Comparison of ASTM Comparison of ASTM D 6730 (DHA) and ASTM D 6730 (DHA) and ASTM

D 6839 (PIONA/D 6839 (PIONA/ ReformulyzerReformulyzer))

25th Anniversary Seminar Series 2006

Comparison of D 6730 and D 6839 2

Number of Possible Number of Possible HydrocarbonsHydrocarbons

Paraffins

Naphthenes

Aromatics

Olefins

050

100150200250300350400450500

5 6 7 8 9 10 11C-number

#

i

s

o

m

e

r

s

Comparison of D 6730 and D 6839 3

Individual ComponentsIndividual Components1961 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

ChromatogramsChromatogramsDHA

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

nPar af f ins iPar af f ins Naphthenes Ar omatics

DHA

REF

%

Comparison of D 6730 and D 6839 7

Light Straight RunLight Straight RunDHAThe DHA separation andidentification of LSR is highly reliable.

ReformulyzerPNA, PiPNA and PIANO mode can be used to determine the hydrocarbon types in LSR.

02468

10121416

LSR

C

a

r

b

o

n

#

DHAReformulyzer

A light straight run is a saturatednaphtha with a boiling range of30-100 C consisting of C4 - C8hydrocarbons.

Comparison of D 6730 and D 6839 8

Heavy Straight RunHeavy Straight RunDHADue to the high amount ofhigh boiling isomers, DHAdoes not provide a completeseparation on the capillarycolumn.

ReformulyzerThe PNA, PiPNA and PIANOmode can very well be usedto determine thehydrocarbon types.

02468

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HSR

C

a

r

b

o

n

#

DHAReformulyzer

A heavy straight run is a saturatednaphtha with a boiling range of60 - 185 C consisting of C5 - C12hydrocarbons, that includes a largenumber of isomers, especiallynaphthenes.

Comparison of D 6730 and D 6839 9

ReformateReformateComposition:n,i-Paraffins, Naphthenes, Aromatics (incl. Benzene), Olefins

0

10

20

30

40

50

60

70

nPar af f ins iPar af f ins Naphthenes Ar omatics

DHAREF

%

Comparison of D 6730 and D 6839 10

ReformateReformateDHAThe DHA analysis provides a complete separation and identifies the components

ReformulyzerThe PNA and PIANO modes provide an accurate hydrocarbon typeclassification per carbonnumber.

Reformate is a converted naphthathat consists of paraffins, somenapthenes, aromatics and smallamounts of olefins. The carbonnumber range of reformate consistsof C4 - C10 hydrocarbons andsome naphthalenes. The boilingrange is 30 - 185C.

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Reformate

C

a

r

b

o

n

#

DHA

Reformulyzer

Comparison of D 6730 and D 6839 11

FCC FCC NaphthaNaphthaComposition:Paraffins, Naphthenes, Aromatics (incl. Benzene), Olefins

0

10

2 0

3 0

4 0

5 0

Par af f i ns Ol ef i ns Naphthenes Ar omat i cs

DHA

REF

%

Comparison of D 6730 and D 6839 12

FCC NaphthaFCC NaphthaDHAThe capillary column is notable to separate all individual components; theidentification is not reliablefor components abovetoluene.

ReformulyzerThe PHONA mode provides correct carbon number/ hydrocarbon type information.

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FCC Naphtha

C

a

r

b

o

n

#

DHAReformulyzer

The FCC naphtha is unsaturatedand consists of paraffins,naphthenes, olefins and aromaticswith a carbon number range ofC4 -C12. The boiling range is30 - 200 C.

Comparison of D 6730 and D 6839 13

Gasoline + EthanolGasoline + EthanolBlended from:Reformate, Isomerate, Alkylate, FCC, Oxygenate, Reformer Feed

0

10

2 0

3 0

4 0

5 0

6 0

Par af f in s Olef in s Napht hen es Ar omat ics Oxygen at es

DHA

REF%

Comparison of D 6730 and D 6839 14

FinishedFinished GasolineGasolineDHA AnalysisIf the gasoline is blendedfrom saturates and one ortwo oxygenates, DHAprovides sufficient data.If the blend contains olefins, the DHA data is only reliable up to toluene.

ReformulyzerASTM D 6893 provides therequired data for bothenvironmental regulationsand process control.

0 2 4 6 8

10 12 14 16

GasolineC

arbon #

DHAReformulyzer

Finished gasoline is a hydrocarbonblend of paraffins, naphthenes,olefins, aromatics and possiblysome oxygenates. The boilingrange is 30 -185C and the carbonnumber range is C4 - C10.

Comparison of D 6730 and D 6839 15

SampleSample ScopeScope

DHA Multi-DimensionalStraight Run + +FCC -- +

Reformate + +

Isomerate + +

Alkylate + +

Oxygenates + +

Gasoline -- +

Comparison of D 6730 and D 6839 16

ApplicationApplication ComparisonComparisonDHA Multi-Dimensional

Standard Method

D 6729, D 6730, D 6733, D 5134

D 6839, EN 14517, D 6293

Analysis Time 120 150 min28 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

ApplicationApplication ComparisonComparisonDHA 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

ConclusionsConclusions

Both DHA & Reformulyzer are suitable foranalyzing refinery streams

DHA is recommended when mainly detailedinformation is needed at component level

Reformulyzer is required when samples containing higher amounts of Olefins and/orNaphthenes above C7 8 are present in the sample

Comparison of D 6730 and D 6839 19

QuestionsQuestions

?

Comparison of ASTM D 6730 (DHA) and ASTM D 6839 (PIONA/ Reformulyzer)25th Anniversary Seminar Series 2006Number of Possible HydrocarbonsChromatogramsReformer Feed (HSR)Light Straight RunHeavy Straight RunReformateReformateFCC NaphthaFCC NaphthaGasoline + EthanolFinished GasolineSample ScopeApplication ComparisonApplication ComparisonConclusionsQuestions