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Copyrights: Restek Corporation

Latest developments in GC technology for petro and chemical applicationsLatest developments in GC technology for petro and chemical applications

Jaap de ZeeuwRestek Corporation

Middelburg, The Netherlands

[email protected]


Special columns with high Inertness/Low degradationSpecial columns with high Inertness/Low degradation

Rxi- series columns

Non-polar PolarPolarity


Low Degradation = Low Bleed: AdvantagesLow Degradation = Low Bleed: Advantages

• Higher signal/noise, especially at higher temperatures;

• Less maintenance;

• Cleaner mass spectra;

• Short stabilization times;

• Longer column life-time;


Bleed behavior of comparable phasesType: Non PolarBleed behavior of comparable phasesType: Non Polar

“Agilent” -5ms, type 1

“Agilent ” -5ms, type 2

Restek Rxi-5Sil MS

Columns: 30m x 0.25mm Sil-arylene stabilized phases

Identical conditioning, GC-type, detector en conditions of measurement

350 ºC

330 ºC

135 ºC

1 ng C13

Rxi-5Sil MS shows very low degradationRxi-5Sil MS shows very low degradation


Polar phasesPolar phases

Agilent -624ms, type 1 Rxi-624Sil MS

Rxi-624Sil MS has 3 x lower bleed; T max is now 320ºCRxi-624Sil MS has 3 x lower bleed; T max is now 320ºC

300ºC3.0pA

300ºC3.0pA

300ºC8.3pA

300ºC8.3pA

280 ºC280 ºC

300 ºC

300 ºC


Inertness: AdvantagesInertness: Advantages

• Components elute as “sharper” peaks• Higher response• Higher peak area’s (less adsorption)

• Polar components at lower levels

• Components elute at predictable retention times, independent of concentration*


Columns for comprehensive GCColumns for comprehensive GC

Comprehensive GC = Real 2 dimensional Gas ChromatographyComprehensive GC = Real 2 dimensional Gas Chromatography

Separation in first dimension on a 30m x 0.25mm column, typical a Rxi-1ms or a Rxi-5Sil MS;

Via the modulator the eluting fractions are injected on the second dimensioncolumn

Separation in second dimension is on a short column with different selectivity

This is mostly a polar column, typical a Rxi-17Sil MS, Stabilwax or a Rtx-200

Very high peak capacity: used for very complex samples.Very high peak capacity: used for very complex samples.


Rxi-XLB

Rxi

-17S

il M

S

Rxi-17Sil MS

Rxi

-5m

s

Rtx

-1m

s

Rtx

-200

Rxi-5Sil MS

Rxi-17Sil MS

BFr’s en PCB’s

Hydrocarbon oils

cannabinoids

Terpenes cannabinoids

Pesticiden

First column : polar

Second column : non-polar


Rxi-XLB

Rxi

-17S

il M

S

Rxi-17Sil MS

Rxi

-5m

s

Rtx

-1m

s

Rtx

-200

Rxi-5Sil MS

Rxi-17Sil MS

BFr’s en PCB’s

Hydrocarbon oils

cannabinoids

Terpenes cannabinoids

Pesticiden

First column : non-polar

Second column : polar


New practical programNew practical programRestek supplies the 2nd dimension columns in practical lengths of 2 m for

0.15mm x 0.15µm, 0.18mm x 0.18µm, and 0.25mm x 0.25µm

See Blog: http://blog.restek.com/?p=3171 and http://www.restek.com/gcxgc-combo

On the website an overview is listed which column combinations are recommended per application


Application of metal tubing for high temperature applications

Goal: make columns more reliable and predictable in high temperature work.

Simdist

Biodiesel


Lifetime = nr. of analysis per columnLifetime = nr. of analysis per column

• Lifetime of Simdis columns is indirect proportional with bleed level

• The lower the bleed, the longer the expected lifetime


0 10 20 30 40Time (min)

0 10 20 30 40Time (min)

0 10 20 30 40Time (min)

Supplier V

Restek

Supplier A

Comparison Bleed valuesComparison Bleed values

5m x 0.53mm x 0.2μm

5m x 0.53mm x 0.17μm

5m x 0.53mm x 0.15μm

53 pA @ 430 ºC

32 pA @ 430 ºC32 pA @ 430 ºC

81 pA @ 430 ºC81 pA @ 430 ºC


Life time expectation Life time expectation

If the bleed is 2 x higher, the column will loose its phase 2x faster..If the bleed is 2 x higher, the column will loose its phase 2x faster..

• Faster decrease of retention times

• More calibrations necessary

• 2x more columns needed for same nr. of analysis


Rt Alumina BOND columnsRt Alumina BOND columns

Alumina BOND / KCl

Alumina BOND / Na2SO4

Alumina BOND / MAPDNEW


New Alumina technology: Rt Alumina BOND / MAPDNew Alumina technology: Rt Alumina BOND / MAPD

Using a different alumina and deactivation procedure:

• Highest response for polar hydrocarbons• Constant response factor – in time-• No compromise in loadability• Extended temperature range to 250 ºC


Impact of injected amount on peak shapePropadiene and acetyleneImpact of injected amount on peak shapePropadiene and acetylene


counts

0

50000

100000

150000

200000

250000

300000

350000

400000

450000

FID1 A, (MAPD\TEST0176.D) FID1 A, (MAPD\TEST0175.D) FID1 A, (MAPD\TEST0170.D) FID1 A, (MAPD\TEST0177.D) FID1 A, (MAPD\TEST0178.D) FID1 A, (MAPD\TEST0180.D)

butane

acetylene

propadiene

C i ht R t k C ti min3 6 3 8 4 4 2 4 4 4 6

counts

0

100000

200000

300000

400000

500000

600000

700000

, ( ) FID1 A, (MAPD\TEST0193.D) FID1 A, (MAPD\TEST0192.D) FID1 A, (MAPD\TEST0191.D) FID1 A, (MAPD\TEST0190.D) FID1 A, (MAPD\TEST0189.D)

acetylene

propadiene

butane

Rt AluminaBOND / MAPD CP-Al2O3/MAPD

Rt Alumina BOND/MAPD has higher loadability = more symmetrical peaksRt Alumina BOND/MAPD has higher loadability = more symmetrical peaks


Restek MAPDPropadiene / n-butane Peak Area Ratio

0.400

0.450

0.500

0.550

0.600

0.650

0.700

0.750

0.800

0 5 10 15 20 25 30 35 40 45 50

Constant response – in time - for PropadieneConstant response – in time - for Propadiene

Stability of response factor in time:

Rt Alumina BOND / MAPD

Stability of response factor in time:

Rt Alumina BOND / MAPD


2 [min]

acetylene methylacetylenepropadiene

C1-C5 separation within 2 minutes C1-C5 separation within 2 minutes

Note high responses for polar HCNote high responses for polar HC


Max temperature extended to 250 CMax temperature extended to 250 C

• Faster elution of higher hydrocarbons

• Faster regeneration if exposed to water

• Broader application for GC as second channel can also be operated higher


Rt Alumina BOND MAPD can take 250 CRt Alumina BOND MAPD can take 250 C

Decane elutes 2.5 times faster when the column can be heated to 250 CDecane elutes 2.5 times faster when the column can be heated to 250 C


Crude 1,3-butadiene on Rt Alumina BOND / MAPD70°C (hold 5 min), 10°C/min to 200°C (hold10 min), Helium @ 20psiCrude 1,3-butadiene on Rt Alumina BOND / MAPD70°C (hold 5 min), 10°C/min to 200°C (hold10 min), Helium @ 20psi

0 5 10 15 20 25

counts

0

100000

200000

300000

400000

500000 3

.750 5.4

04 5

.943

6.3

08

8.3

16

9.5

49 9

.855

10.

292

10.

625

11.

116

11.

660

12.

205

12.

545

14.

900

15.

764


Other applications Rt Alumina BOND MAPD?Other applications Rt Alumina BOND MAPD?


Alumina BOND / MAPD are available in Fused silica AND metal MXT

MXT is preferred for:

• Process applications

• If oven is having extreme high ventilation speed

• Smaller GC-Platforms

• Direct heating

MXT is preferred for:

• Process applications

• If oven is having extreme high ventilation speed

• Smaller GC-Platforms

• Direct heating


Additional UNIQUE Restek developmentAdditional UNIQUE Restek development

Development of metal PLOT en Liquid phase coated columns

In PROCES type applications they are looking for

RELIABILITY

Metal columns provide extra securityMetal columns provide extra security


Molecular Sieve 5A in MXTMolecular Sieve 5A in MXT

15 [min]0 105

argonnitrogen

oxygen

Column : 30m x 0.53mm MXT-MSieve 5A, df = 50 μm

Oven : 30ºC

Carrier : H2

Injection : split

Detection : Agilent micro-TCD

Column : 30m x 0.53mm MXT-MSieve 5A, df = 50 μm

Oven : 30ºC

Carrier : H2

Injection : split

Detection : Agilent micro-TCD

methane carbon monoxide

helium

Argon-Oxygen separation

Peak shape of CO

Perfect symmetryPerfect

symmetry


min2.5 5 7.5 10 12.5 15 17.5 20

1

3

24

5

67

8 9

1011

12

131415

16

17

18 19

20 21

1. methane2. ethane3. ethylene4. propane5. propylene6. isobutane7. n-butane8. propadiene9. acetylene10. trans-2-butene11. 1-butene12. isobutylene13. cis-2-butene14. isopentane15. n-pentane16. 1,3-butadiene17. trans-2-pentene18. 2-methyl-2-butene19. 1-pentene20. cis-2-pentene21. hexanes

Column: MXT-Alumina BOND /Na2SO4 30m, 0.53mm ID, 10.0µm df Sample: Refinery Gas StandardInj.: 10.0µL split, split vent flow rate – 80ml/min, 2mm split inlet linerInj. temp.: 200°CCarrier gas: He, constant pressure (10 psi, 68.9 kPa) Linear velocity: 31 cm/sec. @ 45°COven temp.: 45°C (1) to 200°C @ 10°C/min. (8.50 min.) Det.: FID @ 200°C

Column: MXT-Alumina BOND /Na2SO4 30m, 0.53mm ID, 10.0µm df Sample: Refinery Gas StandardInj.: 10.0µL split, split vent flow rate – 80ml/min, 2mm split inlet linerInj. temp.: 200°CCarrier gas: He, constant pressure (10 psi, 68.9 kPa) Linear velocity: 31 cm/sec. @ 45°COven temp.: 45°C (1) to 200°C @ 10°C/min. (8.50 min.) Det.: FID @ 200°C

MXT-Alumina BONDMXT-Alumina BOND


0 2 4 6 8 10

Solvent test on Metal porous polymer Q-type 30/0.53mm df = 20 umSolvent test on Metal porous polymer Q-type 30/0.53mm df = 20 um

Column : 30m x 0.53mm MXT Q-BOND, df = 20 μm

Oven : 150ºC

Carrier : H2, 40 cm/s

Injection : split, 200 mL/min

Detection : FID

Column : 30m x 0.53mm MXT Q-BOND, df = 20 μm

Oven : 150ºC

Carrier : H2, 40 cm/s

Injection : split, 200 mL/min

Detection : FID

methane

diethylether

ethanol

methanol

acetone

ethylacetate

hexane

Peak shape of alcoholsPeak shape of alcohols

3.02.10 2.2

methanolethanol

MXT-Q-BONDMXT-Q-BOND


For users that does not like PLOT columns there is an interesting alternative..

MXT Micro packed columns of 0.53mm IDMXT Micro packed columns of 0.53mm ID


0.53mm micro packed0.53mm micro packed

• Can be coiled very small• Fit is ALL capillary inlet/detection systems• Flow 1-5 mL/min• Length of few cm to several meters• Applicable for near al packing materials


Shincarbon 1m x 0.53mm micro gepaktShincarbon 1m x 0.53mm micro gepakt

6 [min]

Column : 1m x 0.53mm MXT Shincarbon 80/100 mesh

Oven : 25ºC

Carrier : He, 165 kpa

Split : 1 : 30

Detection : micro-TCD

Column : 1m x 0.53mm MXT Shincarbon 80/100 mesh

Oven : 25ºC


Split : 1 : 30


O2

N2

CO

CH4 CO2

O2

N2

CO

30


Molsieve 5A 1m x 0.53mm micro packedMolsieve 5A 1m x 0.53mm micro packed

Column : 1m x 0.53mm MXT Molsieve 5A 80/100 mesh

Oven : 80 ºC


Split : 1 : 30; Injection: 15 μl; Sample: 2-5% in He + H2


Column : 1m x 0.53mm MXT Molsieve 5A 80/100 mesh

Oven : 80 ºC


Split : 1 : 30; Injection: 15 μl; Sample: 2-5% in He + H2


1.2 [min]0

H2, Rt=0.165 min

O2

CH4

N2

CO

72 sec72 sec


Hayesep D 1m x 0.53mm MXT Micro-gepaktHayesep D 1m x 0.53mm MXT Micro-gepakt

Column : 1m x 0.53mm MXT HayeSep Q 80/100 mesh

Oven : 100 ºC, 1min.,→200 ºC, 10 ºC/min

GC : Agilent 6890;

Carrier : He, 23 psi kpa

Split : 1 : 30; Injection: 15 μl; Sample head space

Detection : FID

Column : 1m x 0.53mm MXT HayeSep Q 80/100 mesh

Oven : 100 ºC, 1min.,→200 ºC, 10 ºC/min

GC : Agilent 6890;

Carrier : He, 23 psi kpa

Split : 1 : 30; Injection: 15 μl; Sample head space

Detection : FID

14[min]

100 5

1 methanol

2 ethanol

3 methylene chloride

4 isopropanol

5 ethylether + pentane

6 MEK

7 ethylacetate

8 hexane

9 heptane

10 MIBK

1

96 8

7

5

4

3

2

10


New stable solution for volatile amines separations

Rtx Volatile Amines

New stable solution for volatile amines separations

Rtx Volatile Amines


Before and After 40 injectionsBefore and After 40 injections

m6 8 10 12 14 16

pA

15

17.5

20

22.5

25

27.5

30

32.5

FID1 A, (09WEVAL\STD2_A_1.D)

5.1

82 5.7

98 -

?

6.9

37 -

DMA

7.5

89

7.9

74 -

TMA

10.

161

- I S

11.

264

- MEA

- Ipr

op

12.

523

- DMEA

= TX

1

13.

832

14.

049

- DEA

15.

192

16.

798

- TE

A

FID1 A, (09WEVAL\STD2_D_5.D)

5.2

08

5.8

29 -

MeO

H

6.9

73 -

EA

7.6

17

7.9

99

10.

203

11.

274

12.

549

13.

854

14.

063

15.

207

- MDEA

16.

814

Column response virtually does not changeColumn response virtually does not changeColumn : 60 m x 320µm Rtx-Volatile amines

GC : Agilent 6890 Injection : Split; Spit 1/15 = 30 ml/minInjection volume: 1.0µl, Fast plunger modeInjection temp : 220°CCarrier Gas : H2, flow = 2 ml/min; constant flow; 64.2 kPa – 35 cm/secOven : Initial 40°C – 10 min., 20°C/min to 250°C -10 tot 30 min isothermalOven maximum : 265°CDetection :: FID, temp. 250C

Column : 60 m x 320µm Rtx-Volatile aminesGC : Agilent 6890 Injection : Split; Spit 1/15 = 30 ml/minInjection volume: 1.0µl, Fast plunger modeInjection temp : 220°CCarrier Gas : H2, flow = 2 ml/min; constant flow; 64.2 kPa – 35 cm/secOven : Initial 40°C – 10 min., 20°C/min to 250°C -10 tot 30 min isothermalOven maximum : 265°CDetection :: FID, temp. 250C

Ref: G Baele, Taminco


2000

4000

Ammonia headspace, 60ºCAmmonia headspace, 60ºC

water

ammonia

Column : 60m x 0.32mm Rtx-Volatile amines

GC : HP5890

Oven : 45 ºC

Carrier : He, 2 mL/min;

Injection : split, 30 μL, 1:15

Detection : u-TCD

Column : 60m x 0.32mm Rtx-Volatile amines

GC : HP5890

Oven : 45 ºC

Carrier : He, 2 mL/min;

Injection : split, 30 μL, 1:15

Detection : u-TCD

6 [min]0

air

Good chromatography

Good chromatography


New application using aluminaCFC separations

New application using aluminaCFC separations


0.0 1.0 2.0 3.0 4.0Time (min)

200

Halocarbons @ 135ºC iso on Rt-AluminaBOND-CFCHalocarbons @ 135ºC iso on Rt-AluminaBOND-CFC

1 1,1 dichloroethylene

2 Methylene chloride

3 Tr-1,2 dichloroethylene

4 Tetrachlormethane

5 unknown

6 Cis-1,2 dichloroethylene

7 Trichloroethylene

8 1,1,1-trichloroethane

9 Chloroform

9

82 3

5

46 7

1

Column : 30m x 0.53mm Rt AluminaBOND CFC

Carrier : H2, 8 ml/min, 5 psi;

Oven : 135C

Injection : Split 20:1; 170 mL/min

Detection : FID @ 220C

Column : 30m x 0.53mm Rt AluminaBOND CFC

Carrier : H2, 8 ml/min, 5 psi;

Oven : 135C

Injection : Split 20:1; 170 mL/min

Detection : FID @ 220C


Application for CFC analysis: Impuritie in R134aApplication for CFC analysis: Impuritie in R134aColumn : 30m x 0.53mm Rt Alumina – CFC

Carrier gas : He

Oven : 80°C for 6 min., 10°C/min to 140°C, 140°C hold for 2 min.

Injection : gas sampling, 500 ul

Column : 30m x 0.53mm Rt Alumina – CFC

Carrier gas : He

Oven : 80°C for 6 min., 10°C/min to 140°C, 140°C hold for 2 min.

Injection : gas sampling, 500 ul

1 R 115 = Chloropentafluoroethane2 R 12 = Dichlorodifluoromethane3 R 22 = Chlorodifluoromethane4 R 134a = 1,1,1,2 Tetrafluoroethane

Ref: André HähnelWestfalen AG

1

23

4

User had big problems with Conventional Al2O3 PLOT columns

User had big problems with Conventional Al2O3 PLOT columns


CFC compoundsCFC compounds

CFC-143a

CFC-125

CFC-134a

CFC-115

Ref: Klaas van Dijk, Crealis Nederland B.V.

Column : 30m x 0.53mm Rt Alumina BOND / CFCOven : 100 oC isothermInjector : valve oven op 75 oC, split 100 mL/minInj. volume : 50 uLCarrier gas : HeliumDetector : TCD

Column : 30m x 0.53mm Rt Alumina BOND / CFCOven : 100 oC isothermInjector : valve oven op 75 oC, split 100 mL/minInj. volume : 50 uLCarrier gas : HeliumDetector : TCD


LimitationsLimitations

Residual activity is still present for compounds that can split-off HCl• Dichloro ethane => vinylchloride• 2-chloropropane => propene

Dichloroethane decomposition @ 135C, 1 ul neatDichloroethane decomposition @ 135C, 1 ul neat

0.0 1.0 2.0 3.0 4.0Time (min)

0

2000

4000Decomposition product Many users will be happily

surprised for CFC applicationsMany users will be happily surprised for CFC applications


• Quality improvement of capillary columns will continue

• Columns will become more stable, have higher upper temperature limits and become more selective

• Aside from that, ease-of-use will develop, especially for making a faster (correct)connection

• We will also see more solutions implemented for achieving a fast(er) analysis


Want to keep up to speed with developments? ChromaBLOGraphyWant to keep up to speed with developments? ChromaBLOGraphy

Restek scientists publish all interesting developments in GC, LC and SPE via the blog far before the application is published.. www.restek.com


Thank you for your attention

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