GC×GC: A petroleomics approach to unravel petroleum refinery processes

Confidential 1st Nordic GC×GC workshop

5 March 2013, Haldor Topsøe/DK

Asger B. Hansen

GC×GC: A petroleomics approach to

unravel petroleum refinery processes

Confidential

Presentation outline

Petroleomics

– Petroleome and petroleomics technology

Petroleum refining – refinery streams

– Hydrotreating processes (HDT)

GC×GC: unravelling the petroleomics of refinery processes

– Desulfurization of fuel oil (HDS)

Conversion of sulfur compounds

– Upgrading of shale oil

Conversion of oxygen compounds (HDO)

– Aromatics in unconverted oil (UCO)

Conversion of aromatics (HDA) – PNAs and ”mystery compound”

Conclusion

1st Nordic GC×GC workshop


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Petroleome – Petroleomics

Petroleome

– The ”genome” of crude oil –

a listing of all chemical compounds

Petroleomics

– Prediction of petroleum properties based on elucidating the

chemistry of all constituents in crude oil (~ 40,000)

– Petroleum science moving from phenomelogical description to

establishing structure-function/reactivity relationships



GC×GC

FTICR-MS

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Petroleomics technology

Targeting reaction products

– Molecular-level understanding of the composition and reactivity

of feedstocks helps determining the most efficient method for

producing target reaction products

Molecule-based kinetic modeling

– Detailed chemical composition analysis enables molecule-based

reaction simulation and kinetic modeling



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Petroleum refining – refinery streams



Visbreaker – thermal cracking

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Petroleum refining – hydrotreatment (HDT)



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Hydrotreating processes



Sulphur conversion (hydrodesulfurization - HDS)

Nitrogen conversion (hydrodenitrogenation - HDN)

Metals removal (hydrodemetallation - HDM)

Oxygen conversion (hydrodeoxygenation - HDO)

Hydrogenation of:

– Aromatic saturation (hydrodearomatization - HDA)

– Olefins (HYD)

Hydrocracking (HYC)

(Isomerisation, Ring Opening)

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GC×GC-FID



Diaromatics

Monoaromatics

Saturates

Triaromatics

Dibenzothiophenes (DBTs)

Benzothiophenes (BTs)

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Characterization of middle distillates -

saturates

Characterization of paraffins/naphthenes



GC×GC-

FID

GC×GC-

ToFMS

Naphthenes

Paraffins

Aromatics

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Characterization of middle distillates -

aromatics



Characterisation of aromatics/naphthenoaromatics

GC×GC-

FID

GC×GC-

ToFMS

DiAro

monoAro

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Reactivity of hydrocarbons

during HDT



Unsaturated compounds

0

2

4

6

8

10

12

14

0 20 40 60 80 100

% HDS conversion

are

a, %

mAro NmAro diAro NdiAro triAro NtriAro tetAro

Saturated compounds

0

10

20

30

40

50

60

0 10 20 30 40 50 60 70 80 90 100

% HDS conversion

are

a, % Paraffins

Naphthenes

triAro

diAro

BT mAro

NmAro

NmAro

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Component based description of HDS



CoMo

cat.

SR gas oil

Product with

varying S content

T = 325 °C

P = 30 barg

H2/oil = 250 Nl/l

WHSV: 0.4 – 240 h-1

Obtain product samples with

varying HDS conversion and

rationalize results from

GC×GC analysis

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GC×GC-SCD



BenzoNaphtho-

thiophenes (NBT)

Phenanthro-

thiophenes (NDBT)

Benzothiophenes (BT)

Dibenzothiophenes (DBT)

Thiophenes (T)

Naphtheno-

thiophenes (NT)

Naphthenobenzo-

thiophenes (NBT)

C0 C1

C2 C3

C4 C5

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HDS as a function of catalyst volume



LG.X.SK.B4

S = 13000 wt ppm

CoMo

cat.

Feed LG.X.SK.B4

S ≈ 2000 wt ppm.

All Ts and BTs has

been removed 5%

33%

S ≈ 120 wt ppm. 2/3 of the catalyst volume

is being used for removal of

4,6-alkylsubstituted DBTs !

S ≈ 800 wt ppm. Most

DBT without substituents

in 4,6 or both has been

removed

10%

T

BT

DBT

DBT

DBT

DBT

Confidential

Overall reactivity of S-compounds



Most abundant sulfur compounds

0

1000

2000

3000

4000

5000

6000

0 20 40 60 80 100

% HDS conversion

Su

lfu

r, w

t p

pm

0

20

40

60

80

100

120

140

160

180

200

Nit

rog

en

, w

t p

pm

BTsDBTsNBasic N

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Reactivity of benzo-

thiophenes (BTs)



Carbon number and HDS rate for BTs

0

10

20

30

40

50

60

70

BT-C

8-C10

BT-C

11-xC3

BT-C

12-xC4

BT-C

13-xC5

BT-C

14-xC6

BT-C

15-xC7

BT-C

16-xC8

BT-C

17-xC9

BT-C

18-xC10

BT-C

19-xC11

BT-C

20-xC12

BT-C

21-xC13

BT-C

22-xC14

BT-C

23-xC15

BT-C

24-xC16

All B

Ts

1.

ord

er

k,h

-1

1. order rate constants for BTs as a function of carbon atoms

In contrast to DBTs,

the substitution pattern

has no effect on the

reactivity of BTs

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Reactivity of dibenzothio-

phenes (DBT and C1-DBTs)



0

50

100

150

200

250

0 20 40 60 80 100

%HDS conversion

S, w

t p

pm

DBT-C12

DBT-C13-1M

DBT-C13-2/3M

DBT-C13-4M

Reactivity order

4-MethylDBT

k = 6 h-1

k = 0.5 h-1

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Reactivity of

C2-DBTs



0

50

100

150

200

250

300

0 10 20 30 40 50 60 70 80 90 100

%HDS conversion

S, w

t p

pm

DBT-C14-2.3dM DBT-C14-1.3/3.4/1.8dM

DBT-C14-1.4/1.6/2.8dM DBT-C14-2.4dM

DBT-C14-3/2.6dM DBT-C14-4.6dM

DBT-C14-4/3Et

0

20

40

60

80

100

0 20 40 60 80 100

%HDS conversion

S, w

t p

pm

DBT-C14-1.2dM DBT-C14-1.7/1.9/2.3dM

DBT-C14-1Et DBT-C14-2/3.7dM

4,6-DimethylDBT

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Fate of DBTs during HDS



Direct conversion of DBT and

M-DBTs to BPs

Hydrogenation of DBTs to

CHBs

1M-DBT 2M-BP + xM-CHB




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Direct conversion of M-DBTs to M-BPs



Feed 63%68% 73%

79% 85%90%

96%

DBT

BP

0

5

10

15

20

25

30

35

40

45

Re

l. A

mo

un

t

Conversion (%)

DBT

BP

Feed63% 68% 73%

79%85%

90%96%

1M-DBT

2M-BP

0

2

4

6

8

10

12

Re

l. A

mo

un

t

Conversion (%)

1M-DBT

2M-BP

Feed 63%68% 73%

79% 85%90%

96%

3M-DBT

4M-BP

0

2

4

6

8

10

12

14

16

Re

l. A

mo

un

t

Conversion (%)

3M-DBT

4M-BP

Feed 63% 68% 73%79%

85%90%

96%

4M-DBT

3M-BP

0

5

10

15

20

25

30

35

Re

l. A

mo

un

t

Conversion (%)

4M-DBT

3M-BP

M-DBT M-BP

DBT

BP

3M-DBT

4M-BP

1M-DBT

2M-BP

3M-BP

2/4M-DBT

m/z 198 m/z 168

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Shale oil (immature - unconventional oil)

Mining

– Oil shale (kerogen shale): organic-rich sedimentary rock that contains solid mixtures of chemical compounds

– Surface mining (open pit, strip mining)

– Underground mining (room and pillar method)

Extraction (ex-situ or in-situ)

– Oil shale is immature: kerogen not converted to oil by heat/pressure

– Pyrolysis/retorting (450-500°C): converts kerogen to shale oil (synthetic crude oil) and gas

Refining/upgrading

– Hydrotreating/-cracking



//upload.wikimedia.org/wikipedia/commons/2/2b/Oil_shale_extraction_overview.png

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Shale oil properties



Shale

kerogen

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Shale oil refining (HDO) - 1

GCxGC-MS and ChromaTof classification



SO.X.NAO.B2 (feed) 1.SO.X.NAO.B2 (HT)

HYK 1231 625 APF1 HYK 1231 1243 APF1

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Shale oil processing (HDO) - 2

Oxygen speciation



0,00

0,10

0,20

0,30

0,40

0,50

0,60

0,70

0,80

SO.X.NAO.B21.SO.X.NAO.B2

HYK 1231 625APF1 HYK 1231 1243

APF1

No

rmal

ised

Pea

k A

rea

(TIC

- P

ara

ffin

s)

Sample Name

Oxygen-containing compounds

Ketones

Phenols

DiHydBenz

Naphthols

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Hydrotreating/hydrocracking of

PNAs in unconverted oil (UCO)



Gasoil feed (350-550°C,

2% S,

1500 wt ppm N)

Make-up

hydrogen

Light ends

Naphtha

Jet

Diesel

UCO

HPS

Recycle

hydrogen

Hydro-

treating

Hydro-

cracking

Recycle of UCO

Interstage

APF

Confidential

PNA reactions during hydroprocessing



Polycondensation

polymerisation

Hydrogenation /

dehydrogenation

Coke

Hydrocracking

A + nH2 ↔ AH

exothermic: 63-71 kJ/mol H2

T ↑ A P ↑ AH

Confidential

Effect of temperature on PNA conversion

in UCO during HDT



Feed (UCO)

PAH/HPNA

HYC @ RH 402 - 250°C

HYC @ RH 478 - 300°C HYC @ RH 611 - 350°C

Confidential

Fate of PNAs in uncoverted oil (UCO)

during hydrotreatment



Sample

Hydrotreatment (°C)

Feed

(pretreated UCO)

HYC @ RH 402

(250°C)

HYC @ RH 478

(300°C)

HYC @ RH 611

(350°C)

1-ring compounds (m/e)

unspec

mononaphthenes


unspec

dinaphthenes


206-220-234

182-196-(210)-224

178-192-206-220-234-248

unspec

phenanthrenes

H4-phenanthrenes

phenalenes

trinaphthenes


202-216-230-244-258

228-242-256-270-284

(204)-218-(232)-246

208-222-236

218-232-246-260-274

pyrenes

chrysenes

H2-pyrenes

H6-pyrenes

H16-pyrenes

H16-pyrenes

H16-pyrenes


252-266-280

244-258

252-266-280

258-272-286-300

benzo(x)pyrenes

H6-benzo(xy)pyrenes

H12-benzo(xy)pyrenes





276-290-304

278-292

298-312

benzo(ghi)perylenes

H2-benzo(ghi)perylenes




benzo(ghi)perylene



300-314

316

324-338

coronenes

H2-dibenzoperylenes

H24-coronenes

coronene

H24-coronenes

coronene

H24-coronenes

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Conclusion



To control and predict refinery processes using tailor-made

catalysts improved knowledge about refinery streams, their

composition, properties and reactivity based on a petroleo-

mics approach with comprehensive separation and identifi-

cation of component classes and individual compounds is

needed. In such processes, GC×GC seems a very strong

analytical and diagnostic tool.

Confidential

Acknowledgement



I wish to acknowledge collegues and collaborators for

contributing to this presentation:

Asbjørn S. Andersson (HTAS)

Sylvain Verdier (HTAS)

Rasmus G. Egeberg (HTAS)

Jon E. Johansen (Chiron, NO)

Thank you for your attention

Confidential 100 years 2013

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GC×GC: A petroleomics approach to unravel petroleum refinery processes