Download AC Reformulyzer

AC Reformulyzer Course
AC Analytical Controls
January 2001
1
AC Reformulyzer
Determining Gasoline
Specifications Efficiently
2
AC Reformulyzer
• Hydrocarbon type/ Carbon number analysis
• Dedicated to Gasoline and Gasoline-related
streams
• Multi-dimensional analysis system
• Incorporates ASTM, DIN and IP standard test
methods
3
AC Reformulyzer
Hydrocarbon type analysis of finished
gasoline and feedstocks
4
AC Reformulyzer
• multi-column GC method
• separates hydrocarbon groups: paraffins,
isoparaffins, naphthenes, oxygenates,
aromatics and olefins in finished gasoline and
gasoline related streams, such as reformate,
FCC naphtha, isomerate and alkylate
• incorporates standard test methods ASTM D
6293 and Draft method DIN 51448-2
5
AC Reformulyzer
• Characterizes total composition of finished
gasoline and blending stocks in one analysis
• Conducting one analysis rather than several
reduces potential human bias and results in a
more cost effective lab
6
AC Reformulyzer
determines carbon number distribution of:
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•
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•
•
Paraffins
Isoparaffins
Olefins
Naphthenes
Aromatics
Oxygenates
7
AC Reformulyzer
Application Range
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•
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•
Reformate
FCC naphtha
Isomerate
Alkylate
Straight naphtha
Gasoline
8
Reported group types
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paraffins
iso-paraffins
olefins
naphtenes
aromatics
oxygenates
9
Hydrocarbon Structure
Paraffins:
• Formula: CnH 2n+2
• Straight chain components
• Saturates
10
Paraffins examples
n-pentane
C-C-C-C-C
iso-pentane
C-C-C-C
C
11
Hydrocarbon Structure
Naphthenes:
• Formula: CnH 2n
• Ring/cyclo compounds
• Saturates
12
Napthenes examples
cyclohexane
methylcyclohexane
13
Polynapthenes
14
Hydrocarbon Structure
Aromatics:
• Formula: CnH n
• Ring/cyclo compounds with
three double bond
• Unsaturated and chemically reactive
15
Aromatics examples
Benzene
Toluene
16
Hydrocarbon Structure
Olefins:
• Formula: CnH 2n
• Compounds with one double bond
• Unsaturated and chemically reactive
17
Olefins examples
n-butene
C-C-C=C
iso-pentene
C-C=C-C
C
18
Trivial names
• paraffin = alkane = saturate
• olefin = alkene = unsaturate
19
Trivial names
•
•
•
•
•
straight alkanes =
branched alkanes =
straight alkenes =
branched alkenes =
cyclo-alkanes
=
normal paraffin's
iso-paraffin's
normal olefins
iso-olefins
naphtenes
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Number of possible hydrocarbon
isomers
Carbon No. Paraffins
5
3
6
5
7
9
8
18
10
75
Olefins
6
17
36
92
>1000
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AC Reformulyzer
Configuration
22
Reformulyzer Flow
n-Paraffins
MS-5A
Olefins
Olefin
trap
Par + Naphth
Non polar route
Non-Polar + Ethers +
C6/C7 Aromatics route
Sample
Alcohol
Trap
OV-275
Alc/Ether
Trap
Molsieve
13X
Aromatics + Ethers and Alcohols
Detector
Ethers + Alcohols + Aromatics route
Aromatics + Alcohols route
OV-101
Porapak
Ethers + C6/C7 Aromatics
Alcohols + Aromatics route
23
Reformulyzer columns
• OV 275
• Ether/alc trap (tenax)
•
•
•
•
•
•
Olefin trap
5A trap
13X
HP-1 (OV 101)
PT catalyst
Alc. Pre-column
: polar Pre-column
: (1) Adsorption of ethers
: (2) Adsorption of aromatic fractions
: Adsorption of olefins
: Adsorption of n-Paraffins
: sep. of Nap/Par by carbon number
: separation of Aromatic fractions
: hydrogenation of Olefins
: Alcohol retaining column
24
OV 275
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•
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•
packed polar column
mounted in the GC oven
130°C , isothermal
conditioned in a separate GC
25
Olefin trap
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•
•
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•
Adsorption temperature
:approx 140°C
Desorption temperature
:250°C
Conditioning
: with FCC sample
Mounted in the AC left side compartment
Controlled by heater 4 of the ACI
26
13 X column
•
•
•
•
Temperature programmed 100°C - 430°C
Conditioning temp maximum 490°C
Mounted in the AC compartment
Controlled by heater 1 of the ACI
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Ether/ Alcohol Trap
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•
•
•
•
•
Adsorption temperature 70°C
Separation temperature approx. 100°C
Desorption temperature 280°C
Conditioned for 5 minutes at 280°C Max.
Mounted in the AC compartment
Controlled by heater 3 of the ACI
28
5A trap
•
•
•
•
•
Adsorption temperature approx. 140°C
Desorption temperature 450°C
Conditioned for 25 minutes at 450°C Max.
Mounted in the AC compartment
Controlled by heater 5 of the ACI
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HP 1 (OV 101) column
•
•
•
•
non polar capillary column
mounted inside the oven
130°C isothermal.
separation by boiling point
30
PT column
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•
•
•
Temperature 180°C (220°C)
Hydrogenation of Olefins
Mounted in the AC compartment
controlled by heater 2 of the ACI
31
Alcohol pre-column
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•
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•
Initial temperature approx. 160 °C
Alcohol retaining column
Mounted at the GC injector B position
Controlled by Auxilary 2 heating zone
32
Reformulyzer flow diagram
33
Reformulyzer left side compartment
34
Reformulyzer oven compartment
35
Piona flow diagram
36
Piona left side compartment
37
Piona oven compartment
38
Piona prefractionator flow diagram
39
C4 stream
Various hydrocarbon types by
Carbon number range
40
Straight Run
Various hydrocarbon types by
Carbon number range
41
Reformulyzer - Reformer Feed
42
Reformate
Various hydrocarbon types by
Carbon number range
43
Reformulyzer - Reformate
44
FCC Naphtha
Various hydrocarbon types by
Carbon number range
45
Reformulyzer - FCC Naphtha
46
Isomerate
Various hydrocarbon types by
Carbon number range
47
48
Alkylate
Various hydrocarbon types by
Carbon number range
49
50
Oxygenates
Various hydrocarbon types by
Carbon number range
51
MTBE
Various hydrocarbon types by
Carbon number range
52
Finished Gasoline
C#
4
8
12
16
Paraffins
Naphthenes
Olefins
Aromatics
Ethers (MTBE)
53
Gasoline mode
54
OPNA Mode
55
Winterspec Mode
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Reformulyzer Report
Normalized weight percent results
C-nr
3
4
5
6
7
8
9
10
Total
Naph.
1.52
1.72
0.58
0.10
3.92
High boiling aromatics
High boiling saturates
Total hydrocarbons
Paraf.
1.02
13.94
16.38
3.15
14.76
1.70
0.49
51.44
Cycl Ol.
Olef.
0.07
0.18
0.08
0.31
2.15
1.34
0.37
0.08
0.33
4.24
Arom.
Total
0.87
4.58
17.71
9.10
1.64
33.90
0.00
1.33
17.68
20.49
8.76
32.64
10.80
2.13
93.84
0.33
0.73
94.89
57
Reformulyzer Report
Normalized volume percent results
C-nr
3
4
5
6
7
8
9
10
Total
Naph.
1.48
1.64
0.56
0.09
3.77
High boiling aromatics
High boiling saturates
Total hydrocarbons
Paraf.
1.31
16.61
18.18
3.35
15.18
1.70
0.49
56.82
Cycl Ol.
Olef.
0.07
0.17
0.08
0.37
2.42
1.44
0.39
0.08
0.31
4.69
Arom.
Total
0.72
3.85
14.88
7.63
1.37
28.46
0.00
1.68
20.58
22.15
8.22
30.24
9.32
1.85
94.05
0.28
0.64
94.97
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Reformulyzer Report
O
xygenatesresults
Oxygenate
M
TBE
W
t%
LV%
O2%
5.11
5.03
0.93
DIN51448-2 Draft
Benzene
Total Aromatics
Total Olefins
Total Saturates
Total Oxygen
0.72LV%
28.7LV%
5.0LV%
61.2LV%
0.9W
t%
59
Site Specific Testing
No. Sample
Name
Composition
Characteristics
1
Reformer
Feed
 No olefins
 Low concentration of
aromatics
2
Reformate
3
FCC
Naphtha
 Paraffins,
Naphthenes
 Aromatics,
Benzene
 Paraffins,
Naphthenes
 Aromatics,
Benzene
 Olefins
 Paraffins,
Naphthenes
 Aromatics,
Benzene
 Olefins
 Low concentration of
olefins
 High concentration
of aromatics
 Benzene: 5 vol%
 High concentration
of olefins
 Benzene: < 1 vol%
60
Site Specific Testing
No. Sample
Name
Composition
Characteristics
4
Gasoline 1
5
Gasoline 2
6
Gasoline 3
7
Gasoline 4
 Reformate
 FCC Naphtha
 Oxygenate
 Reformate
 FCC Naphtha
 Oxygenate
 Reformate
 Isomerate,
Alkylate
 FCC Naphtha
 Oxygenate
 Gasoline 3 but
excluding
oxygenates
 Reformate 50%
 FCC Naphtha 40%
 MTBE: 10 weight%
 Reformate 50%
 FCC Naphtha 40%
 ETBE: 10 weight%
 Reformate 20%
 Isomerate 10%,
Alkylate 15%
 FCC Naphtha 50%
 Ethanol 5 weight %
 Reformate 20%
 Isomerate 10%,
Alkylate 15%
 FCC Naphtha 55%
61
Methods & Developments
Methods
PNA
SMS 2343
X
UOP 870
X
IP 382
X
DIN 51448-1
X
ASTM D 5443
X
ASTM draft
PIONA Reformulyzer
X*
X**
ASTM D 6293
X
Draft DIN 51448-2
X
*
**
no precision data
withdrawn
62
Method Comparison
Correct
Data
Less
Information
ASTM D 3606
ASTM D 5580
ASTM D 4815
ASTM D 6296
ASTM D 5599
ASTM D 6293 - Reformulyzer
MSD
A lot of
Information
Single column
Incorrect
Data
63