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