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CMR+ Precooling Process in Hydrogen

Liquefaction Plants
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Contents
Abstract..................................................................................................... ii
1 Background .......................................................................................... 1
2 Process Description ................................................................................ 1
3 Model Description .................................................................................. 1
4 Simulation Results ................................................................................. 3
5 Conclusion ............................................................................................ 5

Abstract
This ASPEN HYSYS example models alternative Cascade Mixed Refrigerant (CMR+)
precooling process in large-scale hydrogen liquefaction plants (150 tonne/d).

The CMR+ precooling process is introduced in the model; it is an extension of the

CMR process with single R290 refrigeration circuit as a partial precooling process.
Feed with a mass flow ratio of mH2/mnelium = 1/10 is cooled down by this CMR+
process. Ortho-para hydrogen conversion is modeled with Chemistry.

It can be used as a starting point for more complex models for process design and
optimization, debottlenecking, and plant and equipment design.

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1 Background
In Paris, December 2015, the Paris Agreement among 195 nations was fulfilled with
commitment of reaching the two degrees global warming target and reduce the global
greenhouse emissions per capita with 8% in 2025 and 9% by 2030. The growth of
demand forecast for a green and clean energy carrier, points in direction of hydrogen,
as an energy commodity for decarbonization of the next-generation transport sector,
as well as to the power generation industry.

Hydrogen from a gravimetric point of view, conceals large amounts of energy. To

store and transport the extensive energy amount, hydrogen gas density must be
increased significantly to compete with other energy storage alternatives, such as
state-of-the-art batteries. The two methods of high-density storage of hydrogen are
by liquefaction or compression.

2 Process Description
The CMR+ precooling process is an extension of the CMR process. The process flow
diagram indicated in Figure 1 shows the basic principle of the cascade. The CMR+
process is equivalent to CMR process except for single propane (R290) refrigeration
circuit as a partial precooling process before the main heat exchanger. The process
flow diagram indicated in Figure 1 shows the basic principle of the cascade; two
separate Single Mixed Refrigerant (SMR) cycles are connected where the first heat
exchanger pre-cools the second cycle, reaching for a temperature level of 130 K.
Similar as the single PRICO+ process the hydrogen and nelium feed conditions are
unchanged, except for a new intermediate temperature level between R290_HEX_1
and MCR_HEX-2.

This ASPEN HYSYS example models CMR+ precooling process in large-scale hydrogen
liquefaction plants (150 tonne/d). It can be used as a starting point for more complex
models for process design and optimization, debottlenecking, and plant and
equipment design.

The model includes the following key features:

 Two SMR cycles
 Cascade Mixed Refrigerant cycle
 Single R290 refrigeration circuit
 LNG heat exchangers model precooling
 Ortho-para hydrogen conversion
 If conditional statement for MCR return stream position

3 Model Description
The alternative Cascade Mixed Refrigerant (CMR+) process was modeled using
ASPEN HYSYS as shown in Figure 1. In this simulation, Hydrogen Package is chosen
for hydrogen, noble gas mixture of neon and helium; the MR mixture are calculated
with Peng-Robinson (PR).

1
 Figure 1: Alternative Cascade Mixed Refrigerant (CMR+) Flowsheet in ASPEN HYSYS

The MR part of the system comprises two closed cycles with multi-stage compression
and after-cooling. The two cycles are designed with respect to the hydrogen cooling
temperature target at each heat exchanger outlet, which results in different working
fluid composition, mass flow, and pressure levels.

The MR streams is entering a two-stage compressor train at a pressure of 4 bar,

which is assumed as a reasonable LP level. The compression is assumed isothermal,
by implementing inter- and after-coolers with an intermediate temperature level of
300 K (to avoid overheating inside the compressor) between the stages. The MR
stream is further cooled by its own LP return stream, counterflow-wise in the main
heat exchanger, down to 210 K for cycle A and 130 K for cycle B. The cold HP stream
is throttled in the expansion valve, resulting in the necessary temperature drop
(below 210 K/310 K) that creates the main cooling power.

The liquid fraction in the return stream (suction stream) is dependent on both
temperature and pressure. In the MR circuit(s), some liquid may be generated in the
return stream(s), as a result of the considerable lower temperature level generated
by the predefined outlet temperature at the cold side of the second heat exchanger
in the CMR process. To avoid liquid in the gas compressors, the liquid fractions are
separated before the compressor inlet, where it is guided through a pumping system,
while gas vapor is guided through the gas compressors. At the end of the compressor
train, the two streams are mixed. For cycle A it goes to R290_HEX_1; for cycle B, it
goes to MCR_HEX-1 or MCR_HEX-2 according to different mixed temperature which
is model with an if conditional statement in the calculator.

The partial precooling approach is single R290 refrigeration circuit, where simple
refrigerators were proposed implemented in the upper temperature region, chilling
the streams to temperatures 268 K (-5 °C) before entering the cryogenic cold box
processes.

For H2 and Nelium, feed with a mass flow ratio of mH2/mnelium=1/10 is cooled down
by this CMR+ cycle. Ortho-H2 and Para-H2 fraction can be viewed in stream H2
conversion tab. Ortho-para hydrogen conversion is modeled with case study Ortho-
Para.

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4 Simulation Results
The chemistry parameter settings are shown in the following Table 1. The initial
conditions of the CMR+ precooling process are given in Table 2. The Ortho-Para
conversion for para-hydrogen composition between temperature 20-300 K is shown
in Table 3. The results for the R290_HEX_1, MCR_HEX-1and MCR_HEX-2 are shown
in Table 4.

Table 1: Chemistry parameter settings

Reaction Type Stoichiometry

1 Equilibrium H2-PARA <--> H2-ORTHO
2 Dissociation H2 --> H2-PARA
Equilibrium Constants
ln(Keq)=A+B/T+C*ln(T)+D*T
A 5.18192049
B -195
C -0.61661082
D 0.000318
Keq Basis Mole fraction

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 Table 2: Parameters applied to CMR+ precooling system

Parameter Value
Hydrogen feed
Feed pressure [Bar] 20
Feed temperature [K] 300
Mass flow [ kg/s] 1.736
Intermediate temperature [K] 210
Precooling temperature [K] 130
Ortho-para fraction (inlet) mol% 75.22-24.78
Para fraction (at 210 K) mol% 26.44
Para fraction (at 130 K) mol% 32.70
Mixed refrigerant cycle A
HX inlet temperature [K] 300
Multi-compression 2+Pump
HX outlet temperature [K] 210
Low pressure [Bar] 4
Isentropic efficiency, compressor [%] 75
Mixed refrigerant cycle B
HX inlet temperature [K] 210
Multi-compression 2+Pump
HX outlet temperature [K] 130
Low pressure [Bar] 4
Isentropic efficiency, compressor [%] 75
Nelium feed
Feed pressure [Bar] 80
Mass flow [ kg/s] 17.36
Neon fraction mol% 25
Helium fraction mol% 75

Table 3: Para-hydrogen composition between temperature 20-300 K

H2 Temp [K] Para-H2 H2 Temp [K] Para-H2 H2 Temp [K] Para-H2

10 - 110 0.3668 210 0.2644
20 0.9984 120 0.3446 220 0.2612
30 0.9679 130 0.3270 230 0.2584
40 0.8760 140 0.3129 240 0.2561
50 0.7529 150 0.3015 250 0.2541
60 0.6396 160 0.2922 260 0.2524
70 0.5501 170 0.2845 270 0.2510
80 0.4830 180 0.2781 280 0.2497
90 0.4331 190 0.2728 290 0.2487
100 0.3955 200 0.2682 300 0.2478

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 Table 4: Stream results for LNG

Inlet T Outlet T Molar Flow Duty UA Hot/

LNG Pass Name
[K] [K] [kmol/h] [kW] [kJ/C-h] Cold
C_4-C_1 259.0 298.0 3965 18691 5.6E+06 Cold
MCR_2a-
291.2 268 6396 -14984 3.4E+06 Hot
MCR_2a-2
R290_H MCR_2b_1-
294.6 268 4315 -1461 7.7E+05 Hot
EX_1 MCR_2b-2'
H2_1-H2_1-2 300.0 268 3100 -797 5.1E+05 Hot
Nelium_1-
300.0 268 7766 -1449 9.3E+05 Hot
Nelium_1-2
MCR_4a-
204.1 260.0 6396 28417 6.6E+07 Cold
MCR_1a
Nelium_1-2-
268 210 7766 -2635 6.3E+06 Hot
Nelium_2
MCR_HE
H2_1-2-H2_2 268 210 3100 -1418 3.4E+06 Hot
X_1
MCR_2a-2-
268 210 6396 -16242 2.9E+07 Hot
MCR_3a
MCR_2b'-
268 210 4315 -8122 2.7E+07 Hot
MCR_3b
MCR_5b-
118.9 204.9 4315 15711 2.1E+07 Cold
MCR_1b
Nelium_2-
MCR_HE 210 130 7766 -3669 4.6E+06 Hot
Nelium_3
X_2
H2_2-H2_3 210 130.0 3100 -1876 2.3E+06 Hot
MCR_3b-
210 130 4315 -10166 1.4E+07 Hot
MCR_4b

5 Conclusion
Development of the next-generation hydrogen liquefaction plant targets in the
direction of Mixed Refrigerant Precooling integration. The Ortho-Para conversion
results for para-hydrogen composition between temperature 20-300 K has a good
match for experimental data. The process simulation in this model has shown the
results of a hydrogen liquefaction precooling process.

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References
[1] Jørgen Eckroll. Concepts for large scale hydrogen liquefaction plants. Norwegian
University of Science and Technology, June 2017