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ABSORTION OF BIOLUBRICANT OXIDATIONABSORTION OF BIOLUBRICANT OXIDATION
PRODUCTS IN NANOPOROUS MATERIALPRODUCTS IN NANOPOROUS MATERIAL
B. Cot o, A. Marcaide, A. Aranzabe, C. Zubizarreta
Fundación Tekniker, Avda. Otaola 20, Eibar, Spain
bcoto@tekniker.es
www.tekniker.es
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Outline
Frame of t he work
Met hodology
Absor t ion simulat ions of oxidat ion products
Molecular Dynamics simulat ions
Fut ure Work
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Frame of t he work
To develop an eco-indicatorbased on biodegradability andtoxicity measurements to fill
the gap for a reliableenvironmental impact
evaluation of lubricants
To promote the use crudeglycerine obtained from usedvegetable oil FAME process
(biodiesel production)transforming it from a no-valueby-product to an added-value
renewable raw material.
To obtain polyglycerol esterderivates from purified crude
glycerine for compressorapplications
To replace harmful antioxidantcompressor oil additives by
means the design of a newcompressor device based on amolecular sieve for a selectivetrapping of oxidation products
The aim of t he project is
the optim isation of t he new
sustainable lif e cycle of an environm entally f riendly and safe compressor oil
6th Framework Programe. I. P.
Soilcy ( 515848)
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Biolubricants
Biolubricants
Additives
Improvedperformance
Enviromentally
Unfrendly
Additives
??????
Biolubricants
Additives
Improvedperformance
Additives
Enviromentally
Unfrendly
??????
Biolubricants
Additives
Improvedperformance
Additives
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Molecular Sieve
Biolubricants
Improvedperformance
Enviromentally
Unfrendly
???
Molecular
Selective
Trap
Additives
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Compressor oil application
Model l ing can help t o select proper mat er ials
Sorpt ive behaviour of t he oxidat ion product s f rom a a t r imet hylolpropane (TMP) est er base oil
inside a nanoporous mat er ial Compressor working condi t ions of pressure and
temperature
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Computational methods
Molecular Dynamics
Simulations
Monte Carlo Absortion
Simulations
Minimun Energy
Configuration Structures
At omist ic model l ing aproach
Forcefield based calcultions
Each at om has a pot ent ial energy associat ed t o surrounding
at oms Forcef ields contains paramet ers
for t he energy expresions
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Mat er ials St udio and Compass Forcefield
Mat er ials St udio 4.2
COMPASS Forcef ield
Widely Val idat ed
13 Terms
Bond and non bonding
interactions
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Molecules and Sorbent
Cromatographic Analysis 2-Decanone2-
UndecenalDecanoic
Acid
Nonanoic
AcidDecanal NonanalNanoporous Material
Oxidation Products Molecules
9 9.5 10 10.5 11 11.5 12 12.5 13 13.5 14 14.5
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
0.05
s e ñ a l
c r o m a t o g r a f i c a ( U . A . )
GCM.chrom. TMP oleate 120h
GCM.chrom. TMP oleate 72h
GCM.chrom. TMP oleate 48h
GCM.chrom. TMP oleate 27h
GCM.chrom. TMP oleate 0h
Tiempo de retención (min)
Pico 1
Pico 2
Pico 3
Pico 4
Pico 5
Pico 6
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Energy minimizat ion
242,810209,81011,510Decanoic Acid
241,840205,12012,3202-Undecenal
227,430194,09011,546Decanal
226,800193,50011,5052-Decanone
215,570183,47010,197Nonanoic Acid
208,330175,66010,122Nonanal
Surface Area ( Ǻ2)Occupied Volume ( Ǻ
3)Length ( Ǻ)Molecule
Connolly Surfaces:Occupied Volume and
Surface Area2-Undecenal
Geometry
optimization
·Steepest Descents
·Conjugated Gradient
Energy
Minimization
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Comput at ional Uni t Cel l
Free Pore Volume:
3.4 nm3
• (100) Surface
• Vacuum Slab: 2D Boundary
Condition• Computational Cell:
a = 2 nm; b = 1.33 nm; c = 8 nm
• Geometry optimization• Connolly Surfaces
• Occupied Volume = 7.23 nm3
• Surface area = 2.89 nm3
• Free Volume = 14.05 nm3
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Mont e Car lo Met hods
Grand Canonical ensamble
Syst em can exchange energy and part icles wi t h a surrounding reservoir
Resorvoir is described by t emperature and fugacit ies so i t is not necessary to simulat e i t in a explici t way
Mont e Car lo Biased Method
Fixed pressure simulat ions
Trial configurations are generated with a probability
Acceptance probabil i t y depends on t he energy of t he
system congigurat ion generated Torsional degrees of f reedom are taken into account
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Absort ion Isotherms
• Sorpt ion was studied for T andP from room condit ions up tothe working condit ions of a
compressor for each molecule
• Sorpt ion Isotherms werecalculated
1,173-525,93717,21518,000Nonanal
1,073-545,81815,74417,000Decanal
1,066-1005,99215,64117,000Nonanoic Acid
0,998-988,18914,65515,000Decanoic Acid
0,990-591,86814,52716,0002-Decanona
0,889-973,82513,04814,0002-Undecenal
Maximun Density
(molecules/nm3)
Average Energy
(kcal/mol)
Average LoadMaximun
Load
Molecule
298 K
1 Atm
2-decanone sorption Isotherms
10
11
12
13
14
15
16
17
18
19
20
0 1 2 3 4 5 6 7 8 9 10 11
P (Atm)
N u m b e r o f a b s o r b e d m o l e c u l e s
2-Decanona 298 K
2-Decanona 358 K
2DEcanona 378 K
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Sorpt ion isobares, Isost er ic heat s and prefer red absor t ion si t es
Sorption Isobares 10 atm
12
13
14
15
16
17
18
19
20
21
278 298 318 338 358 378
T (K)
N u m
b e r o f a b s o
r b e d
m
o l e c u l e s
Nonanal
Decanal
Nonanoic Acid
Decanoic Acid
2-Decanone
2- Undecenal
Isosteric heats
25
30
35
40
45
50
0 2 4 6 8 10 12
P (Atm)
I s o s t e r i c
h e a t ( k c a l / m o l )
Decanoic Acid 298 K
Decanoic acid 358 K
Decanoic Acid 378 K
Density of absorption profiles of
nonanal at 358 K 10 atm
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Fixed Pressure Calculat ions
• Fixed Pressure calculations
allow to obtain the
minimun energy
configurations for givenconditions
• Detailed view of the
system is available to
study specific interationsand conformational
analysis
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Molecular Dynamics Simulat ions
Molecular Dynamics
Simulations
Minimun Energy
Configuration Structures
Monte Carlo Absortion
Simulations
Minimun Energy
Configuration Structures
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Molecular Dynamics
Newt on’ s equat ion is solved for a given pot ent ial (COMPASS)
Verlet integration
1.5 ns simulat ions St ep 2 f s.
NPT Ensemble
Berendsen Thermost at Berendsen Barost at
• Atomic Trajectories
• Dinamical Behaviour
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Molecular Dynamics
Nonanal 298 K 1 atm Nonanal 358 K 10 atm
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Traj ect or ies Analysis
Nonanal Mean Square Displacement
0
100
200
300
400
500
600
700
0 200 400 600 800 1000 1200 1400 1600
Time (ps)
M e a n
S q u a r e D i s p l a c e m
e n t ( Å 2 )
T = 298 K; P = 1 Atm
T = 358 K; P = 5 Atm
T = 358 K; P = 10 Atm
Diffusion Coefficient
6,79·10-45,84·10-44,12·10-4Diffusivity(nm2 s-1)
T=358K; P=10atmT=358 K; P=5atmT=298 K; P=1atmNonanal
Conformational analysis
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Work in Progress & Fut ure Work
Molecular Dynamics Simulat ions Fut ure Work
Absort ion simulat ions wit h mixtures of molecules
Dif ferent mat erials
Compare wit h experiment s
Funct ional izat ion and/ or doping of t he nanopororus mat erials
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Summary
Molecular Model l ing simulat ions have been carr ied out t o
st udy t he absort ion of oxidat ion producs of an TMP est er oil in a porous nanomat er ial f or compressor applicat ions Geomet ry opt imizat ion was done t o obtain lengt hs and
volumes f or t he modelled syst em MC simulat ions were per formed t o st udy t he sorpt ion
behaviour of t he oxidat ion product s MD calculat ions were per formed in order t o st udy t he
dynamic behaviour of t he syst em
Next st eps wi l l involve ot her sorbent nanomat er ials and comparison with experimental results
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Acknowledgement s
U.E. - 6t h FP –IP Soi lcy (Cont ract 515848 ) Basque Count ry Government . Saiot ek
Program
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THANK YOU FOR YOUR ATTENTION