rapid analysis of polymers and petroleum by ion-mobility mass spectrometry
TRANSCRIPT
Rapid analysis of polymers and petroleum by I bilit t tIon-mobility mass spectrometry
Carlos AfonsoCarlos AfonsoUniversité de RouenLaboratoire COBRAPl t t h i C2iPlateau technique C2iorga
1
Context
Carlos AFONSO Pierre GIUSTI Brice BOUYSSIERECarlos AFONSO, Pierre GIUSTI, Brice BOUYSSIERE
2
Ionization of polymers
• Polymer : large molecular diversitydiversity– Heteroatoms (PEG, PMMA…)– Unsaturated (PB)
A ti (PS) PMMA 2
CH3
O OCH3 n
PS 7
n
PDMS 1
n
SiO
CH3
CH3
– Aromatics (PS)– Saturated (PE, PP…)
• Ionization– M+•
– [M+H]+, [M+Na]+, [M+Met]+
Solubility• Solubility– In mass spectrometry the majority of
ionization methods implies to l bili lsolubilize samples
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ASAP: Atmospheric Solids Analysis Probe • Sample deposited onto glass tube
– Use of pure sampleno solvent required– no solvent required
• Desorption using a hot N2 flux• Ionization from plasma generated
by a corona dischargeby a corona dischargeCharge transfer (M+•)
N2 + e– → N2+• + 2e–
N +• + 2N → N +• + NN2 + 2N2 → N4 + N2N4
+• (or N2+•) + M → M+• + xN2
Proton transfer (MH+)N4
+• + H2O → H2O+• + 2N2H2O+• + H2O → H3O+ + HO•
H3O+ + n(H2O)+N2 → H+(H2O)n+N2H+(H O) M MH+ (H O)
Proton transfer (MH )
H+(H2O)n + M → MH+ + n(H2O)
C.N. McEwen, R.G. McKay, and B.S. Larsen, Anal. Chem. 2005, 77, 7826-78314
ASAP: examplesParaffins
C72
2×CH2
• Change conditions to control ionizationN2 + MeOH MH+
M+•M+•M+•
MH+MH+MH+
N2 MM+•
M+•M+ 2
5
APPI, APCI, ASAP, ESI• ESI
– Polar compoundsL l l t i
Complementary ion sources to analyse molecular diversity
– Large molecules, proteins, polymers…
– Fragile Molecules• APCI ESI
100,000
10 000DP-APCI(pyrolysis)• APCI
– Low polarity– < 2000u
Small molecules
ESI
APPI
10,000
1,000
Mas
s (u
)
(pyrolysis)
– Small molecules• APPI/ASAP
– Non polar moleculesASAP l l l
APPIDP-APCI APCI
100
– ASAP can analyze low polar high mass molecules (pyrolysis)
Non polar very polarPolarity
6
Chromatographic separation ?• Drift tube
– Electric field and buffer gas
IM spectrum
• Ion mobilityvd K E
• Ω Collision cross section (Å2)– Related to size and shape
d
7
IMSTR1000 Handheld Explosive Trace Detector
• Homeland securityy
Smiths Detection (Ionscan 400B)Smiths Detection (Ionscan 400B)
8G. Reid Asbury et al. / Talanta 50 (2000) 1291–1298
T. Khayamian et al. / Talanta 69 (2006) 795–799
Ion Mobility - Mass Spectrometry
2D map
nten
sity Mass
spectrum
m/z
in
9
• Ion coordinats = m/z + drift time + intensity
Molecular mapping by ASAP-IM/MS• The 2D-MAP allows to spread the ions
– Increase peak capacity 1103084.raw : 1
Ion detection algorithm
DBE:n-paraffins: CnH2n+2
CcHhNnOoSs
DBE = c – h/2 + n/2 + 1DBE
perylene
10
Polypropylene (PP) and additives
Recycling ?
11C. Barrere, F. Maire, C. Afonso, P. Giusti, Anal. Chem. 2012, 84, 9349-9354
ASAP-IMMS of PP1: stabilizers study
TWIM
m/z mobility plotASAP-MS spectrum
TWIM allo additionalNo pyrolysis residue ? TWIM allow additional signals to be evidenced
C. Barrere, F. Maire, C. Afonso, P. Giusti, Anal. Chem. 2012, 84, 9349-9354 12
ASAP-IMMS of PP2: polymer and stabilizers
(- 4.9 ppm)
m/z mobility plot
(+ 4.9 ppm)Pyrolysisresidues
(+ 1 1 ppm)
(- 2.2 ppm)
(+ 1.1 ppm)
2 stabilizers identifiedPyrolysis residues distributions similar to PP1
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ASAP or DIP-APCI: a complex ionization processprocess
e−
IonizationBy charge exchange
N2 N2+•
e
Traces of O2
pyrolysis
Traces of O2and H2O
?PP
PyrolysisPyrolysisproducts
R.B. Cody, Anal. Chem. 2009, 81, 1101–110714
PE/PPPE PP
339.3621 391.2842
295.2995323.3308
339.3621353.3414365.3778379.3934
391.2842
(a) PE
PE PP
419.3155
300 325 350 375 m/z
353.3414395 3884
(b) PP
311.2945
395.3884437.4353479.4823
521.5292563.5762
C3H6C3H6 C3H6
PP
269.2475605.6231
647.67010689.7170
731.7640
200 300 400 500 600 700 m/z
15Differentiation of PP and PE
PE-PP
PEDBE 0 5
DBE 0.5
DBE 0.5
PPPP
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Oxygen containing species for PE and PPLow DBE species detected for PE not for PP
PP vs PEPE PPPE PP
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C. Afonso, M. Farenc, M. Witt, K. Craven, C. Barrère-Mangote, P. Giusti, 63rd ASMS conf. 2015 Saint Louis, USA
IM-MS m/z 300-400
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IM-MS m/z 313-327
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IM-MS m/z 323
DBE 2.5
DBE 1.5DBE 0.5
DBE 2.5
DBE 3.5
DBE 4.5
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Cyclic species at low drift time ?
Biodegradable polymers and blends: on the road of materiomicsthe road of materiomics
• Aliphatic polyestershydrolysable ester bonds– hydrolysable ester bonds
• Renewable Resource: polylactic acid (PLA)
HOO
OHn
• Polyethylene
72.0211
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ASAP MS of PLA-PE blend 30:70
[PLA6+H]+
[PLA +H]+
[PLA10+H]+
[PLA5+H]+
[PLA +H]+
• No detection of PE ions !
[PLA16+H]
• Only PLA ions detected
22C. Barrère, W. Selmi, M. Hubert-Roux, T. Coupin, B. Assumani, C. Afonso and P. Giusti, Polym. Chem., 2014, 5, 3576
ASAP-IMSMS PLA-PE blend 30/70PE
PLA
PLA ions are easily distinguished from PE ions as they are significantly more compact (folded)
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Polymer chemistry (back cover)24
Oil and petroleum distillates
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Diesel hydrodesulfurization (HDS)
Catal. Sci. Technol., 2011, 1, 23–42
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F. Maire, K. Neeson, R. Denny, M. McCullagh, C. Lange, C. Afonso, and P. Giusti, Anal. Chem.
2013, 85, 5530−5534
Molecular mapHydrodesulfurization
• Comparison of 2D map• Collaboration with Waters
– Developement of HDMS compare.
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Comparaison Moléculaire • HDMS compare• HDMS compare
SSS
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F. Maire, K. Neeson, R. Denny, M. McCullagh, C. Lange, C. Afonso, and P. Giusti, Anal. Chem.
2013, 85, 5530−5534
Petroleum analysis in refineries
0
Conventional crude composition(Arabian Light)
0
Marketdemand
Increase of middle fractions cuts (diesel) demand: conversion units
Need for hydrodemetallation, hydrodesulfuration,
0
10
20
Light fractions
0
10
20Light
fractionshydrodenitrogenation and hydrocracking process understanding at the molecular level : 30
40Middle
fractions
30
40
50
60
70
50
60
70
Middle fractions Better feed and products
h t i ti i d d80
90
Heavy fractions 80
90Heavy fractions
characterization is needed
100wt %
100fractionswt %
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Analysis of heavy petroleum product
Ultra high resolution Ion mobility spectrometry t tim
e (m
s)
2D separation1D separationUltra high resolution
FT-ICR• Expensive• Rare
Ion mobility spectrometryHigh resolution Mass Spectrometry
Synapt G2 Waters (QToF) m/z
Drif
t
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Comparison of ultra high resolution mass spectrometry and ion mobility spectrometry coupled with mass
spectrometry
330.2353330 23754
spectrometry• Ultra High Resolution mass
spectrometry• Ion mobility spectrometry-mass
spectrometry2D separation330.23754
330.23417 +CH2
ms)
o 2D separation
R=900000R= 40000
DBE rift t
ime
(m330.1996
330 20 330 25/
m/z
Dr
DBE=double bond equivalent
330.20 330.25m/zm/z
Structural information-Organization of ion in series
Separation of isomers
1 peak = 1 elemental compositionChemical formula assignment of all
resolved species -Separation of isomersresolved species
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METHODS: Atmospheric pressure ionization techniques
• APPIAtmospheric Pressure Photo Ionization
• APCIAtmospheric Pressure Chemical Ionization
• ESIElectrospray Ionization
Gas phase ionizationUsing a corona discharge
Gas phase ionizationUsing a UV lamp hυ = 10.6 eVLiquid phase ionization
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Sources comparison: heavy petroleum fraction sample
294 2205
C21H28N+
• ESI : only nitrogen
containing species are ESI
%
100 294.2205
294 1867294 1304
observed
ASAP
%
100
m/z294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260
0294.1867294.1304
294.2343
294.1442C23H18
+•
C H O+•
C22H30+•
• ASAP and APPI show
the same ionization 100
m/z294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260%
0294.1105
294.2005
294.2358
C21H26O+•
C H N+ C H +•C H +•profile APPI
m/z294 100 294 120 294 140 294 160 294 180 294 200 294 220 294 240 294 260
%
0
294.1420
294.1082294.1983
C21H28NC21H26O+•
C22H30C23H18+
• APCI ionized several
species but ions overlapAPCI%
100
294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260
294.2230
294.1405
294.2305C21H28N+12C21
13C1H29+
C23H18+•
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m/z294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260
0
294.1967
Data treatment
• Collaboration with the Future Fuel Institute, Tallahassee, Florida:
• PetroOrg: software development in progress o Treatment of 2D data
o Peak assignment
o Data display
.
Targeting settings
p y
.
330..20 330.25m/z
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Data treatment
• Collaboration with the Future Fuel Institute, Tallahassee, Florida:
• PetroOrg: software development in progress o Treatment of ion mobility data
o Peak assignment
o Data display p y
F l l i i h dl
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From a mass spectrum to elemental composition more easy to handle
PetroOrg: data representation
• Data representation based on the elemental composition:Double Bond Equivalent vs C#:o Double Bond Equivalent vs C#:
AromaticD
BE
AromaticD
Paraffin
C#
Paraffin
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Application 1 : sulfur speciation
• Analyze of a heavy petroleum fraction using APPI-IMMS
• Comparison before and after hydrotreatment of the S1 class :
Feed Effluent
Effect of the hydrodesulfurization
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Application 1 : sulfur speciation
• 2D plot Carbon number vs. DBE for the feed:
DBE = 12
DBE = 9
DBE = 6
DBE 9
M l l h t i ti
DBE = 6
Molecular characterization
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Application 2: nitrogen speciation
• ESI in positive mode:
• Ion mobility display :
cans
)
cans
) C=31
Drif
t tim
e (s
c
• C=22 Drif
t tim
e (s
c• DBE 6
C=22
H h C A H d i k C L R d R P M h ll A G E & F l 2001 15 (5) 1186 1193
m/z
• C=31
C#
• DBE 8
Hughey, C. A.; Hendrickson, C. L.; Rodgers, R. P.; Marshall, A. G., Energy & Fuels 2001, 15 (5), 1186-1193.
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Application 2: isomeric separation
s)ft
time
(sca
nsD
rif
• DBE 8
C#• The lines might correspond to two isomer families:
R
• Work in progressN
R
R
NR
DBE = 8N1
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Conclusion on ASAP-IMMS of polymers
• ASAP source – No sample preparation
No sol ent– No solvent– Ionization saturated → polar (universal)– robustness (atmospheric pressure, no spray)
• ASAP of polymers and oil• ASAP of polymers and oil– Pyrolysis products or small oligomers– Py-CI/MS)– Results can be compared with previous dataResults can be compared with previous data– Much easier and faster than most analytical
methods
• IM-MS couplingp g– 2D separation– Identification of ion families with different size– Investigation of differential molecular content
41
Acknowledgments
Florian Maire
Marie Hubert-Roux
Florian MaireCaroline BarrèreMathilde Farenc
Pierre Giusti
Eleanor RichesKirsten Craven
EFRD42Normandy region
Kieran Neeson, Richard Denny,
Michael McCullagh