Transcript Simdis Course

Simdis Course
AC Analytical Controls
January 2001
Simdis - Introduction

Distillation is the most widely used
separation process in the petrol industry
 Knowledge of the boiling range is essential
for
quality assurance
regulatory compliance
refinery process control
physical property predictions
Simdis Vs. Physical 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 Distallation
GC analysis simulates a “true boiling point”
 Simdis provides TBP of the individual
components in a mixture at a given point
 Automated
 Accurate results
 Fast
 Detection of contamination or entrainment

Simdis 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 Methods
Final boiling point

ASTM 3710
 ASTM 2887
 2887 extended
 Ht 750
260 °C
538 °C
620 °C
750 °C
ASTM D 3710

Gasoline, naphtha, kerosene
 Final boiling point (FBP)<260°C
 Packed or capillary column
ASTM D 2887

Petroleum products
 Final boiling point (FBP)<538°C
 Packed or capillary column
 Cryogenic option
ASTM D 2887 Extended

Petroleum products
 Final boiling point (FBP)<620°C
 Capillary column
 Cryogenic option
Ht 750

Crude's and crude fractions, petroleum
products
 Boiling range from 35°C-750°C
 Capillary column
 Cryogenic option
Requirements

non-polar stationery phase
 linear temperature program
 compensation of column bleeding
Hardware

Gas chromatograph
 Programmable temperature vaporizer (PTV
injector)
 FID detector
 Column
Typical Gas Chromatograph
Mol-Sieve
Traps
Fixed
Restrictors
Injection
Port
Regulators
Detector
Flow
Controller
Electrometer
PC
Column
Carrier
Hydrogen
Gas
Air
PTV
Flame Ionization Detector
Schematic
FID Detector
Assembly
Air
Inlet
Capillary Column
End-Position
(1-2 mm from Top of Jet)
Jet
H2 Inlet
+
Make-Up
Exit End of Column
Flame Ionization Detector
CO
2
+
CHO
H0
2
H0
2 CHO+
CO
2
+
CHO
+
CHO
CO
+
CHO
2
H0
2
H0
2
H
2
H
H
H
H
H
H
CH
4
H
2
CH
2
CH
2
CH
CH
2
CH
2
2
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.
4
H
4
4
H
4
H
4
H
2
2
2
Column
2
Jet
2
System Startup

Electrical connections
 Gas connections – carrier, FID
 GC and auto sampler configuration
 Installation of liner & column
 Installation of septum and syringe
 Check flows
Simdis 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 D 2887 Calibration
Carbon
Number
Component
5
6
7
8
9
10
11
12
14
15
16
17
18
20
24
28
32
36
40
44
n-Pentane
n-Hexane
n-Heptane
n-Octane
n-Nonane
n-Decane
n-Undecane
n-Dodecane
n-Tetradecane
n-Pentadecane
n-Hexadecane
n-Heptadecane
n-Octadecane
n-Eicosane
n-Tetracosane
n-Octacosane
n-Dotriacantane
n-Hexatriacantrane
n-Tetracantane
n-Tetratetracantane
AC SIMDIS Analyzers
19
Calibration Report
AC Simdis version 04.10
SIMDIS 4003001 ASTM D 2887
TEST
2
Sample name
Method name
Sample type
Sequence name
: cal
: C:\HPCHEM\1\METHODS\D2887C.M
: Calib 25950.150
: D0501A.S
Instrument
Vial
Injection
Seq. line
:1
: 102
:1
:2
Operator
Acquired on
Processed on
: saskia
: 5/1/00 4:48:40 PM
: 5/2/00 9:14:36 AM
Sample (g)
Solvent (g)
ISTD (g)
: 0.0000
: 0.0000
: 0.0000
Data File
: D051A\102F0201.D\FID1A.CH
Calibration report:
Nr
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Component
C5
C6
C7
C8
C9
C10
C11
C12
C14
C15
C16
C17
C18
C20
C24
C28
C32
C36
C40
C44
BP(°F)
97
156
208
259
304
345
385
421
489
520
549
576
601
651
736
808
871
925
972
1013
Rt(min)
0.978
1.984
3.161
4.347
5.472
6.521
7.498
8.417
10.097
10.869
11.596
12.292
12.955
14.193
16.378
18.258
19.907
21.368
22.687
23.882
Skew Resolution
0.63
1.16
1.17
1.23
1.27
1.24
1.17
1.15
1.16
1.15
1.08 R 10.3
1.09
1.09 R
1.08
1.10
1.06
1.09
1.03
0.93
0.16
AC SIMDIS Analyzers
20
Calibration Curve
AC Simdis vers ion 04.10
SIMDIS 4003001 ASTM D 2887
TEST
Sample name
Metho d name
Sample type
Sequence name
:
:
:
:
cal
C:\HPCHEM\1\METHODS\D2887C.M
Calib 25950.150
D0501A.S
Operator
Acquired on
Processed on
: saskia
: 5/1/00 4:4 8:40 PM
: 5/2/00 9:14:36 AM
Data File
: D051A\10 2F0201.D\FID1A.CH
3
Instrument
Vial
Injection
Seq. line
:
:
:
:
1
102
1
2
Sample (g)
Solvent (g)
ISTD (g)
: 0.0000
: 0.0000
: 0.0000
Boiling point Retention time plot:
24
17
22
16
20
15
18
13
Retention time (min)
14
16
11
12
14
9
10
12
7
8
10
5
6
8
4
6
2
3
4
1
2
0
0
100
200
300
400
500
600
700
800
900
1000
1100
Boiling point (°F)
The numbers refer to the calib ratio n report tab le
AC SIMDIS Analyzers
21
Boiling Point Curve
HP/ AC Si m d i s v e rs i o n 3 .2
XYZ Company
SIMDIS
3
Sample name
Method name
Sample type
Sequence name
: Calibrant
: D:\ASTERIX\1\METHODS\mha30.M
: Cal 25950.100
: D1016A.S
Instrument
Vial
Injection
Seq. line
:1
: 90
:1
:3
Operator
Acquired on
Processed on
: AC
: 16 Oct 95 12:15 PM
: 14/12/95 10:56:03 AM
Sample (g)
Solvent (g)
ISTD (g)
: 0.0000
: 0.0000
: 0.0000
Data File
: D1016A\090F0301.D\FID1A.CH
Boiling point Retention time plot:
40
52
51
R e t e nt ion t ime ( min)
35
30
3
30
29
28
27
26
25
24
23
22
21
20
25
20
50
4489
47
46
45
44
43
42
41
40
39
38
37
36
35
34
33
32
1
19
18
15
17
16
10
15
14
5
13
12
11
10
9
0
1
0
50
2
100
3
4
150
5
6
200
7
8
250
300
350
400
450
500
550
600
650
700
750
800
Boiling point (°C)
The numbers refer to the calibration report table
AC SIMDIS Analyzers
22
Simdis Theory

Every analysis should be corrected for
column bleeding
 Analyze a blank in every sequence
 The blank signal is automatically subtracted
from every sample and reference signal
Simdis Theory

The net signal is used to determine boiling
points
 IBP at 0.5 % of the total area
 FBP at 99.5 % of the total area
 The total area lies between start and end
elution point
 The start and end time are determined by
elution algorithms
Simdis Theory

A reference sample is analyzed to check
system performance
AC SIMDIS D 2887 Reference
AC SIMDIS Analyzers
26
AC SIMDIS D 2887 reference reports
0
AC Simdis version 04.10
SIMDIS 4003001 ASTM D 2887
TEST
2
Sample name
Method name
Sample type
Sequence name
: ref
: C:\HPCHEM\1\METHODS\D2887C.M
: Ref 25650.150
: D0501A.S
Instrument
Vial
Injection
Seq. line
:1
: 103
:1
:3
Operator
Acquired on
Processed on
: saskia
: 5/1/00 5:31:06 PM
: 5/2/00 9:14:58 AM
Sample (g)
Solvent (g)
ISTD (g)
: 0.0000
: 0.0000
: 0.0000
Data File
: D051A\103F0301.D\FID1A.CH
Chromatogram:
200
8000
Boiling point (°F)
300
400
500
600
700
800
900
1000
1100
7000
6000
5000
Signal
4000
3000
End Time
FBP
IBP
1000
Start Time
2000
0
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
Retention time (min)
AC SIMDIS Analyzers
27
AC SIMDIS D 2887 Reference Reports
AC Simdis version 04.10
SIMDIS 4003001 ASTM D 2887
TEST
1
Sample name
Method name
Sample type
Sequence name
: ref
: C:\HPCHEM\1\METHODS\D2887C.M
: Ref 25650.150
: D0501A.S
Instrument
Vial
Injection
Seq. line
:1
: 103
:1
:3
Operator
Acquired on
Processed on
: saskia
: 5/1/00 5:31:06 PM
: 5/2/00 9:14:58 AM
Sample (g)
Solvent (g)
ISTD (g)
: 0.0000
: 0.0000
: 0.0000
Data File
Blankused
BP Calibrant
Last Reference
: D051A\103F0301.D\FID1A.CH
: D051A\101F0101.D\FID1A.CH corrected
: D051A\102F0201.D\FID1A.CH
: D0501\104F0101.D\FID1A.CH On spec.
Start Elution
End Elution
: 0.13
: 23.88>
Refe re nce sample re sults:
Target values
Mass% BP (°F)
dBP (°F)
IBP
286
21
10
406
6
20
455
6
30
489
6
40
520
6
50
549
6
60
577
6
70
606
6
80
640
6
90
680
6
FBP
748
13
Determined values
BP (°F)
dBP (°F)
292
6
408
2
457
2
491
2
521
1
550
1
578
1
606
0
641
1
681
1
752
4
Front channe l O N spe cification
AC SIMDIS Analyzers
28
Starting Analysis

Make & run a sequence
 Calibration
 Observe results
 Reprocess if necessary
Non Fitting Blank
Chromatogram:
0200
70000100
Boiling point (°C)
300
400
500
600
700
800
65000
60000
55000
50000
45000
Signal
40000
35000
30000
25000
20000
End Time
FBP
5000
IBP
10000
Start Time
15000
0
0
5
10
15
20
25
Retention time (min)
30
35
40
45
End Time Found Incorrectly
Chromatogram:
200
3000
300
Boiling point (°C)
400
500
600
700
800
2800
2600
2400
2200
2000
1800
Signal
1600
1400
1200
1000
800
End Time
200
FBP
400
Start Time
IBP
600
0
0
5
10
15
20
25
30
35
Retention time (min)
40
45
50
55