Transcript AC Reformulyzer

AC Reformulyzer Course
AC Analytical Controls
January 2001
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AC Reformulyzer
Determining Gasoline
Specifications Efficiently
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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
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AC Reformulyzer
Hydrocarbon type analysis of finished
gasoline and feedstocks
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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
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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
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AC Reformulyzer
determines carbon number distribution of:
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Paraffins
Isoparaffins
Olefins
Naphthenes
Aromatics
Oxygenates
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AC Reformulyzer
Application Range
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Reformate
FCC naphtha
Isomerate
Alkylate
Straight naphtha
Gasoline
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Reported group types
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paraffins
iso-paraffins
olefins
naphtenes
aromatics
oxygenates
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Hydrocarbon Structure
Paraffins:
• Formula: CnH 2n+2
• Straight chain components
• Saturates
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Paraffins examples
n-pentane
C-C-C-C-C
iso-pentane
C-C-C-C
C
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Hydrocarbon Structure
Naphthenes:
• Formula: CnH 2n
• Ring/cyclo compounds
• Saturates
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Napthenes examples
cyclohexane
methylcyclohexane
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Polynapthenes
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Hydrocarbon Structure
Aromatics:
• Formula: CnH n
• Ring/cyclo compounds with
three double bond
• Unsaturated and chemically reactive
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Aromatics examples
Benzene
Toluene
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Hydrocarbon Structure
Olefins:
• Formula: CnH 2n
• Compounds with one double bond
• Unsaturated and chemically reactive
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Olefins examples
n-butene
C-C-C=C
iso-pentene
C-C=C-C
C
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Trivial names
• paraffin = alkane = saturate
• olefin = alkene = unsaturate
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Trivial names
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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
C a rb o n N o . P a ra ffin s
5
3
6
5
7
9
8
18
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75
O le fin s
6
17
36
92
>1000
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AC Reformulyzer
Configuration
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Reformulyzer Flow
n-Pa ra ffins
M S-5 A
O le fins
Pa r + Na p hth
O le fin
tra p
No n p o la r ro ute
No n-Po la r + Ethe rs +
C 6/C 7 Aro m a tic s ro ute
Sa m p le
Alc o ho l
O V-27 5
Tra p
Alc /Ethe r
M o lsie ve
13X
Aro m a tic s + Ethe rs a nd Alc o ho ls
De te c to r
Tra p
Ethe rs + Alc o ho ls + Aro m a tic s ro ute
Aro m a tic s + Alc o ho ls ro ute
O V-10 1
Po ra p a k
Ethe rs + C 6/C 7 Aro m a tic s
Alc o ho ls + Aro m a tic s ro ute
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Reformulyzer columns
• OV 275
• Ether/alc trap (tenax)
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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
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OV 275
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packed polar column
mounted in the GC oven
130°C , isothermal
conditioned in a separate GC
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Olefin trap
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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
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13 X column
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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
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5A trap
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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
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non polar capillary column
mounted inside the oven
130°C isothermal.
separation by boiling point
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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
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Alcohol pre-column
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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
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Reformulyzer flow diagram
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Reformulyzer left side compartment
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Reformulyzer oven compartment
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Piona flow diagram
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Piona left side compartment
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Piona oven compartment
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Piona prefractionator flow diagram
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C4 stream
Various hydrocarbon types by
Carbon number range
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Straight Run
Various hydrocarbon types by
Carbon number range
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Reformulyzer - Reformer Feed
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Reformate
Various hydrocarbon types by
Carbon number range
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Reformulyzer - Reformate
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FCC Naphtha
Various hydrocarbon types by
Carbon number range
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Reformulyzer - FCC Naphtha
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Isomerate
Various hydrocarbon types by
Carbon number range
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Alkylate
Various hydrocarbon types by
Carbon number range
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Oxygenates
Various hydrocarbon types by
Carbon number range
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MTBE
Various hydrocarbon types by
Carbon number range
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Finished Gasoline
C#
4
8
12
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Pa ra ffin s
Na p hthe n e s
O le fin s
Aro m a tic s
Ethe rs (M TBE)
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Gasoline mode
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OPNA Mode
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Winterspec Mode
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Reformulyzer Report
N or m a liz ed w eigh t p e rc e nt r e su lts
C -n r
N aph.
Pa raf.
C ycl O l.
O lef.
A ro m .
3
0 .0 0
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1.52
1.72
0.58
0.10
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T o tal
T ota l
3.92
H ig h bo iling a ro m atics
H ig h bo iling sa tu ra tes
T o ta l h y dro c a rb on s
1 .0 2
13 .9 4
16 .3 8
3 .1 5
14 .7 6
1 .7 0
0 .4 9
51 .4 4
0.07
0.18
0.08
0.31
2.15
1.34
0.37
0.08
0.33
4.24
0 .8 7
4 .5 8
1 7 .7 1
9 .1 0
1 .6 4
3 3 .9 0
1 .3 3
1 7 .6 8
2 0 .4 9
8 .7 6
3 2 .6 4
1 0 .8 0
2 .1 3
9 3 .8 4
0.33
0.73
9 4.89
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Reformulyzer Report
N orm a lized volu m e p ercen t results
C -n r
N aph.
Pa raf.
C ycl O l.
O lef.
A ro m .
3
4
5
1.48
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1.64
0.56
0.09
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8
9
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T o tal
3.77
H ig h bo iling a ro m a tic s
H ig h bo iling sa tu ra te s
T o ta l h y dro c a rb on s
1 .3 1
16 .6 1
18 .1 8
3 .3 5
15 .1 8
1 .7 0
0 .4 9
56 .8 2
0.07
0 .0 0
1 .6 8
2 0 .5 8
0.37
2.42
0.17
0.08
1.44
0.39
0.08
0.31
4.69
T ota l
0 .7 2
3 .8 5
1 4 .8 8
7 .6 3
1 .3 7
2 8 .4 6
2 2 .1 5
8 .2 2
3 0 .2 4
9 .3 2
1 .8 5
9 4 .0 5
0.28
0.64
9 4.97
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Reformulyzer Report
Oxygenates results
Oxygenate
MTBE
Wt%
LV%
O2%
5.11
5.03
0.93
DIN51448-2 Draft
Benzene
Total Aromatics
Total Olefins
Total Saturates
Total Oxygen
0.72 LV%
28.7 LV%
5.0 LV%
61.2 LV%
0.9 Wt%
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Site Specific Testing
N o . S a m p le
Nam e
C o m p o sitio n
C h a ra cte ristics
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R e fo rm e r
Feed
 N o o le fin s
 L o w co n ce n tra tio n o f
a ro m a tics
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R e fo rm a te
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FCC
N a p h th a
 P a ra ffin s,
N a p h th e n e s
 A ro m a tics,
B e n ze n e
 P a ra ffin s,
N a p h th e n e s
 A ro m a tics,
B e n ze n e
 O le fin s
 P a ra ffin s,
N a p h th e n e s
 A ro m a tics,
B e n ze n e
 O le fin s
 L o w co n ce n tra tio n o f
o le fin s
 H ig h co n ce n tra tio n
o f a ro m a tics
 B e n ze n e : 5 vo l%
 H ig h co n ce n tra tio n
o f o le fin s
 B e n ze n e : < 1 vo l%
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Site Specific Testing
N o . S a m p le
Nam e
C o m p o sitio n
C h a ra cte ristics
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G a so lin e 1
5
G a so lin e 2
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G a so lin e 3
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G a so lin e 4
 R e fo rm a te
 F C C N a p h th a
 O xyg e n a te
 R e fo rm a te
 F C C N a p h th a
 O xyg e n a te
 R e fo rm a te
 Iso m e ra te ,
A lkyla te
 F C C N a p h th a
 O xyg e n a te
 G a so lin e 3 b u t
e xclu d in g
o xyg e n a te s
 R e fo rm a te 5 0 %
 F C C N a p h th a 4 0 %
 M T B E : 1 0 w e ig h t%
 R e fo rm a te 5 0 %
 F C C N a p h th a 4 0 %
 E T B E : 1 0 w e ig h t%
 R e fo rm a te 2 0 %
 Iso m e ra te 1 0 % ,
A lkyla te 1 5 %
 F C C N a p h th a 5 0 %
 E th a n o l 5 w e ig h t %
 R e fo rm a te 2 0 %
 Iso m e ra te 1 0 % ,
A lkyla te 1 5 %
 F C C N a p h th a 5 5 %
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Methods & Developments
M e th o d s
PNA
SM S 2343
X
UO P 870
X
IP 3 8 2
X
D IN 5 1 4 4 8 -1
X
ASTM D 5443
X
A S T M d ra ft
P IO N A
R e fo rm u lyze r
X*
X **
ASTM D 6293
X
D ra ft D IN 5 1 4 4 8 -2
X
*
**
no precision data
withdrawn
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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
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