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Comparison of ASTM

Comparison of ASTM
D 6730 (DHA) and ASTM
D 6730 (DHA) and ASTM
D 6839 (PIONA/
D 6839 (PIONA/
Reformulyzer
Reformulyzer

)
)
25
th
Anniversary Seminar Series 2006
Comparison of D 6730 and D 6839 2
Number of Possible
Number of Possible
Hydrocarbons
Hydrocarbons
Paraffins
Naphthenes
Aromatics
Olefins
0
50
100
150
200
250
300
350
400
450
500
5 6 7 8 9 10 11
C-number
#

i
s
o
m
e
r
s
Comparison of D 6730 and D 6839 3
Individual Components
Individual Components
1961 Packed Columns C3 C9 122 peaks
1968 Glass Capillary Naphthas 240 peaks
1979 Fused Silica Naphthas 380 peaks
1996 Fused Silica Gasoline 900+ peaks
Comparison of D 6730 and D 6839 4
Hydrocarbon Type/Carbon #
Hydrocarbon Type/Carbon #
1965 TCEP Aromatics
1968 Molsieve 13X Paraffins/Naphthenes
1970 Molsieve 5A Iso/n-paraffins
1983 Irreversible adsorption Olefins
1985 Reversible adsorption Olefins
1992 Reversible adsorption Oxygenates
Comparison of D 6730 and D 6839 5
Chromatograms
Chromatograms
DHA
Reformulyzer
Comparison of D 6730 and D 6839 6
Reformer Feed (HSR)
Reformer Feed (HSR)
Composition:
n,i-Paraffins, Naphthenes, Aromatics (incl. Benzene)
0
5
10
15
20
25
30
35
nParaf f ins iParaf f ins Naphthenes Aromatics
DHA
REF
%
Comparison of D 6730 and D 6839 7
Light Straight Run
Light Straight Run
DHA
The DHA separation and
identification of LSR is
highly reliable.
Reformulyzer
PNA, PiPNA and PIANO
mode can be used to
determine the
hydrocarbon types in LSR.
0
2
4
6
8
10
12
14
16
LSR
C
a
r
b
o
n

#
DHA
Reformulyzer
A light straight run is a saturated
naphtha with a boiling range of
30-100 C consisting of C4 - C8
hydrocarbons.
Comparison of D 6730 and D 6839 8
Heavy Straight Run
Heavy Straight Run
DHA
Due to the high amount of
high boiling isomers, DHA
does not provide a complete
separation on the capillary
column.
Reformulyzer
The PNA, PiPNA and PIANO
mode can very well be used
to determine the
hydrocarbon types.
0
2
4
6
8
10
12
14
16
HSR
C
a
r
b
o
n

#
DHA
Reformulyzer
A heavy straight run is a saturated
naphtha with a boiling range of
60 - 185 C consisting of C5 - C12
hydrocarbons, that includes a large
number of isomers, especially
naphthenes.
Comparison of D 6730 and D 6839 9
Reformate
Reformate
Composition:
n,i-Paraffins, Naphthenes, Aromatics
(incl. Benzene), Olefins
0
10
20
30
40
50
60
70
nParaf f ins iParaf f ins Naphthenes Aromatics
DHA
REF
%
Comparison of D 6730 and D 6839 10
Reformate
Reformate
DHA
The DHA analysis
provides a complete
separation and identifies
the components
Reformulyzer
The PNA and PIANO
modes provide an
accurate hydrocarbon type
classification per carbon
number.
Reformate is a converted naphtha
that consists of paraffins, some
napthenes, aromatics and small
amounts of olefins. The carbon
number range of reformate consists
of C4 - C10 hydrocarbons and
some naphthalenes. The boiling
range is 30 - 185C.
0
2
4
6
8
10
12
14
16
Reformate
C
a
r
b
o
n

#
DHA
Reformulyzer
Comparison of D 6730 and D 6839 11
FCC
FCC
Naphtha
Naphtha
Composition:
Paraffins, Naphthenes, Aromatics (incl. Benzene),
Olefins
0
10
20
30
40
50
P ar af f i ns Ol ef i ns Naphthenes Ar omati cs
DHA
REF
%
Comparison of D 6730 and D 6839 12
FCC Naphtha
FCC Naphtha
DHA
The capillary column is not
able to separate all
individual components; the
identification is not reliable
for components above
toluene.
Reformulyzer
The PHONA mode
provides correct carbon
number/ hydrocarbon type
information.
0
2
4
6
8
10
12
14
16
FCC Naphtha
C
a
r
b
o
n

#
DHA
Reformulyzer
The FCC naphtha is unsaturated
and consists of paraffins,
naphthenes, olefins and aromatics
with a carbon number range of
C4 -C12. The boiling range is
30 - 200 C.
Comparison of D 6730 and D 6839 13
Gasoline + Ethanol
Gasoline + Ethanol
Blended from:
Reformate, Isomerate, Alkylate, FCC, Oxygenate,
Reformer Feed
0
10
20
30
40
50
60
Paraf f i ns Ol ef i ns Naphthenes Aromati cs Oxygenates
DHA
REF
%
Comparison of D 6730 and D 6839 14
Finished
Finished
Gasoline
Gasoline
DHA Analysis
If the gasoline is blended
from saturates and one or
two oxygenates, DHA
provides sufficient data.
If the blend contains
olefins, the DHA data is
only reliable up to toluene.
Reformulyzer
ASTM D 6893 provides
therequired data for both
environmental regulations
and process control.
0
2
4
6
8
10
12
14
16
Gasoline
C
a
r
b
o
n

#
DHA
Reformulyzer
Finished gasoline is a hydrocarbon
blend of paraffins, naphthenes,
olefins, aromatics and possibly
some oxygenates. The boiling
range is 30 -185C and the carbon
number range is C4 - C10.
Comparison of D 6730 and D 6839 15
Sample
Sample
Scope
Scope
DHA Multi-Dimensional
Straight Run
+ +
FCC -- +
Reformate + +
Isomerate + +
Alkylate + +
Oxygenates + +
Gasoline -- +
Comparison of D 6730 and D 6839 16
Application
Application
Comparison
Comparison
DHA Multi-Dimensional
Standard
Method
D 6729, D 6730,
D 6733, D 5134
D 6839, EN 14517,
D 6293
Analysis Time 120 150 min
28 min on fast DHA
75 min for Winterspec
mode
Columns 1 or 2 7 (including traps)
User Group Not planned Yes
Crude Oil Yes, light end in crude
analysis (combi design)
No, FBP is
275C/527F
Comparison of D 6730 and D 6839 17
Application
Application
Comparison
Comparison
DHA Multi-Dimensional
Individual Components Benzene, Toluene,
Oxygenates
Group-type Group-type
RON RON
Mol.Weight Mol.Weight
Specific Gravity Density
TBP C:H:O ratio
Cal.Value
Comparison of D 6730 and D 6839 18
Conclusions
Conclusions
Both DHA & Reformulyzer are suitable for
analyzing refinery streams
DHA is recommended when mainly detailed
information is needed at component level
Reformulyzer is required when samples
containing higher amounts of Olefins and/or
Naphthenes above C7 8 are present in the
sample
Comparison of D 6730 and D 6839 19
Questions
Questions
?

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