Simdis Course AC Analytical Controls January 2001.
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Transcript of Simdis Course AC Analytical Controls January 2001.
Simdis CourseSimdis Course
AC Analytical Controls
January 2001
SimdisSimdis - Introduction- Introduction
Distillation is the most widely used separation process in the petrol industry
Knowledge of the boiling range is essential for quality assurance
regulatory compliancerefinery process controlphysical property predictions
Simdis Vs. Physical Simdis Vs. Physical Distillation Distillation
D86, D1160 generates an average boiling point of a mixture at a given point
D 2892, 15 theoretical plate, true boiling point
Time consuming, labor intensive, imprecise
Simdis Vs Physical Simdis Vs Physical DistallationDistallation
GC analysis simulates a “true boiling point”Simdis provides TBP of the individual
components in a mixture at a given pointAutomatedAccurate results FastDetection of contamination or entrainment
Simdis TheorySimdis Theory
The technique of simulated distillation is based upon the assumption that individual components of a sample elute from a GC column in order of their boiling point.
Available Simdis MethodsAvailable Simdis Methods
Final boiling point
ASTM 3710 260 °CASTM 2887 538 °C2887 extended 620 °CHt 750 750 °C
ASTM D 3710ASTM D 3710
Gasoline, naphtha, keroseneFinal boiling point (FBP)<260°CPacked or capillary column
ASTM D 2887ASTM D 2887
Petroleum productsFinal boiling point (FBP)<538°CPacked or capillary columnCryogenic option
ASTM D 2887 ExtendedASTM D 2887 Extended
Petroleum productsFinal boiling point (FBP)<620°CCapillary columnCryogenic option
Ht 750Ht 750
Crude's and crude fractions, petroleum products
Boiling range from 35°C-750°CCapillary columnCryogenic option
RequirementsRequirements
non-polar stationery phaselinear temperature programcompensation of column bleeding
HardwareHardware
Gas chromatographProgrammable temperature vaporizer (PTV
injector)FID detectorColumn
Typical Gas Typical Gas ChromatographChromatograph
Purpose Of This CourseTo learn the operations of the 6890 G.C. while achievinga basic understanding of the function and impact each ofof the G.C. components has on sample analysis and to learn beginning troubleshooting skills.
Column
Flow
Controller
Regulators
Air
Hyd
rog
en
Carrie
r G
as
Mol-SieveTraps
Fixed
InjectionPort
Detector Electrometer
PC
Restrictors
PTVPTV
Exit End of Column
Jet
Air
H2 Inlet+
Make-Up
FID DetectorAssembly
Inlet
Capillary ColumnEnd-Position
(1-2 mm from Top of Jet)
Flame Ionization Detector Flame Ionization Detector SchematicSchematic
The FID is a destructive, mass sensing detector.Cations generated in the flame are counted and produce the detector signal. Analytes that have the greatest number of low oxidation state carbons produce the largest signal.H
2
H2
H2
H2
H2
H2
CH 4
CH 4
CH 4
CH 4
CH 4
CH 4
CHO+
CHO+
CHO+
CHO+ CHO+
CO2
CO2
CO2
H 02
H 02
H 02
H 02
H2
H2
H2
H2
H2
H2
Column
Jet
Flame Ionization DetectorFlame Ionization Detector
System StartupSystem Startup
Electrical connectionsGas connections – carrier, FIDGC and auto sampler configurationInstallation of liner & columnInstallation of septum and syringeCheck flows
Simdis TheorySimdis Theory
A n-paraffin standard is analyzed to determine retention times
The times relate to the n-paraffin boiling points
A boiling point calibration curve is created by the software
AC SIMDIS Analyzers 19
AC SIMDIS D 2887 AC SIMDIS D 2887 CalibrationCalibration
Carbon ComponentNumber
5 n-Pentane6 n-Hexane7 n-Heptane8 n-Octane9 n-Nonane10 n-Decane11 n-Undecane12 n-Dodecane14 n-Tetradecane15 n-Pentadecane16 n-Hexadecane17 n-Heptadecane18 n-Octadecane20 n-Eicosane24 n-Tetracosane28 n-Octacosane32 n-Dotriacantane36 n-Hexatriacantrane40 n-Tetracantane44 n-Tetratetracantane
20AC SIMDIS Analyzers
Calibration ReportCalibration ReportAC Simdis version 04.10
TESTSIMDIS 4003001 ASTM D 2887 2
Sample name : cal Instrument : 1Method name : C:\HPCHEM\1\METHODS\D2887C.M Vial : 102Sample type : Calib 25950.150 Injection : 1Sequence name : D0501A.S Seq. line : 2
Operator : saskia Sample (g) : 0.0000Acquired on : 5/1/00 4:48:40 PM Solvent (g) : 0.0000Processed on : 5/2/00 9:14:36 AM ISTD (g) : 0.0000
Data File : D051A\102F0201.D\FID1A.CH
Calibration report:Nr Component BP(°F) Rt(min) Skew Resolution1 C5 97 0.978 0.632 C6 156 1.984 1.163 C7 208 3.161 1.174 C8 259 4.347 1.235 C9 304 5.472 1.276 C10 345 6.521 1.247 C11 385 7.498 1.178 C12 421 8.417 1.159 C14 489 10.097 1.1610 C15 520 10.869 1.1511 C16 549 11.596 1.08 R 10.312 C17 576 12.292 1.0913 C18 601 12.955 1.09 R14 C20 651 14.193 1.0815 C24 736 16.378 1.1016 C28 808 18.258 1.0617 C32 871 19.907 1.0918 C36 925 21.368 1.0319 C40 972 22.687 0.9320 C44 1013 23.882 0.16
21AC SIMDIS Analyzers
Calibration CurveCalibration CurveAC Simdis version 04.10
TESTSIMDIS 4003001 ASTM D 2887 3
Sample name : cal Instrument : 1Method name : C:\HPCHEM\1\METHODS\D2887C.M Vial : 102Sample type : Calib 25950.150 Injection : 1Sequence name : D0501A.S Seq. line : 2
Operator : saskia Sample (g) : 0.0000Acquired on : 5/1/00 4:48:40 PM Solvent (g) : 0.0000Processed on : 5/2/00 9:14:36 AM ISTD (g) : 0.0000
Data File : D051A\102F0201.D\FID1A.CH
Boiling point Retention time plot:
0 100 200 300 400 500 600 700 800 900 1000 1100
Boiling point (°F)
0
2
4
6
8
10
12
14
16
18
20
22
24
Reten
tion tim
e (min
)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
The numbers refer to the calibration report table
22AC SIMDIS Analyzers
HP/AC Simdis version 3.2
XYZ Company
SIMDIS 3
Sample name : Calibrant Instrument : 1Method name : D:\ASTERIX\1\METHODS\mha30.M Vial : 90Sample type : Cal 25950.100 Injection : 1Sequence name : D1016A.S Seq. line : 3
Operator : AC Sample (g) : 0.0000Acquired on : 16 Oct 95 12:15 PM Solvent (g) : 0.0000Processed on : 14/12/95 10:56:03 AM ISTD (g) : 0.0000
Data File : D1016A\090F0301.D\FID1A.CH
Boiling point Retention time plot:
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
0
5
10
15
20
25
30
35
40
Boiling point (°C)
Re
ten
tio
n t
ime
(m
in)
1 2 3 4 5 6 78
910
1112
1314
15
16
17
18
19
2021
2223
2425
2627
282930
3132333435363738394041424344454647484950
5152
The numbers refer to the calibration report table
Boiling Point CurveBoiling Point Curve
Simdis TheorySimdis Theory
Every analysis should be corrected for column bleeding
Analyze a blank in every sequenceThe blank signal is automatically subtracted
from every sample and reference signal
Simdis TheorySimdis Theory
The net signal is used to determine boiling points
IBP at 0.5 % of the total areaFBP at 99.5 % of the total areaThe total area lies between start and end
elution pointThe start and end time are determined by
elution algorithms
Simdis TheorySimdis Theory
A reference sample is analyzed to check system performance
AC SIMDIS Analyzers 26
AC SIMDIS D 2887 AC SIMDIS D 2887 ReferenceReference
27AC SIMDIS Analyzers
AC SIMDIS D 2887 reference reports
AC Simdis version 04.10
TESTSIMDIS 4003001 ASTM D 2887 2
Sample name : ref Instrument : 1Method name : C:\HPCHEM\1\METHODS\D2887C.M Vial : 103Sample type : Ref 25650.150 Injection : 1Sequence name : D0501A.S Seq. line : 3
Operator : saskia Sample (g) : 0.0000Acquired on : 5/1/00 5:31:06 PM Solvent (g) : 0.0000Processed on : 5/2/00 9:14:58 AM ISTD (g) : 0.0000
Data File : D051A\103F0301.D\FID1A.CH
Chromatogram:
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Retention time (min)
0
1000
2000
3000
4000
5000
6000
7000
8000
Signal
0
200 300 400 500 600 700 800 900 1000 1100
Boiling point (°F)
Star
t Tim
e
End
Tim
e
IBP
FBP
28AC SIMDIS Analyzers
AC SIMDIS D 2887 Reference AC SIMDIS D 2887 Reference ReportsReports
AC Simdis version 04.10
TESTSIMDIS 4003001 ASTM D 2887 1
Sample name : ref Instrument : 1Method name : C:\HPCHEM\1\METHODS\D2887C.M Vial : 103Sample type : Ref 25650.150 Injection : 1Sequence name : D0501A.S Seq. line : 3
Operator : saskia Sample (g) : 0.0000Acquired on : 5/1/00 5:31:06 PM Solvent (g) : 0.0000Processed on : 5/2/00 9:14:58 AM ISTD (g) : 0.0000
Data File : D051A\103F0301.D\FID1A.CH Start Elution : 0.13 Blank used : D051A\101F0101.D\FID1A.CH corrected End Elution : 23.88>BP Calibrant : D051A\102F0201.D\FID1A.CHLast Reference : D0501\104F0101.D\FID1A.CH On spec.
Reference sample results:
Target values Determined valuesBP (°F) BP (°F)dBP (°F) dBP (°F)Mass%
IBP 286 29221 610 406 4086 220 455 4576 230 489 4916 240 520 5216 150 549 5506 160 577 5786 170 606 6066 080 640 6416 190 680 6816 1
FBP 748 75213 4
Front channel ON specification
Starting AnalysisStarting Analysis
Make & run a sequenceCalibrationObserve resultsReprocess if necessary
Non Fitting BlankNon Fitting BlankChromatogram:
0 5 10 15 20 25 30 35 40 45
Retention time (min)
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
65000
70000
Sign
al
0100200 300 400 500 600 700 800Boiling point (°C)
Star
t Tim
e
End
Tim
e
IBP
FBP
End Time Found End Time Found IncorrectlyIncorrectly
Chromatogram:
0 5 10 15 20 25 30 35 40 45 50 55
Retention time (min)
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
Sign
al
200 300 400 500 600 700 800Boiling point (°C)
Sta
rt T
ime
End
Tim
e
IBP
FB
P