MthdDl tf AiAliUi Method Development or Amine Analysis Using … · 2015. 9. 11. · pppH Gradient...

M th d D l t f A i A l i U i

1

Method Development for Amine Analysis Using Ion‐Pair based High Performance Liquid

Chromatography (IP‐HPLC)

T d t S *Teeradet Supap*Raphael Idem*

Don Gelowitz#Don GelowitzColin Campbell#Max Ball#

*Clean Energy Technologies Research Institute (CETRI), University of Regina#Saskatchewan Power Corporation (SaskPower)

September 8, 2015

2

Importance of Accurate Amine Analysis

Confirm amine qualityConfirm amine qualityq yq yConfirm amine blend formulationConfirm amine blend formulationCheck for amine carryCheck for amine carry‐‐over in offover in off‐‐gasgasProvide early detection of process anomaliesProvide early detection of process anomalies

Faculty of Engineering& Applied Science

Common Chromatographic based techniques used for amine capture solvents

Technique Concerns

for amine capture solvents

Gas Chromatography (GC)

Peak tailing for highly polar amines, not preferred for solid amine

Ion‐Exchange Based Liquid Chromatography

Strong salt and acid based mobile phases limits the use with MS

(IE‐LC)

Reversed Phase Liquid Chromatography(RP‐LC)

Not polar enough to retain amines( )

Ion‐Pair based Liquid Chromatography(IP‐LC)

Rare for amines in CO2 capture application but promising

3Faculty of Engineering& Applied Science

I P i B d Li id Ch h (IP LC)Ion‐Pair Based Liquid Chromatography (IP‐LC)

Higher affinity to polar amines leading to a successful separation (compared to RP-LC)

S l ti it fi t bl i i i t d t IC LCSelectivity fine-tunable via ion-pair types compared to IC-LC

Peak tailing more manageable compared to GC-MS

Can be modified for analysis of amines and anionic species in one single column

HPLC_ION PAIR TECHNIQUE FOR AMINE SEPARATIONHPLC_ION PAIR TECHNIQUE FOR AMINE SEPARATION• Non‐polar column with the internal surface containing long chain hydrocarbon

5

(e.g. C8 and C18), normally will not effectively retain amines especially high polaramines.

C (CH ) CH A i NOT ENOUGH RETENTIONCH (CH ) CH2 2 16 3 Amine+ NOT ENOUGH RETENTION

Non-polar & hydrophobic

• Ion‐pair reagent with one side of the molecule being non‐polar long chainhydrocarbon (e.g. C4 – C8) and the other side containing positively charged groupcan be used to modify the column internal surface more suitable for amineseparation

OPolar_positively charged

Ion Pair reagent : Perfluoroheptanoic acid (PFHA)

CF (CF ) CO

O H- +

3 2CF (CF ) C4

OO H- +

Non-polar

CH (CH ) CH2 2 16 3AmineH++

3 2CF (CF ) C4

O HRETENTION POSSIBLE


Ion Pair Mechanism for Amine Separation

6

Amine Elution++Amine SeparationColumn surface

Ion Pair Mechanism for Amine Separation

AMINE2++

++++++

++++++

++p

modification

‐‐‐‐ ‐‐ AMINE2++

AMINE2++ AMINE1++

AMINE2++++‐‐‐‐

‐‐‐‐

‐‐

‐‐‐‐‐‐

‐‐‐‐ AMINE2++

++ ‐‐‐‐‐‐ ‐‐

AMINE1++

‐‐ ‐‐

‐‐‐‐

‐‐

‐‐ ‐‐‐‐

‐‐‐‐

‐‐ ‐‐

‐‐ ‐‐++

AMINE1

++ ++‐‐ ‐‐ ‐‐ ‐‐AMINE1

++

AMINE1++

‐‐ ‐‐++


Research Objectives

To develop the IP-HPLC method capable of analysis of different types ofTo develop the IP HPLC method capable of analysis of different types of amines commonly used in the CO2 capture process (e.g. single and bi and tri blends)

Optimization of isocratic run conditionOptimization of isocratic run condition

Optimaztion of pH step gradient condition

To explore different mobile phase combinations to separate amines.

Faculty of Engineering& Applied ScienceFaculty of Engineering& Applied Science

Target Amines

Conventional Amines (1, 2, 3)

8

NH2 OH

MEA

( , , )

NHOHOH N

OHOH

CH3

MDEAMEA DEA

Hindered Amines

CH3 OHNH2

CH3AMP

OH

NH

NOH

NOH

Cyclic Amines

N

OH

N

NH

N

NH

N

N

N

NHH H

OH

PZ HEP DIHEP

H

1‐PZpropanol


Hypersil Gold aq Column

9Ion pair test conditions

Hypersil Gold aq Column• Highly pure encapped silica• Functionalized with carbon 18 for compound separationp p

Selected Ion pair reagents for test• Perfluorobutanoic acid (PFBA, with C4)( , )• Pefluoroheptanoic acid (PFHA, with C7)• Perfluorooctanoic acid (PFOA, with C8)

Strong ion pair reagents

• Pentanoic acid (C5 without fluorine) Weak ion pair reagent

Mobile phases• Formic acidA i f A ( l )• Ammonium formate, Acetate (salt)

• Triethylamine (TEA), NH3 in methanol, and NH4OH (pH)


10

Optimizing Isocratic Mobile Phase Condition

Results and DiscussionOptimizing Isocratic Mobile Phase Condition

Establish a baseline aqueous mobile phase mixed with an organic modifierSeveral screening tests were done using PFBA, PFHA, and PFOA

PFBA: Did not exhibit sufficient retention of all the aminesPFOA: Unsuitable due to surfactant effect making mobile phase foamy

PFHA: Able to retain most amines at minimum concentration, thus selected for further development

RID1 A, Ref ractiv e Index Signal (SASK\HYPEG018.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG019.D)

nRIU

80000

100000

120000

, g ( ) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG020.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG022.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG023.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG024.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG025.D)

100000nse

MEA DE

A

MDE

A Mobile Phase10 mM PFHA

0

20000

40000

60000

80000

60000

200000RI

D respo M M

PZ

HEP

HPP

BHP

10 mM PFHA aqueous containing; (a) 1% formic acid @ pH 3

min2.5 5 7.5 10 12.5 15 17.5 20 22.5

-20000

00

5 10 15 20 25 Retention time (min)

R @ pH 3


( )

10mM PFHA + 0 5% formic acid and 0 15 M 10 mM PFHA + 0 15 M ammonium formate/ACN

11Effect of Mobile phase Ingredients (e.g. pH)

10mM PFHA + 0.5% formic acid and 0.15 M ammonium formate/ACN @ 95:5

volume ration @ pH 3.8

10 mM PFHA + 0.15 M ammonium formate/ACN @ volume ration 95:5 @ pH 4.7

RID1 A, Ref ractiv e Index Signal (SASK\HYPEG036.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG037.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG038.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG040.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG041.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG042.D)RID1 A R f ti I d Si l (SASK\HYPEG043 D)A nRIU

RID1 A, Ref ractiv e Index Signal (SASK\HYPEG045.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG046.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG047.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG049.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG050.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG051.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG052.D)

A DEA

DEA

nRIU

100000

150000

200000

RID1 A, Ref ractiv e Index Signal (SASK\HYPEG043.D)

200000

150000

100000respon

se

MEA

DEA

MDE

A

HEP

HPPHP 50000

100000

150000

200000200000

150000

100000

50000D respon

se MEA MD

PZHEP HPP

BHP

min2 4 6 8 10 12 14 16 18

0

50000

5 10 15 Retention time (min)

50000

0

RID PZ

H HBH

min0 2.5 5 7.5 10 12.5 15 17.5-50000

0

5 10 15

Retention time (min)

0RI


nRIU

RID1 A, Ref ractiv e Index Signal (SASK\HYPEG027.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG028.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG029.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG031.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG032.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG033.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG034.D)

DEA

DEA


10 mM PFHA + 0.3 M ammonium formate/ACN @ 95:5 volume ratio @ pH 4.8

• pH is key in amine separation•Cyclic amines require higher pH for a complete separation100000

150000

200000

250000

300000300000

200000

100000respon

se

MEA

DMD

BHP

ZHEP

HPP p p

min2 4 6 8 10 12 14 16 18-50000

0

50000

5 10 15

R t ti ti ( i )

0RID PH



Effect of PFHA Concentration

nRIU

100000

120000

RID1 A, Ref ractiv e Index Signal (SASK\HYPEG055.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG056.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG058.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG059.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG060.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG061.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG062.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG054.D)

120000

onse

EADE

AMDEA

BHP nRIU

150000

175000

, g ( ) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG065.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG066.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG068.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG069.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG070.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG071.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG075.D)

175000

125000onse

A DEA

MDE

A BHP

EP

5 mM PFHApH 5.1

2 mM PFHApH 5.8

0

20000

40000

60000

8000080000

40000

0

RID respo M

PZ

HEP HPP

AMP

0

25000

50000

75000

100000

125000125000

75000

250000

RID respo

MEA M HE

HPP

PZAMP

min0 2.5 5 7.5 10 12.5 15 17.5 20

-20000

5 10 15 20


0min0 2 4 6 8 10

-25000

2 4 6 8 10


nRIU

200000

250000

RID1 A, Ref ractiv e Index Signal (SASK\HYPEG078.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG079.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG080.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG081.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG082.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG083.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG085.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG086.D)

250000

ponse

EA MDEA

BHPHEP

PP

0.5 mMPFHA • 5 mM was the optimized PFHA

0

50000

100000

150000150000

50000

0

RID resp

MEA

DE HP

PZ

AMP PFHA

pH 6.1

pconcentration

min0 1 2 3 4 5 6 7 8

-50000

1 2 3 4 5 6 7 8


0


13

Effect of Fine-Tuning pH in Improving Separation and Elution ofHeterocyclic AminesHeterocyclic Amines

nRIU

, g ( ) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG105.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG106.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG108.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG109.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG110.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG111.D) RID1 A, Ref ractiv e Index Signal (SASK\HYPEG112.D)

BHP 5 mM PFHA + 0.3 M Ammonium acetate

125000

150000

175000

ponse 175000

125000

ADE

AMDE

AB

HEP

PP

pH 6.4

MEA-MDEA, MEA-BHP, HEP HPP MEA AMP

25000

50000

75000

100000

RID res

75000

25000MEA HP

AMP

PZ

HEP-HPP, MEA-AMP, DEA-HEP, DEA-BHPMEA-MDEA-AMP

min0 2 4 6 8 10 12

0

250000

2 4 6 8 10 12

P


To successfully retain, elute, and separation cyclic amines containing 2 amino groups;

Mobile phase pH must be adjusted between 2 pKa of amines


14

Formulation of pH Step Gradient Mobile Phase Conditions

To further improve the use of this technique so as to allow all amines in

any mixtures to be analyzed

pH Gradient Step 1: MEA, DEA, MDEA

Run condition: 5 mM PFHA and 0.3 M ammonium acetate @ pH 4.5/1%ACN

nRIU

120000


120000

e DEA

EA40000

60000

80000

100000

80000

40000respon

se

MEA MDE

MP P

0

20000

4000040000

0RID r

AM BH

min0 2 4 6 8 10 12 14

2 4 6 8 10 12 14 Retention time (min)


pH Gradient Step 2: AMPp p

Run condition: 5 mM PFHA and 0.3 M ammonium acetate @ pH 4.5/5% ACN

nRIU

70000


e

40000

50000

6000060000

40000espo

nse

AMP BHP

0

10000

20000

30000

20000

0

RID re A

min2 4 6 8 10 12 14

0


0



16

pH Gradient Step 3: BHPp p

Run condition: 5 mM PFHA and 0.3 M ammonium acetate @ pH 5.5 /5% ACN

nRIU

120000


120000 BHP

60000

80000

100000

120000120000

80000

ponse

EP

B

0

20000

4000040000

0RID resp H

min1 2 3 4 5 6 7

-40000

-20000

1 2 3 4 5 6 7

R



17

pH Gradient Step 4: HEP and HPP

Run condition: The opitimum isocratic run condition with 5 mM PFHA and 0.3 M ammonium acetate @ pH 6.4 /5% ACN

pH Gradient Step 4: PZ

Run condition: 5 mM PFHA and 0.3 M ammonium acetate @ pH 8 /5% ACNnRIU

100000

120000


100000se

PZ

40000

60000

80000

60000

respon

s

-20000

0

2000020000

0RID r

min1 2 3 4 5 6 7



18

Mobile Phase Volume (%)

Summary of pH Step Gradient Run conditions

pHMobile Phase Volume (%)

Amine Separated1A 2B ACN@ pH 4.5 @ pH 8

4.5 99 0 1 MEA, DEA, MDEA4.5 95 0 5 AMP5.5 15 80 5 BHP6.4 2 93 5 HEP and HPP8.0 0 95 5 PZ8.0 0 95 5 PZ

15 mM PFHA and 0.3 M ammonium acetate adjusted to pH 4.5 by acetic acid25 mM PFHA and 0.3 M ammonium acetate adjusted to pH 8.0 by NH4OH

NOH

N

OH NH

NH

8.00

A HP

HEP

HPP

PZ

NH

2O

H

NHO

HO

NO

HOH

CH3

N

N

OH

OH

N

NH

NH

CH 3

OH

NH2

CH3pH Step

Gradient 6.40

4 50

5.50pH

MEA

DEA

MDE

A B

AMP

H HGradient Separation Chart


4.50

0


ConclusionsCo c us o s

Isocratic condition based ion-pair HPLC method has been developed which can analyze various industrial mixtures such as MEA-MDEA, MEA-BHP, HEP-HPP, MEA-AMP, or MEA-MDEA-HEP/HPP

H t di t diti h l b d l d bl fpH step gradient run conditions have also been developed capable of analysis of complex amine mixture containing any amines used this study; MEA, DEA, MDEA, AMP, BHP, HEP, HPP, and PZ


Acknowledgements

Innovation Saskatchewan (Government of Saskatchewan)

Saskatchewan Power Corporation (Saskpower)

Clean Energy Technologies Institute (CETRI), Univerisity of Regina


MthdDl tf AiAliUi Method Development or Amine Analysis Using … · 2015. 9. 11. · pppH Gradient...

Documents

Transcript of MthdDl tf AiAliUi Method Development or Amine Analysis Using … · 2015. 9. 11. · pppH Gradient...