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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:

• Paraffins

• Isoparaffins

• Olefins

• Naphthenes

• Aromatics

• Oxygenates

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AC Reformulyzer Application Range

• Reformate

• FCC naphtha

• Isomerate

• Alkylate

• Straight naphtha

• Gasoline

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Reported group types

• 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-pentaneC-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

• straight alkanes = normal paraffin's

• branched alkanes = iso-paraffin's

• straight alkenes = normal olefins

• branched alkenes = iso-olefins

• cyclo-alkanes = naphtenes

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Number of possible hydrocarbon isomers

Carbon No. Paraffins Olefins 5 3 6 6 5 17 7 9 36 8 18 92 10 75 >1000

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AC Reformulyzer Configuration

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Reformulyzer Flow

O V-275

O le fin tra p

M S-5A

M o lsie ve

De te c to r

13X

Alc /Ethe rAlc o ho lSa m p le Tra p Tra p

O V-101 Po ra p a k

No n-Po la r + Ethe rs + C 6/C 7 Aro ma tic s ro ute

Aro ma tic s + Alc o ho ls ro ute

Ethe rs + A lc o ho ls + Aro ma tic s ro ute

Alc o ho ls + Aro m a tic s ro ute

No n p o la r ro ute

O le fins

n-Pa ra ffins

Ethe rs + C 6/C 7 Aro ma tic s

Pa r + Na p hth

Aro ma tic s + Ethe rs a nd Alc o ho ls

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Reformulyzer columns

• OV 275 : polar Pre-column

• Ether/alc trap (tenax) : (1) Adsorption of ethers

: (2) Adsorption of aromatic fractions

• Olefin trap : Adsorption of olefins

• 5A trap : Adsorption of n-Paraffins

• 13X : sep. of Nap/Par by carbon number

• HP-1 (OV 101) : separation of Aromatic fractions

• PT catalyst : hydrogenation of Olefins

• Alc. Pre-column : Alcohol retaining column

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OV 275

• packed polar column

• mounted in the GC oven

• 130°C , isothermal

• conditioned in a separate GC

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Olefin trap

• 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

• 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

• 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

• 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

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PT column

• 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

• 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 streamVarious hydrocarbon types by

Carbon number range

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Straight RunVarious hydrocarbon types by

Carbon number range

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Reformulyzer - Reformer Feed

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ReformateVarious hydrocarbon types by

Carbon number range

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Reformulyzer - Reformate

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FCC NaphthaVarious hydrocarbon types by

Carbon number range

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Reformulyzer - FCC Naphtha

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IsomerateVarious hydrocarbon types by

Carbon number range

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AlkylateVarious hydrocarbon types by

Carbon number range

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OxygenatesVarious hydrocarbon types by

Carbon number range

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MTBEVarious hydrocarbon types by

Carbon number range

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Finished Gasoline

Pa ra ffins

Na p hthe ne s

O le fins

Aro m a tic s

Ethe rs (M TBE)

4C # 8 12 16

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Gasoline mode

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OPNA Mode

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Winterspec Mode

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N or m a liz ed w eigh t p e rc e n t r e su lt sC - n r P a r a f . O le f .N a p h . C y c l O l . A r o m .

3

4

5

6

7

8

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1 0

1 .0 2

0 .4 91 .7 0

1 4 .7 63 .1 5

1 6 .3 81 3 .9 4

0 .0 80 .1 80 .0 7

0 .0 80 .3 71 .3 42 .1 50 .3 1

0 .1 00 .5 81 .7 21 .5 2

1 .6 49 .1 0

1 7 .7 14 .5 80 .8 7

T o t a l 3 .9 2 5 1 .4 4 0 .3 3 4 .2 4 3 3 .9 0

T o t a l

0 .0 01 .3 3

1 7 .6 82 0 .4 9

8 .7 63 2 .6 41 0 .8 0

2 .1 39 3 .8 4

H ig h b o il in g a ro m a tic s 0 .3 3H ig h b o il in g s a tu ra te s 0 .7 3T o ta l h y d ro c a rb o n s 9 4 .8 9

Reformulyzer Report

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N orm a lized v o lu m e p ercen t re sultsC - n r P a r a f . O le f .N a p h . C y c l O l . A r o m .

3

4

5

6

7

8

9

1 0

1 .3 1

0 .4 91 .7 0

1 5 .1 83 .3 5

1 8 .1 81 6 .6 1

0 .0 80 .1 70 .0 7

0 .0 80 .3 91 .4 42 .4 20 .3 7

0 .0 90 .5 61 .6 41 .4 8

1 .3 77 .6 3

1 4 .8 83 .8 50 .7 2

T o t a l 3 .7 7 5 6 .8 2 0 .3 1 4 .6 9 2 8 .4 6

T o t a l

0 .0 01 .6 8

2 0 .5 82 2 .1 5

8 .2 23 0 .2 4

9 .3 21 .8 5

9 4 .0 5

H ig h b o il in g a ro m a tic s 0 .2 8H ig h b o il in g s a tu ra te s 0 .6 4T o ta l h y d ro c a rb o n s 9 4 .9 7

Reformulyzer Report

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M T B E 5 .1 1 5 .0 3 0 .9 3

O x yg en ates re su ltsO x y g e n a t e W t % L V % O 2 %

D IN 5 1 4 48 -2B e n z e n e 0 .7 2 L V %T o ta l A r o m a tic s 2 8 .7 L V %T o ta l O le f in s 5 .0 L V %T o ta l S a tu ra tes 6 1 .2 L V %T o ta l O x y g e n 0 .9 W t%

D ra ft

Reformulyzer Report

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Site Specific Testing

No. SampleName

Composition Characteristics

1 ReformerFeed

Paraffins,Naphthenes

Aromatics,Benzene

No olefinsLow concentration of

aromatics

2 Reformate Paraffins,Naphthenes

Aromatics,Benzene

Olefins

Low concentration ofolefins

High concentrationof aromatics

Benzene: 5 vol%3 FCC

NaphthaParaffins,

NaphthenesAromatics,

BenzeneOlefins

High concentrationof olefins

Benzene: < 1 vol%

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Site Specific Testing

No. SampleName

Composition Characteristics

4 Gasoline 1 ReformateFCC NaphthaOxygenate

Reformate 50%FCC Naphtha 40%MTBE: 10 weight%

5 Gasoline 2 ReformateFCC NaphthaOxygenate

Reformate 50%FCC Naphtha 40%ETBE: 10 weight%

6 Gasoline 3 ReformateIsomerate,

AlkylateFCC NaphthaOxygenate

Reformate 20%Isomerate 10%,

Alkylate 15%FCC Naphtha 50%Ethanol 5 weight %

7 Gasoline 4 Gasoline 3 butexcludingoxygenates

Reformate 20%Isomerate 10%,

Alkylate 15%FCC Naphtha 55%

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Methods & Developments

Methods PNA PIONA Reformulyzer

SMS 2343 X

UOP 870 X

IP 382 X

DIN 51448-1 X X*

ASTM D 5443 X

ASTM draft X**

ASTM D 6293 X

Draft DIN 51448-2 X

* no precision data** withdrawn

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Method Comparison

ASTM D 3606ASTM D 5580ASTM D 4815ASTM D 6296ASTM D 5599

ASTM D 6293 - Reformulyzer

MSD

Single column

Less Information

A lot ofInformation

CorrectData

IncorrectData