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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
Jaap.dezeeuw@restek.com
Copyrights: Restek Corporation
Special columns with high Inertness/Low degradationSpecial columns with high Inertness/Low degradation
Rxi- series columns
Non-polar PolarPolarity
Copyrights: Restek Corporation
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;
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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*
Copyrights: Restek Corporation
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.
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
Application of metal tubing for high temperature applications
Goal: make columns more reliable and predictable in high temperature work.
Simdist
Biodiesel
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
Copyrights: Restek Corporation
Copyrights: Restek Corporation
Rt Alumina BOND columnsRt Alumina BOND columns
Alumina BOND / KCl
Alumina BOND / Na2SO4
Alumina BOND / MAPDNEW
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
Impact of injected amount on peak shapePropadiene and acetyleneImpact of injected amount on peak shapePropadiene and acetylene
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
Other applications Rt Alumina BOND MAPD?Other applications Rt Alumina BOND MAPD?
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Carrier : He, 165 kpa
Split : 1 : 30
Detection : micro-TCD
O2
N2
CO
CH4 CO2
O2
N2
CO
30
Copyrights: Restek Corporation
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
Carrier : He, 180 kpa
Split : 1 : 30; Injection: 15 μl; Sample: 2-5% in He + H2
Detection : micro-TCD
Column : 1m x 0.53mm MXT Molsieve 5A 80/100 mesh
Oven : 80 ºC
Carrier : He, 180 kpa
Split : 1 : 30; Injection: 15 μl; Sample: 2-5% in He + H2
Detection : micro-TCD
1.2 [min]0
H2, Rt=0.165 min
O2
CH4
N2
CO
72 sec72 sec
Copyrights: Restek Corporation
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
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New stable solution for volatile amines separations
Rtx Volatile Amines
New stable solution for volatile amines separations
Rtx Volatile Amines
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
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New application using aluminaCFC separations
New application using aluminaCFC separations
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
• 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
Copyrights: Restek Corporation
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
Copyrights: Restek Corporation
Thank you for your attention
For a complete PDF copy of this talk, please sent an email to: Jaap.dezeeuw@restek.com
Thank you
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