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

3

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

13

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

16

Oxygen containing species for PE and PPLow DBE species detected for PE not for PP

PP vs PEPE PPPE PP

17

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

18

IM-MS m/z 313-327

19

IM-MS m/z 323

DBE 2.5

DBE 1.5DBE 0.5

DBE 2.5

DBE 3.5

DBE 4.5

20

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

21

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)

23

Polymer chemistry (back cover)24

Oil and petroleum distillates

25

Diesel hydrodesulfurization (HDS)

Catal. Sci. Technol., 2011, 1, 23–42

26

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

28

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 %

29

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

30

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

31

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

32

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+•

33

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

34

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

35

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

36

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

37

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

38

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.

39

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

40

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