Latest developments in petro2 - Restek's Chromatography Blog ...

Latest developments in GC technology for petro 

and chemical applications 

Jaap de Zeeuw 

Restek Corporation 

Middelburg, The Netherlands 

Jaap.dezeeuw@restek.com 

Copyrights: Restek Corporation

Special columns with high Inertness/Low degradation 

Rxi- series columns 

Non-polar 

Polarity 

Polar 


Low 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 phases 

Type: Non Polar 

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

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

135 ºC 

1 ng C13 

330 ºC 

350 ºC 

Rxi-5Sil MS shows very low degradation 

“Agilent” -5ms, type 1 

“Agilent ” -5ms, type 2 

Restek Rxi-5Sil MS 


Polar phases 

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

280 ºC 

300ºC 

8.3pA 

300 ºC 

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

300ºC 

3.0pA 

300 ºC 

280 ºC 


Inertness: 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 GC 

Comprehensive GC GC = Real Real 2 dimensional Gas 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 dimension 

column 

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 for very complex samples. 


Rxi-17Sil MS 

Rtx-1ms 

BFr’s en PCB’s 

Rxi-XLB 

Hydrocarbon oils 

Rxi-17Sil MS 

Rxi-5ms 

Rtx-200 

Pesticiden 

First column : polar 

Second column : non-polar 

Rxi-5Sil MS 

Terpenes cannabinoids 

Rxi-17Sil MS 

cannabinoids 


Rxi-17Sil MS 

Rtx-1ms 

BFr’s en PCB’s 

Rxi-XLB 

Hydrocarbon oils 

Rxi-17Sil MS 

Rxi-5ms 

Rtx-200 

Pesticiden 

Rxi-5Sil MS 

Terpenes cannabinoids 

First column : non-polar 

Second column : polar 

Rxi-17Sil MS 

cannabinoids 


New practical program 

Restek supplies the 2 nd 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 

On the website an overview is listed which column combinations are 

recommended per application 

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


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 column 

• Lifetime of Simdis columns is indirect proportional with bleed 

level 

• The lower the bleed, the longer the expected lifetime 


Comparison Bleed values 

Supplier V 

0 10 20 30 40 

Time (min) 

Restek 

0 10 20 30 40 


Supplier A 

53 pA @ 430 ºC 

0 10 20 30 40 


5m x 0.53mm x 0.17μm 

5m x 0.53mm x 0.2μm 

32 32 pA pA@ @ 430 430 ºC ºC 

81 81 pA pA@ @ 430 430 ºC 

ºC 

5m x 0.53mm x 0.15μm 


Life time expectation 

If If the bleed is 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 columns 

Alumina BOND / KCl 

Alumina BOND / Na2SO4 

Alumina BOND / MAPD 

NEW 


New 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 


counts 

450000 

400000 

350000 

300000 

250000 

200000 

150000 

100000 

50000 

0 

Impact of injected amount on peak shape 

Propadiene and acetylene 

FID1 A, (MAPD\TEST0176.D) 






Rt AluminaBOND / MAPD CP-Al2O3/MAPD 

acetylene 

propadiene 

butane 

Copyrights: Restek Corporation 

counts 

700000 

600000 

500000 

400000 

300000 

200000 

100000 

, ( ) 






butane 

propadiene 

acetylene 

C i ht R t k C ti min 

0 

36 38 4 42 44 46 

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

peaks 


Stability of response factor in time: 

Rt Alumina BOND / MAPD 

0.800 

0.750 

0.700 

0.650 

0.600 

0.550 

0.500 

0.450 

0.400 

Restek MAPD 

Propadiene / n-butane Peak Area Ratio 

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

0 5 10 15 20 25 30 35 40 45 50 


C1-C5 separation within 2 minutes 

propadiene 

Note high responses for for polar HC 

acetylene methylacetylene 

2 [min] 


Max 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 C 

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


counts 

500000 

400000 

300000 

200000 

100000 

0 

Crude 1,3-butadiene on Rt Alumina BOND / MAPD 

70°C (hold 5 min), 10°C/min to 200°C (hold10 min), Helium @ 20psi 

3.750 

5.404 

5.943 

6.308 

8.316 

9.549 

9.855 

10.292 

10.625 

11.116 

11.660 

12.205 

12.545 

0 5 10 15 20 25 

14.900 

15.764 


Other applications Rt Alumina BOND MAPD? 


Alumina BOND / MAPD are available in Fused 

silica AND metal MXT 

MXT is is preferred for: 

• Process applications 

• If If oven is is having extreme high ventilation speed 

• Smaller GC-Platforms 

• Direct heating 


Additional 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 security 


Molecular Sieve 5A Argon-Oxygen in MXT 

helium 

oxygen 

argon 

nitrogen 

separation 

0 5 

10 

Peak shape of CO 

Column 

Column 

: 

: 

30m 

30m 

x 

x 

0.53mm 

0.53mm 

MXT-MSieve 

MXT-MSieve 

5A, 

5A, 

df 

df 

= 

= 

50 

50 

μm 

μm 

Oven 

Oven 

: 

: 

30ºC 

30ºC 

Carrier 

Carrier 

: 

: 

H2 

H2 

Injection 

Injection 

Detection 

Detection 

: 

: 

split 

split 

: 

: 

Agilent 

Agilent 

micro-TCD 

micro-TCD 

Perfect 

symmetry 

methane carbon monoxide 



MXT-Alumina BOND 

Column: MXT-Alumina BOND /Na2SO4 30m, 0.53mm ID, 10.0µm df 

Column: MXT-Alumina BOND /Na2SO4 30m, 0.53mm ID, 10.0µm df 

Sample: Refinery Gas Standard 

Sample: Refinery Gas Standard 

Inj.: 10.0µL split, split vent flow rate – 80ml/min, 2mm split inlet liner 

Inj.: 10.0µL split, split vent flow rate – 80ml/min, 2mm split inlet liner 

Inj. temp.: 200°C 

Inj. temp.: 200°C 

Carrier gas: He, constant pressure (10 psi, 68.9 kPa) 

Carrier gas: He, constant pressure (10 psi, 68.9 kPa) 

Linear velocity: 31 cm/sec. @ 45°C 

Linear velocity: 31 cm/sec. @ 45°C 

Oven temp.: 45°C (1) to 200°C @ 10°C/min. (8.50 min.) 

Oven temp.: 45°C (1) to 200°C @ 10°C/min. (8.50 min.) 

Det.: FID @ 200°C 

Det.: FID @ 200°C 

1 

2 

3 

4 

5 

6 

7 

8 9 

12 

11 

10 13 

14 

15 

2.5 5 7.5 10 12.5 15 17.5 20 

16 

18 19 

17 

20 

21 

1. methane 

2. ethane 

3. ethylene 

4. propane 

5. propylene 

6. isobutane 

7. n-butane 

8. propadiene 

9. acetylene 

10. trans-2-butene 

11. 1-butene 

12. isobutylene 

13. cis-2-butene 

14. isopentane 

15. n-pentane 

16. 1,3-butadiene 

17. trans-2-pentene 

18. 2-methyl-2-butene 

19. 1-pentene 

20. cis-2-pentene 

21. hexanes 

min 


MXT-Q-BOND 

Solvent test on Metal porous polymer Q-type 

30/0.53mm df = 20 um 

methane 

methanol 

ethanol 

acetone 

diethylether 

Peak shape of alcohols 

methanol 

Column 

Column 

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

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

Oven 

Oven 

: 150ºC 

: 150ºC 

Carrier 

Carrier 

: H2, 40 cm/s 

: H2, 40 cm/s 

Injection : split, 200 mL/min 

Injection : split, 200 mL/min 

Detection 2.10 : FID 2.2 

Detection : FID 

ethylacetate 

0 2 4 6 8 10 

hexane 

ethanol 

3.0 


For users that does not like PLOT 

columns there is an interesting 

alternative.. 

MXT Micro packed 

columns of 0.53mm ID 


0.53mm 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 


0 

O2 

Shincarbon 1m x 0.53mm micro gepakt 

N2 

CO 

CH4 

O2 

N2 

3 

CO 

Column 

Column 

: 

: 

1m 

1m 

x 

x 

0.53mm 

0.53mm 

MXT 

MXT 

Shincarbon 80/100 mesh 

Shincarbon 80/100 mesh 

Oven 

Oven 

: 

: 

25ºC 

25ºC 

Carrier 

Carrier 

: 

: 

He, 

He, 

165 

165 

kpa 

kpa 

Split 

Split 

: 

: 

1 

1 

: 

: 

30 

30 

Detection 

Detection 

: 

: 

micro-TCD 

micro-TCD 

CO2 



Molsieve 5A 1m x 0.53mm micro packed 

0 

H2, Rt=0.165 min 

O2 

N2 

Column 

Column 

: 

: 

1m 

1m 

x 

x 

0.53mm 

0.53mm 

MXT 

MXT 

Molsieve 

Molsieve 

5A 

5A 

80/100 

80/100 

mesh 

mesh 

Oven 

Oven 

: 80 ºC 

: 80 ºC 

Carrier 

Carrier 

: 

: 

He, 

He, 

180 

180 

kpa 

kpa 

Split 

Split 

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

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

Detection 

Detection 

: 

: 

micro-TCD 

micro-TCD 

CH4 

72 72 sec 

CO 

1.2 [min] 


0 

Hayesep D 1m x 0.53mm MXT Micro-gepakt 

1 

1 methanol 

2 ethanol 

3 methylene chloride 

4 isopropanol 

5 ethylether + pentane 

6 MEK 

7 ethylacetate 

8 hexane 

9 heptane 

10 MIBK 

2 

3 

5 

4 

5 

Column 

Column 

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

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

Oven 

Oven 

: 

: 

100 

100 

ºC, 

ºC, 

1min.,→200 

1min.,→200 

ºC, 

ºC, 

10 

10 

ºC/min 

ºC/min 

GC 

GC 

: 

: 

Agilent 

Agilent 

6890; 

6890; 

Carrier 

Carrier 

: 

: 

He, 

He, 

23 

23 

psi 

psi 

kpa 

kpa 

Split 

Split 

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

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

Detection 

Detection 

: FID 

: FID 

6 8 

7 

10 

9 

10 

14 

[min] 


New stable solution for volatile amines separations 

Rtx Volatile Amines 


Before and After 40 injections 

Column 

FID1 A, 

: 60 m 

(09WEVAL\STD2_A_1.D) 

x 320µm Rtx-Volatile amines 

Column FID1 A, : 60 (09WEVAL\STD2_D_5.D) 

m x 320µm Rtx-Volatile amines 

GC : Agilent 6890 

GC : Agilent 6890 

Injection pA : Split; Spit 1/15 = 30 ml/min 

Injection : Split; Spit 1/15 = 30 ml/min 

Injection volume: 1.0µl, Fast plunger mode 

Injection volume: 1.0µl, Fast plunger mode 

Injection temp : 220°C 

Injection temp : 220°C 

Carrier Gas : H2, flow = 2 ml/min; constant flow; 64.2 kPa – 35 cm/sec 

Carrier 32.5Gas 

: H2, flow = 2 ml/min; constant flow; 64.2 kPa – 35 cm/sec 

Oven : Initial 40°C – 10 min., 20°C/min to 250°C -10 tot 30 min isothermal 

Oven : Initial 40°C – 10 min., 20°C/min to 250°C -10 tot 30 min isothermal 

Oven maximum : 265°C 

Oven maximum : 265°C 

Detection :: FID, temp. 250C 

Detection 30 :: FID, temp. 250C 

27.5 

25 

22.5 

20 

17.5 

15 

5.208 5.182 

5.829 5.798 - - MeOH ? 

6.937 6.973 - - DMA EA 

7.617 7.589 

7.999 7.974 - TMA 

6 8 10 12 14 16 

Ref: G Baele, Taminco 

10.161 10.203 - IS 

11.264 11.274 - MEA - Iprop 

Column response 

virtually does not change 

12.523 - DMEA 12.549 = TX1 

13.854 13.832 

14.049 14.063 - DEA 

15.192 15.207 - MDEA 

16.798 16.814 - TEA 

Copyrights: Restek Corporation 

m

Ammonia headspace, 60ºC 

Column 

Column 

: 

: 

60m 

60m 

x 

x 

0.32mm 

0.32mm 

Rtx-Volatile 

Rtx-Volatile 

amines 

amines 

GC 

GC 

: 

: 

HP5890 

HP5890 

Oven 

Oven 

: 

: 

45 

45 

ºC 

ºC 

Carrier 

Carrier 

: 

: 

He, 

He, 

2 

2 

mL/min; 

mL/min; 

Injection 

Injection 

: 

: 

split, 

split, 

30 

30 

μL, 

μL, 

1:15 

1:15 

Detection 

Detection 

: 

: 

u-TCD 

u-TCD 

4000 

2000 

0 

air 

ammonia 

Good Good 

chromatography 

water 



New application using alumina 

CFC separations 


Halocarbons @ 135ºC iso on Rt-AluminaBOND-CFC 

Column 

Column 

: 30m x 0.53mm Rt AluminaBOND CFC 

: 30m x 0.53mm Rt AluminaBOND CFC 

Carrier 

Carrier 

: H2, 8 ml/min, 5 psi; 

: H2, 8 ml/min, 5 psi; 

Oven 

Oven 

: 135C 

: 135C 

Injection 

Injection 

: Split 20:1; 170 mL/min 

: Split 20:1; 170 mL/min 

Detection 

Detection 

: FID @ 220C 

: FID @ 220C 

200 

1 

2 3 

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 

0.0 1.0 2.0 3.0 4.0 


4 

5 

6 7 

8 

9 


Application for CFC analysis: Impuritie in R134a 

Column 

Column 

: 

: 

30m 

30m 

x 

x 

0.53mm 

0.53mm 

Rt 

Rt 

Alumina 


– 

– 

CFC 

CFC 

Carrier 

Carrier 

gas 

gas 

: 

: 

He 

He 

Oven 

Oven 

: 

: 

80°C 

80°C 

for 

for 

6 

6 

min., 

min., 

10°C/min 

10°C/min 

to 

to 

140°C, 

140°C, 

140°C 

140°C 

hold 

hold 

for 

for 

2 

2 

min. 

min. 

Injection 

Injection 

: 

: 

gas 

gas 

sampling, 

sampling, 

500 

500 

ul 

ul 

1 R 115 = Chloropentafluoroethane 

2 R 12 = Dichlorodifluoromethane 

3 R 22 = Chlorodifluoromethane 

4 R 134a = 1,1,1,2 Tetrafluoroethane 

User User had had big big problems with with 

Conventional Al2O3 Al2O3 PLOT PLOT 

columns 

Ref: André Hähnel 

Westfalen AG 

1 

2 

3 

4 


CFC compounds 

CFC-115 

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

CFC-143a 

CFC-125 

Column 

Column 

: 

: 

30m 

30m 

x 

x 

0.53mm 

0.53mm 

Rt 

Rt 



BOND 

BOND 

/ 

/ 

CFC 

CFC 

Oven 

Oven 

: 

: 

100 

100 

oC 

oC 

isotherm 

isotherm 

Injector 

Injector 

: 

: 

valve 

valve 

oven 

oven 

op 

op 

75 

75 

oC, 

oC, 

split 

split 

100 

100 

mL/min 

mL/min 

Inj. 

Inj. 

volume 

volume 

: 

: 

50 

50 

uL 

uL 

Carrier 

Carrier 

gas 

gas 

: 

: 

Helium 

Helium 

Detector 

Detector 

: 

: 

TCD 

TCD 

CFC-134a 


Limitations 

Residual activity is still present for compounds that can split-off 

HCl 

• Dichloro ethane => vinylchloride 

• 2-chloropropane => propene 

Dichloroethane decomposition @ 135C, 1 ul neat 

4000 

2000 

0 

Decomposition 

product Many users will will be be happily 

surprised for for CFC CFC applications 

0.0 1.0 2.0 3.0 4.0 



• 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? 

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 

For a complete PDF copy of this talk, please sent an email to: 

Jaap.dezeeuw@restek.com 

Thank you

Latest developments in petro2 - Restek's Chromatography Blog ...

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?