21GRD06 Me CCUS
Repo on
he me ological in as uc u e comp ising he ins umen s adop ed o
de e mine he he mophysical p ope ies o mix u es o in e es o
CCUS p ocesses. The epo will include a leas 2
simpli ied o mula ions o he p edic ion o he densi y o ypical CO2
mix u es (in liquid and gas phase), sui able o use
by low compu e s o suppo he CCUS p ocess design.
D8 - A4.3.6
O ganisa ion name o he lead pa icipan o he deli e able:
Is i u o Nazionale di Rice ca Me ologica
S. Lago (INRiM), P. Albe o Giuliano Albo (INRiM), F. Gugole (VSL), S. Nadi i
(PTB), S. Bell (NPL), P. Ca oll (NPL), S. Kai y (NPL), S. Zhou (NPL), M. Thol
(RUB), R. Span (RUB), A. O ega (UVa), X. Mendez (UVa), A. Fa ee (DTU), L.
Chaube (Ai Liquide FuE)
Due da e o he deli e able:
30.09.2025
Ac ual submission da e o he deli e able:
07.10.2025
Con iden iali y S a us: PU - Public, ully open ( emembe o deposi public deli e ables in a us ed eposi o y)
Deli e able Co e Shee
Funded by he Eu opean Union. Views and opinions exp essed a e
howe e hose o he au ho (s) only and do no necessa ily e lec hose
o he Eu opean Union o EURAMET. Nei he he Eu opean Union no
he g an ing au ho i y can be held esponsible o hem.
The p ojec has ecei ed unding om he Eu opean Pa ne ship on
Me ology, co- inanced om he Eu opean Union’s Ho izon Eu ope
Resea ch and Inno a ion P og amme and by he Pa icipa ing S a es.
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TABLE OF CONTENTS
1 Summa y 3
2 The me eo ological in as uc u e o p ope ies o CO2 he mophysical sys ems 4
4. A dedica ed equa ion o designing CO2 anspo in as uc u es 5
5. CO2 gas mix u es: a compa ison among EOS-CG-2021, Soa e-Redlich-Kwong (SRK) and
Peng-Robinson (PR) equa ions o s a e 7
5.1. Nume ical compa ison on CO2 mix u es ele an o he CCUS indus y 8
6. A dedica ed o mula ion o designing ca bon cap u e sys ems 10
7. Conclusion 14
8. Fo mula ions a ailable on Zedono 14
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21GRD06 Me CCUS
1 Summa y
Wi h he aim o alida e models needed o suppo he design o CCUS p ocesses and o p o ide
he necessa y suppo o low me e ing ope a ions in ol ing CO2 mix u es in he liquid phase,
apou phase o in supe c i ical condi ions, signi ican p og ess was made on he s udy o amines,
hei mix u es wi h CO2 and H2O, and o anspo a ion o CO2 mix u es in pipelines.
This epo desc ibes he cha ac e is ics o he me ological in as uc u e implemen ed du ing he
de elopmen o he Me CCUS p ojec wi h he aim o ob ain he he mophysical p ope ies o CO2
mix u es o in e es o indus ial applica ions. To p o ide a simple access o he measu ed
p ope ies, wo simpli ied equa ions o s a e we e implemen ed: one o designing CO2 anspo
in as uc u e and one o modeling ca bon cap u e p ocesses using aqueous amines.
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2 The me eo ological in as uc u e o p ope ies o CO2 he mophysical
sys ems
Wi h he aim o p o ide p ocedu es, measu emen s and he speci ic ins umen a ion needed o
build up con idence in he sa e and e icien ope a ion o pipelines anspo ing CO2 mix u es,
inno a i e me hods o he online moni o ing o e en ual phase ansi ions in he CO2 h ough he
measu emen s in-si e we e de eloped. In pa icula , wo spec oscopy-based sys ems we e
de eloped o online moni o ing o phase ansi ions in CO2 such as gas o supe -c i ical luid lows.
The i s sys em is based on a -UV me hod and he second one on NIR me hod. Bo h sys ems
we e success ully es ed a labo a o y condi ions wi h use o a comme cial CO2 gas cylinde wi h
deep ube and alida ed a Ex a eX company (Nancy, F ance). The measu emen s a Ex a eX
ha e been done on a p op ie a y dedica ed se up, whe e i was possible o u ilize gas-,
supe -c i ical o liquid- phase CO2 lows. The a -UV and NIR sys ems ha e been coupled o he
Ex a eX’s se up. The a -UV and NIR measu emen s o CO2 gas-supe -c i ical phase ansi ions a
Ex a eX ag ee wi h he labo a o y measu emen s. DTU is in es iga ing he possibili ies o a
pa en applica ion o he NIR me hod.
Mo eo e , conside ing ha e en a small amoun o wa e can chemically eac wi h he CO2 o o m
co osi e compounds, pa o he con ibu ion was dedica ed o he de elopmen o a calib a ion
me hod o he online humidi y senso s ha a e used in CCUS p ocesses. NPL ha e de eloped
a new acili y o co osion es ing o pipeline s eel in impu i y-con aining dense phase CO2
en i onmen . Me hods o con olling and measu ing he concen a ion o impu i ies (H2O and O2)
in dense phase CO2 du ing co osion es ing we e success ully op imised and alida ed.
A obus es me hod was success ully de eloped o assess he co osion a e o X65 pipeline s eel
in dense phase CO2 con aining H2O and O2 a 80 ba and 25 °C. Key s eps o he me hod include:
1. Deae a ion: Adequa e deae a ion (i.e., O2 below 1 ppm ) a ambien p essu e equi es pu ging
he au ocla e wi h CO2 wi h a olume a leas 15 imes g ea e han he au ocla e olume. This
p o ocol p e en s exposu e o es specimens o esidual a mosphe ic O2 du ing es ing,
he eby a oiding a e ac s in co osion a e measu emen s.
2. Tes En i onmen Es ablishmen : G adual p essu isa ion (~ 40 minu es) combined wi h
con inuous s i ing a 700 pm enables apid and uni o m dis ibu ion o impu i ies wi hin he
au ocla e, achie ing a ge concen a ions nea es specimens wi hin 1 hou . This p ocedu e
minimises unce ain y in exposu e ime and es en i onmen composi ion, which is c i ical o
sho -du a ion co osion es s.
3. Dep essu isa ion: Dilu ing he es en i onmen wi h pu e CO2 o educe H2O concen a ion
below 500 ppm , ollowed by con olled dep essu isa ion (1 L/min o 3 L/min), e ec i ely
p e en s a e ac s in co osion a e measu emen s a ising om unin ended H2O condensa ion
on es specimens.
Co osion es s on X65 s eel in H2O-sa u a ed dense phase CO2 conduc ed using he de eloped
obus es me hod demons a ed good epea abili y. The co osion p oduc s we e uni o m and
semi-p o ec i e, wi h no signi ican di e ence be ween ho izon ally and e ically o ien a ed
specimens. This esul con ibu ed o he de elopmen o an in e na ional bes p ac ice guide:
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AMPP Guide 21577 - Labo a o y Co osion Tes ing o CO2 T anspo and Injec ion, suppo ing
s anda disa ion e o s in co osion es ing o CO2 in as uc u e.
A u he ac i i y was dedica ed o he implemen a ion o he s anda d es p ocedu es necessa y o
ensu e he sa e and cos -e ec i e selec ion o ma e ials o CO2 pipelines. A obus and
ep oducible es me hod was de eloped ha is mo e ep esen a i e o condi ions in se ice han
con en ional es me hods ha ha e been employed o da e in he li e a u e.
NPL has adap ed he use o an exis ing comme cially made humidi y gene a o o ope a e wi h
CO2. A Thunde 3900 Low Humidi y gene a o was adap ed so ha i can dynamically gene a e
humidi y alues in CO2 in he os -poin empe a u e ange -60°C o 0 °C (equi alen o wa e
apou amoun ac ion ange 10 µmol mol-1 o 0.5 %). This in ol ed conside ing ma e ials
compa ibili y, ope a ing ange ele an o CCUS, gas-speci ic low measu emen and con ol, he
CO2 phase diag am, sa e exhaus o he gas, and es ablishing ha ope a ion in he ice egime
minimises any issue o dissol ed CO2. Fo CO2, he e is li le published li e a u e o wa e apou
enhancemen ac o , bu NPL has iden i ied a ailable da a and used his o enable con e sion
om os poin o amoun ac ion. The p ima y aceabili y o dew-poin empe a u e uni s (°C) is
ia a e e ence pla inum esis ance he mome e (PRT) calib a ed agains NPL Tempe a u e
S anda ds. The adap ed s anda d was used o calib a e a chilled-mi o hyg ome e in e ms o
os poin in bo h CO2 and ai .
Finally, an expe imen al appa a us comp ising an acous ic/mic owa e esonan ca i y and a
simpli ied sa u a o was designed and ealized in o de o be able o measu e speed o sound
and e ac i e index o gaseous pu e CO2 and CO2 + H2O mix u es. Tes measu emen s we e
ca ied ou in A in o de o e alua e he pe o mances o i . Using he no el expe imen al sys em,
comp ising an acous ic/mic owa e esonan ca i y and a simpli ied sa u a o , measu emen s o
speed o sound and e ac i e index o gaseous pu e CO2 and humid CO2 a wo iso he ms (323
and 330) K, spanning he o e all p essu e ange be ween 0.5 and 1.2 MPa wi h wa e mole
ac ions 0.5% and 1%, espec i ely, we e ca ied ou ; besides along an isocho ic line a 0.7 MPa
a 11 empe a u es be ween 323 K and 357 K, wi h a wa e mole ac ion x = 1.0 % (by mass).
Wi h he aim o es ima e he in e ac ion ca bon dioxide – wa e i ial coe icien , measu emen s will
be con inued spanning beyond he li e ime o he p ojec .
4. A dedica ed equa ion o designing CO2 anspo in as uc u es
Mul ipa ame e s equa ions o s a e ha e p o en o be able o p o ide p edic ions o he
he modynamic p ope ies o mix u es wi h an accu acy ha is compa able o he one o he
expe imen al da a when hei pa ame e s a e adjus ed using a ailable expe imen al measu emen
esul s. Howe e , he upda e o such equa ions eques s ime, especially when hey a e needed o
desc ibe mul icomponen s mix u es. Fo his eason, while upda ed o mula ions will be a ailable, a
simpli ied model is p oposed o suppo he design o CO2 comp ession, lique ac ion and pumping
sys ems. Mo e han he accu acy o he o mula ion, i s simplici y was p i ileged so ha i can be
easily implemen ed in open- and closed-sou ce designing so wa e pla o ms.
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Conside ing ha CO2 applica ions can ange om low o high empe a u e cycles in ol ing
necessa y o some imes undesi ed phase ansi ions, i has been chosen o adop cubic equa ions
o s a e op imized in he ange o CCUS p ocesses. His o ically, cubic equa ions a e u ilized o
designing hyd oca bon dis illa ion and hei coe icien s a e calcula ed speci ically o ep oduce he
sa u a ion cu e and he sa u a ed liquid densi y. Howe e his is no he main scope o he CO2
anspo applica ions whe e he es ima ion o he mophysical p ope ies o CO2 mix u es a e
necessa y o de ine dimensions and ange o ope a i i y o comp esso s and pumping sys ems. So
ha , he coe icien s o a Pa el-Teja equa ion o s a e we e ecalcula ed o pu e CO2, O2, SO2, A ,
CO and N2 o op imize he p edic ions in he ange o empe a u e be ween 263 K and 423 K, and
o p essu e up o 12 MPa. A ailable expe imen al measu emen s o mix u es o he selec ed
componen s we e used o de e mine he bina y in e ac ion coe icien s and hen hey ha e been
used o p edic he densi y o a qua e na y mix u e composed by CO2 + N2 + O2 + A . Compa isons
o he implemen ed model wi h Soa e-Redlich-Kwong (SRK), Peng-Robinson (PR) cubic equa ion
and wi h EOS-CG-2021 undamen al equa ion is p o ided.
De ails o he adop ed Pa el-Teja (PT) equa ion can be ound in [Pa el e al.] while only necessa y
in o ma ion o implemen his model a e he ea e epo ed. PT equa ion is a cubic equa ion
explici in p essu e p as a unc ion o he empe a u e T and mola olume :
𝑝(𝑇,𝑣)= 𝑅 𝑇
𝑣−𝑏 −𝑎(𝑇)
𝑣(𝑣+𝑏)−𝑐(𝑣−𝑏)
(1)
whe e R=8.31446 J/(mol K) is he mola gas cons an , b and c a e he co- olumes and a(T) is he
he mal unc ion. The pa ame e s o he equa ion a e he c i ical empe a u e Tc, and he c i ical
p essu e pc while he coe icien s o be i ed a e ζc and one, o mo e, coe icien s used o de ine
he unc ion a(T) no epo ed in he equa ion (1). F om hose quan i ies a, b and c can be ob ained.
Howe e , o a sake o simplici y, inal exp essions o a, b and c a e explici ly gi en in able 1.
Equa ion (1) has he p ope y o become an SRK equa ion when c=0 and a PR equa ion when c=b.
Thanks o his lexibili y, PT equa ions pe o m, usually, a bi be e han bo h SRK and PR bu i s
quali y emains in he ange o expec ed capabili y o cubic equa ions hus non compa able wi h
pe o mances o mul ipa ame e s equa ions o s a e like BWR and equa ions in Helmhol z ee
ene gy.
To calcula e he densi y exp essed in kilog am pe cubic me e , he p essu e mus be exp essed in
pascal and he empe a u e in kel in. Sol ing equa ion (1), he mola olume , exp essed in cubic
me e s pe mole, is ob ained while he co esponding densi y can be calcula ed as ρ=m/ , when
he mola mass m is exp essed in kilog ams pe mole.
To p edic he p ope ies o a mul icomponen mix u e, a leas he bina y in e ac ion pa ame e s
a e needed when he mixing ules desc ibed in Pa el e al. a e adop ed. Thanks o he s abili y o
cubic equa ions, he de e mina ion o in e ac ion coe icien s can be usually pe o med using e y
ew expe imen al poin s since hey a e app oxima ed by cons an s and hus a e no dependen on
he empe a u e, as epo ed in able 1. In he p oposed app oxima ion, he coe icien s no
epo ed in he able ha e been emo ed om he model since his simpli ied app oxima ion
conside s only mix u es wi h a mola ac ions o CO2 highe han 90 %. No heo e ical o mula ions
o e alua ing he bina y in e ac ion coe icien s we e adop ed. Values epo ed in able 1 seem
un easonable since expec ed alues should be posi i e and in a bounda y o 0.1. This is p obably
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a side o ha ing emo ed some in e ac ions ha canno be conside ed negligible. This p oblem will
be co ec ed in u u e con ibu ions.
Table 1. Bina y in e ac ion coe icien s k12 o be used in he e m (1-k12) o Pa el-Teja mixing ules.
Mix u e
k12
Mix u e
k12
Mix u e
k12
CO2-CO
–0.2231
CO2-O2
0.1860
CO2-SO2
-0.0894
CO2-N2
0.8833
CO2-A
-4.9065
5. CO2 gas mix u es: a compa ison among EOS-CG-2021, Soa e-Redlich-Kwong
(SRK) and Peng-Robinson (PR) equa ions o s a e
Co ec ly es ima ing he he modynamic p ope ies o a eal gas is a challenge ha scien is s ha e
been ying o sol e o mo e han a cen u y. A miles one in ha di ec ion was achie ed by an de
Waals and his p oposed equa ion o s a e (EOS) o eal gases and liquids ( an de Waals, 1873).
This equa ion was he i s EOS ela ing he p essu e, olume, numbe o molecules and
empe a u e in a luid. The Van de Waals EOS o mula ion is cubic in olume and was he i s
EOS ha could ep esen a wo-phase sys em (i.e., liquid and gas). Since hen, many modi ica ions
o his equa ion ha e been p oposed o, e.g., enhance he phase beha iou p edic ions o he
model. Cu en ly, he equa ion p oposed by Soa e-Redlich-Kwong (SRK) (Soa e, 1971) and he
one p esen ed by Peng-Robinson (PR) (Peng & Robinson, 1976) a e he wo cubic EOS ha a e
used he mos bo h in he indus y and in he scien i ic communi y. These EOS ind ample
applica ion hanks o hei ease o use and low compu a ional equi emen s al hough do no always
each he equi ed le el o accu acy.
An al e na i e o cubic EOS is o use Helmhol z-ene gy based EOS. One o he mos no able
examples o his class o EOS is gi en by he GERG-2008 EOS o na u al gas mix u es (Kunz &
Wagne , 2012). EOSs based on he Helmhol z ene gy include a mul icomponen mix u e model
based on he combina ion o bina y mix u e models o he cons i uen s. Each bina y-speci ic model
is buil on highly accu a e Helmhol z ene gy equa ions o s a e o pu e luids, which a e hen
combined wi h in e ac ion pa ame e s i ed o expe imen al da a. The le el o uning o each
bina y sys em hus depends on he a ailabili y o expe imen al da a. Howe e , as mo e and mo e
da a become a ailable, EOS o mula ions based on he Helmhol z ene gy become mo e and mo e
accu a e as i was he case o he GERG-2008 EOS.
The CCUS (ca bon cap u e, u ilisa ion and s o age) indus y has been widely using cubic EOS
howe e CCUS mix u es o en equi e he modelling o chemical associa ion and pola
componen s, which is no p ope ly cap u ed by cubic EOS. I is possible o include such modelling
in cubic EOS, a he expense o inc easing he complexi y o he EOS and limi ing he abili y o he
EOS o ex apola e beyond expe imen al da a, hus losing some o he a ac ion o cubic EOS. In
ecen yea s, he scien i ic communi y has de eloped a Helmhol z ene gy EOS speci ic o
CCUS-mix u es, EOS-CG (Ge ne & Span, 2016), which is being upda ed and cons an ly
imp o ed as mo e and mo e expe imen al da a on CO2 mix u es wi h ele an impu i ies a e being
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collec ed. I is impo an o men ion ha al hough GERG-2008 includes many CCUS- ele an
compounds, hese a e ea ed as mino componen s in he o mula ion o he GERG-2008.
The e o e, when using GERG-2008 o he calcula ion o he modynamic p ope ies o a
CCUS- ele an mix u e he unce ain ies associa ed wi h he EOS esul can exceed hose o he
expe imen al measu emen s.
In Me CCUS, i has been pe o med a nume ical compa ison o he p edic ions p o ided by SRK,
PR and EOS-CG-2021 agains expe imen al measu emen esul s a ailable in he li e a u e on
CO2 mix u es (wi h CO2 as he mos abundan componen ). Fo he compa ison, we use SRK, PR
and EOS-CG as implemen ed in TREND 6.0 (Span, e al., 2025).
5.1. Nume ical compa ison on CO2 mix u es ele an o he CCUS indus y
As a i s compa ison, we analyse he p edic ions o EOS-CG, SRK, PR and PT (as newly
implemen ed in his p ojec ) on bina y mix u es o ca bon dioxide and sul u dioxide, oxygen o
ca bon monoxide. The p esence o any o hese h ee impu i ies may ha e a al consequences o
he CO2 anspo a ion sys em causing, e.g., co osion and unning duc ile ac ion (Simonsen,
Hansen, & Pede sen, 2025). I is he e o e o i al impo ance o moni o he p esence o hese
impu i ies in CCUS p ocesses. The expe imen al da a used o he compa ison a e gi en in
(Gimeno, A al, Velasco, Fe nández, & Blanco, 2018) o he mix u e wi h sul u dioxide,
(Man o ani, Chiesa, Valen i, Ga i, & Consonni, 2012) o he mix u e wi h oxygen, and (Souza,
He ig, Span, & T usle , 2019) o he mix u e wi h ca bon monoxide.
The compa ison is pe o med in e ms o he a e age o absolu e de ia ions (AAD), which is
calcula ed as
𝐴𝐴𝐷= 100
𝑁𝑖=1
𝑁
∑|ρ𝑒𝑥𝑝, 𝑖−ρ𝐸𝑂𝑆,𝑖|
ρ𝑒𝑥𝑝,𝑖
(2)
whe e deno es he expe imen al alue o he densi y o he CO2 mix u e, and he densi y
ρ𝑒𝑥𝑝 ρ𝐸𝑂𝑆
alue p edic ed using an equa ion o s a e. We calcula ed he AAD pe phase, whe e we es ima ed
he c i ical poin based on he cha ac e is ics o he pu e componen s and on he p opo ion o he
componen s. The esul s a e summa ized in Table 2.
In mos cases o he mix u es wi h sul u dioxide and oxygen, he EOS-CG-2021 (Neumann, He ig,
Bell, Beckmülle , Lemmon, Thol & Span, R., 2023). p o ides p edic ions wi h a lowe AAD han he
cubic EOS. Howe e , in he case o he mix u es wi h ca bon monoxide EOS-CG-2021 e u ns
conside ably la ge AAD alues, while he i ed PT equa ion e u ns AAD alues simila as o he
o he mix u es.These esul s emphasize ha some o he bina y models (e.g., o ca bon
monoxide) in EOS-CG-2021 need mo e da a o be e ep esen he in e ac ions be ween he
di e en componen s (o a leas in he empe a u e and p essu e anges he e conside ed).
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Table 2: AAD calcula ed pe phase and pe EOS on bina y mix u es o CO2 wi h CCUS ele an impu i ies.
Fo all mix u es, he amoun ac ion o CO2 is calcula ed as cmol/mol whe e XX is ei he
𝑥𝐶𝑂2=100−𝑥𝑋𝑋
SO2, O2 o CO.
Mix u e
Phase
EOS-CG-2021
SRK
PR
PT
𝑥𝑆𝑂2=.69
cmol/mol
Gas
0.98
1.59
1.63
1.35
Liquid
0.36
11.29
2.59
2.28
𝑥𝑆𝑂2=4.68
cmol/mol
Gas
3.19
3.72
2.36
2.22
Liquid
2.84
12.69
3.16
2.04
𝑥𝑂2=6.07
cmol/mol
Gas
1.44
1.79
2.17
2.30
Supe c i ical
1.70
8.81
2.16
2.31
𝑥𝑂2=12.91
cmol/mol
Gas
1.72
1.90
2.75
2.25
Supe c i ical
2.54
7.78
1.46
2.25
𝑥𝐶𝑂=5.031
cmol/mol
Gas
7.31
8.00
6.22
1.25
Liquid
3.49
12.53
4.40
2.35
Supe c i ical
13.52
20.22
14.34
2.46
𝑥𝐶𝑂=10.107
cmol/mol
Gas
4.13
5.06
3.12
1.78
Liquid
6.27
14.14
5.75
2.13
Supe c i ical
8.10
15.02
8.94
1.95
Alongside he EOS p edic ions o bina y mix u es, we analysed also he p edic ed densi y o a
mo e complex mix u e o ca bon dioxide ( cmol/mol), ni ogen ( cmol/mol),
𝑥𝐶𝑂2=89.83 𝑥𝑁2=5.05
oxygen ( cmol/mol) and a gon ( cmol/mol) o which expe imen al esul s a e
𝑥𝑂2=3.07 𝑥𝐴𝑟=2.05
gi en in (Naze i, Chapoy, Bu gass, & Tohidi, 2017). These impu i ies can se iously comp omise he
in eg i y o he pipelines and hus inc ease he isk o ailu e o CO2 anspo a ion sys ems. Resul s
a e epo ed in Table 3.
In his case, he i ed PT EOS has he lowes AAD o all he h ee phases conside ed, wi h
EOS-CG-2021 e u ning simila AAD alues in wo ou o h ee phases. Howe e , he AAD alues
a e in gene al qui e high, as seen also o he bina y mix u e CO2 + CO and migh no mee he
accu acy equi emen s needed in he CCUS indus y. Thus mo e wo k should be done o imp o e
he bina y-speci ic models in EOS-CG-2021 o he bina y in e ac ion pa ame e s in PR o in he
p oposed PT EOS.
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21GRD06 Me CCUS
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