reboiler)

Distributor LIN
LPC Z
Z
ΔT=0.9K ΔT=1.1K LPC
GAN GOX 150kPa
LPC 94.1K
LOX
GOX+LOX GO2:LO2=1:19 ・A type commonly used in air separation unit
DFR boiling GO2+LO2
・It is operated submerged in liquid oxygen
LOX Condensation
150kPa Vaporization
94.1K TSCR Condensation
GN2 ・LO circulates using thermosiphon effect
GAN
GOX+LOX
LOX
・Oxygen outlet is vapor -liquid mixed phase
LOX
subcool ((LO+GO)/GO > 20)
LOX 549kPa TSCR
540kPa Pump
95.2K LIN
95.0K O N
LIN O N
2 2 2 2 LN2
HPC T HPC LO2
Temp. Temp.
DFR TSCR
DFR：Down Flow Reboiler TSCR：Thermo Syphon Condenser Reboiler
Reboiler ΔT-AC power
ΔT ℃ 2.0 1.5 1.0 0.5
LPC MPaG 0.04
HPC MPaG 455 435 415 395
HPC
AC Power - 100 98 96 94

Mar.13.2019 CONFIDENTIAL Copy right (C) TAIYO NIPPON SANSO CORPORATION 9 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 10

Condenser／Reboiler LOX Purging

The following equation computes the concentration of high boiling components

DFR(Down Flow Reboiler) in the LOX:

伝熱模式図 LOX x , LOX F

CF = =
y , F +K F

GN2 Where
DFR GAN - CF = Concentration factor, relative to the concentration in the air
GAN
-x = Mole fraction of the component in the liquid phase
LPC
-y = Mole fraction of the component in the vapour phase
- Ffeed = Air molar flow rate to the column system
- FLOX = Molar flow rate of LOX from the reboiler
GO2+LO2 -K = y/x for the component at equilibrium
LO2 GO2:LO2=1:2 - FGOX = Molar GOX flow rate from the reboiler
伝熱面

LO2 LOX
LOP
HPC LN2 GOX

Mar.13.2019 CONFIDENTIAL Copy right (C) TAIYO NIPPON SANSO CORPORATION 11 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 12
LOX Purging LOX Purging

LOX purge rate 0.1% of Air LOX purge rate 0.8% of Air
F=98.9 F=98.9
288K 288K
CH4 3000ppb CH4 3000ppb
C2H6 100ppb F=17.3 F=75.8 C2H6 100ppb F=15.6 F=76.9
C2H4 60ppb 1.31barA C2H4 60ppb 1.31barA
C3H8 30ppb 286K C3H8 30ppb 286K
N2O 60ppb CH4 17ppm F=30.9 N2O 60ppb CH4 16ppm F=27.7
C2H6 16ppb C2H6 1.6ppb
C2H4 54ppb F=0.11 C2H4 4.0ppb F=0.78
F=100.0 1.46barA F=100.0 1.46barA
6.1barA 94K TNSC Standard 6.1barA 94K TNSC Standard
283K CH4 56ppm ＜468ppm 283K CH4 54ppm ＜468ppm
CH4 3000ppb C2H6 78ppm ＜117ppm CH4 3000ppb C2H6 13ppm ＜117ppm
C2H6 100ppb C2H4 54ppm ＜117ppm C2H6 100ppb C2H4 8ppm ＜117ppm
C3H8 27ppm ＜78ppm C3H8 4ppm ＜78ppm
C2H2 300ppb C2H2 300ppb
N2O 54ppm ＜100ppm N2O 8ppm ＜100ppm
C2H4 100ppb C2H4 100ppb
C3H6 200ppb C3H6 200ppb
C3H8 50ppb C3H8 50ppb
C4+ 100ppb C4+ 100ppb
CO2 400ppm CO2 400ppm
N2O 300ppb F=47.6 N2O 300ppb F=44.8
F=14.8 5.9barA F=20.7 5.9barA
100K 100K
CH4 5300ppb CH4 5236ppb
C2H6 177ppb C2H6 175ppb
F=84.1 C2H4 106ppb F=78.2 C2H4 105ppb
C3H8 53ppb C3H8 52ppb
N2O 106ppb N2O 105ppb

Mar.13.2019 CONFIDENTIAL Copy

Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 13 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 14

LOX Purging OPERATION

adsorptive FEP system

ASU using DFR N2 O Outlet concentration high alarm 1.0vol.ppm CO2
Removal
Operating limit 10.0vol.ppm CO2
F=20.44 rate DFR inlet
0ppmN2O 90% 0.15ppm If it exceeds 1.0vol.ppm CO2 The operator should switch to the
GO2 F=20.55 80% 0.30ppm other adsorber bed if available
0.15ppmN2O 70% 0.45ppm (i.e., adequately regenerated)
90% Removal
0.03ppmN2O Operating limit
maximize the liquid purge rate and,
(*1) 1.00ppm
where possible, monitor sump
concentrations of hydrocarbons,
nitrous oxide, and carbon dioxide
F=100 (*1)
0.3ppmN2O P
If it exceeds 10vol.ppm CO2 the ASU shall be shutdown if the
adsorber cannot be switched within
30 minutes
Purge LO F=0.11, 27ppmN2O

Mar.13.2019 CONFIDENTIAL Copy

Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 15 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 16
TSCR OPERATION Maximum contaminant levels (TSCR)

Maximum contaminant levels in liquid oxygen

Liquid level thermosyphon reboiler operation at 1.2 bar abs
It should be recognized that the minimum degree of Maximum Allowable
submergence required for safe operation of bath-
Component Concentration
type reboilers is a function of the type of heat
exchanger that is used.
(ppm/v)
Methane CH4 500
Acetylene C2H2 0.5
To ensure operational safety, the depth of the
Ethylene C2H4 200
TSCR reboiler sump liquid shall be maintained at the level NOTES
specified by the plant supplier. Ethane C2H6 250 1. Care shall be taken in sampling cryogenic liquids
Propylene C3H6 35 to achieve accurate, consistent results.
Any continuous liquid stream shall be vaporized
Propane C3H8 100 quickly to ensure that the gas phase concentration
If this value is unknown, the reboiler should be
C4 Hydrocarbons 5 remains the same as the bulk liquid composition.
operated in a fully submerged condition (100% Failure to do this can lead to underestimating
submergence), i.e., the liquid level in the bath shall Total hydrocarbons the hydrocarbon concentration in the bulk.
500
reach the upper end of the reboiler core. (THC) (as CH4)
2. For plants with production of pressurized oxygen
Carbon Dioxide CO2 4 by internal compression see also
Nitrous Oxide N2O 100 EIGA Doc 145 (CGA G-4.9) [6]

IGC DOC 65/13/E SAFE OPERATION OF REBOILERS/CONDENSERS IN AIR SEPARATION UNITS (Appendix E)
Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 17 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 18

Maximum contaminant levels (DFR) Deriming

• Drain all liquids;
Maximum contaminant levels in liquid oxygen downflow reboiler
operation at 1.2 bar abs • Establish the sequence of circuits to be derimed.
NOTES Derime the circuits in that sequence;
Maximum Allowable 1 Any significant increase in
Component Concentration hydrocarbon component concentrations • Force the flow as far as possible through all the sections;
in the reboiler sump during plant load changes
(ppm/v) or shutdowns is a sign that hydrocarbon • Partial deriming should be avoided when proper isolation is not ensured.
Methane CH4 500 accumulation has taken place.
Experience has shown that there is a risk of shifting impurities or deposits
Draining of the reboiler sump liquid or reboiler
Acetylene C2H2 0.5 derime should be considered. from one section to another;
Ethylene C2H4 15 2 It should be noted that care shall be taken • Verify the presence of a flow from all deriming outlets;
Ethane C2H6 15 in sampling cryogenic liquids to achieve
Propylene C3H6 1 accurate, • Open all instrument lines towards the end of the deriming process; and
consistent results.
Propane C3H8 1 Any continuous liquid stream shall be vaporized • If the operating manual gives no specific instructions, deriming for a plant
quickly to ensure that the gas phase
C4 Hydrocarbons 1 concentration remains the same as the bulk with FEP is typically completed when all deriming outlet temperatures are
Total hydrocarbons liquid composition.
approximately 15℃ for at least 2 hours.
500 Failure to do this can lead to underestimating
(THC) (as CH4) the hydrocarbon concentration in the bulk. At this point, a moisture analysis should be performed on several deriming
Carbon Dioxide CO2 0.5 outlets to ensure that the deriming process is successfully finished.
3 For plants with production of pressurized
Nitrous Oxide N2O 5 oxygen by internal compression see also
EIGA Doc 145 (CGA G-4.9) [6]
A dew point of –40℃ to –60℃ verifies that the circuit has been successfully
derimed.

IGC DOC 65/13/E SAFE OPERATION OF REBOILERS/CONDENSERS IN AIR SEPARATION UNITS (Appendix F)
Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 19 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 20
Deriming Internal compression type ASU

Derime the plant every 3 years.

CH4 14.6ppm
The deriming frequency may be lengthened based on operating experience CH4 3000ppb 170kNm3/h 70kNm3/h 35kNm3/h
C2H6 0.5ppm
C2H4 300ppb C3H8
but should be shortened if any of the following abnormalities have occurred: C2H6 100ppb 0.45MPa 5.0MPa 2.5MPa 150ppb
C2H4 60ppb N2O 300ppb
C3H8 30ppb AIR GO2
N2O 60ppb
• abnormal pressure drops in cryogenic equipment Air Booster
(i.e., exchangers, distillation trays);
GN
• high hydrocarbon level in the intake air;
OHX
• frequent switching problems with REVEXs, regenerators, or FEP systems;
0.04MPa CH4 14.6ppm

• repeated instances of minor carbon dioxide breakthrough from the FEP system; P C2H6 0.5ppm
C2H4 300ppb C3H8
150ppb
N2O 300ppb
• change of the environmental conditions to other than the plant design; or

• numerous unplanned plant shutdowns, e.g., power failures.

Internal compression ASU

Mar.13.2019 CONFIDENTIAL Copy

Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 21 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 22

Internal compression type ASU Summary

Physical properties of propane C3H8 in liquefied oxygen In order to safely operate the air separation unit,
Press. Temp. K-value Solubility Concentration the following management is important
[MPaG] [K] [-] [vol.ppm] [vol.ppm]*
0.1013 90.2 3×10 -7 9,800 80,000 Contaminant concentration of the feed air
0.1480 94.0 3×10 -6 10,000 8,000
Contaminant concentration in liquefied oxygen sump
0.3000 102.0 3×10 -5 15,000 800
1.0000 119.6 3×10 -4 30,000 80
Reference
*It shows the liquid composition in the last drop in the liquid phase at equilibrium.
When the C3H8 concentration at the inlet of the oxygen heat exchanger is 24ppb C3H8 . IGC DOC 65/13/E
SAFE OPERATION OF REBOILERS/CONDENSERS IN
In the internal compression type ASU, the operating pressure of the oxygen heat exchanger is designed to be
0.3 MPaA or more, so C3H8 does not precipitate in the oxygen heat exchanger. AIR SEPARATION UNITS

23
Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 23 Mar.13.2019 CONFIDENTIAL Copy
Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 24
 Thank you for your attention.

Mar.13.2019 CONFIDENTIAL Copy

Copy right
right (C)
(C) TAIYO
TAIYO NIPPON
NIPPON SANSO
SANSO CORPORATION
CORPORATION 25