Thermal Conversion of - UGent Steven Pyl... · Thermal Conversion of Fossil and Renewable Feedstocks Steven P. Pyl ... • Kerosene steam cracking • Renewable naphtha steam cracking

Laboratory for Chemical Technology

Thermal Conversion of

Fossil and Renewable Feedstocks

Steven P. Pyl

Advisors

prof. dr. Marie-Françoise Reyniers

prof. dr. ir. Guy B. Marin

Feedstock

molecular

composition

continuity

equations

Fundamental

model

Product

molecular

composition

Process

conditions

Advanced

analytical

techniques

Co

mp

lex

fe

ed

sto

ck C

om

ple

x p

rod

uc

t

Advanced

analytical

techniquesPhysical

transport

phenomena

Microkinetic

model

The Need for Detail…

Fundamental Process Modeling = Molecule-based Modeling

Accurate experimental data is crucial!

Methusalem Advisory Board, 28/06/2010

Outline

Feedstock analyses

• Kerosene

• Renewable Naphtha

• Bio-diesel

Pilot Plant Experiments

• Kerosene steam cracking

• Renewable naphtha steam cracking

• Bio-diesel pyrolysis


GC GC setup

TOF-MS

GC×GC

Heated

Transfer-

line


GC GC setup

Initial objective

Maximal agreement

between

FID and TOF-MS

chromatograms

FID

OVEN

TOF-MS

He

Rtx-1 PONA

BPX-50

BPX-50

injector

Liquid CO2

(1)

(2)

(3)

(3)

(6)

(5)

(4)

(7)

modulator

FID

Quantitative results

TOF-MS

Peak identification

Van Geem, Pyl, et al. J. Chrom. A. 2010


Kerosene

1st dimension retention time (min)

10 5030

2n

d d

ime

nsio

n r

ete

ntio

n tim

e (

s)

0

4

C9

C16

Di-aromatics

naphthenes

Di-naphthenes

Mono-

aromatics

Naphtheno-

aromatics

paraffins


10 5030

2n

d d

ime

nsio

n r

ete

ntio

n tim

e (

s)

0

4

Di-aromatics

C9

C16

naphthenes

Di-naphthenes

Mono-

aromatics

Naphtheno-

aromatics

paraffins

GC GC-FID

GC GC-(TOF-MS)

KEROSENE

Identification and

quantification of 300

components

Confident peak

indentification

Accurate quatification3D view


10 40200

4

benzene

30

toluene

ethyl-

benzene

n-C13n-C12n-C11

n-C10n-C9

n-C8

n-C7

n-C6

propyl-

benzene

butyl-

benzene

Hydrodeoxygenation

Hydrocracking

Renewable Naphtha

GC×GC-FID analysis

n-Paraffins32.4%

iso-Paraffins59.9%

Olefins0.4%

Naphthenes6.5%

Aromatics0.8%Naphtha

Kerosene


Bio-diesel

C16:0

C18:0

C18:1

C18:2

C18:3

C20:1C22:1

C24:1

C16:1

C14:0

GC×GC-FID

wt% :0 :1 :2 :3

C14 0.48 0.00 0.00 0.00

C16 14.01 0.19 0.02 0.04

C18 2.69 57.73 16.49 5.61

C20 0.55 0.98 0.00 0.00

C22 0.27 0.36 0.00 0.00

C24 0.24 0.26 0.00 0.00

Transestrification Glycerol

FAME

O

O

C18:1


Outline

Feedstock analyses

• Kerosene

• Renewable Naphtha

• Bio-diesel

Pilot Plant Experiments

• Kerosene steam cracking

• Renewable naphtha steam cracking

• Bio-diesel pyrolysis


Pilot Plant

Furnace + Reactor

Online Analysis Section


Pilot Plant

cell 1 cell 2 cell 3 cell 4 cell 5 cell 6 cell 7

oil

flare

DHA

FURNACE & REACTOR ONLINE ANALYSISFEED

preheating & mixing reactor zone

P P P PP

condensate

GC×GC

(4)

(5)

(9)

(1)

(1)

(6)

(2)

(3)

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

N2

IR-GA

RGA PGA

(10)

(11)

(8)

(12)

(7)


cell 1 cell 2 cell 3 cell 4 cell 5 cell 6 cell 7

oil

flare

DHA



P P P PP

condensate

GC×GC

(4)

(5)

(9)

(1)

(1)

(6)

(2)

(3)

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

N2

IR-GA

RGA PGA

(10)

(11)

(8)

(12)

(7)

Pilot Plant: On-line Effluent Sampling

Heated transfer lines

300°C

GCGC

DHA


RGA (TCD)

RGA (FID)

PGA (TCD)

DHA (FID)

GC×GC (FID)

H2 CO2 C2H4 C2H6 C2H2 CH4 CON2

C2 C3 C4CH4

CO2 C2H4 C2H6 C2H2 CO CH4

C2 C3 C4CH4 C5 C6 ...

N2

...CH4

ch

eck

C16

C25cell 1 cell 2 cell 3 cell 4 cell 5 cell 6 cell 7

oil

flare

DHA



P P P PP

condensate

GC×GC

(4)

(5)

(9)

(1)

(1)

(6)

(2)

(3)

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

×

N2

IR-GA

RGA PGA

(10)

(11)

(8)

(12)

(7)

Pilot Plant: On-line Quantification Approach

Nitrogen = Internal Standard

DHA and GC×GC temperature program: -40°C 300°C

Methane = Reference Component



0 5025

2n

d d

ime

nsio

n r

ete

ntio

n tim

e (

s)

0

5

2


0 105

sig

na

l in

ten

sity (

mV

)

modulatednot

modulated

paraffins

(a) (b)

methane

propene

1.3-butadiene

ethene

indene

naphthalene

benzene

methyl-

naphthalenes

styrene

toluene

Kerosene Steam Cracking

GCGC chromatogram two parts

1. Conventional 1D part C4-

2. Comprehensive 2D part C5+


0 5025

2n

d d

ime

nsio

n r

ete

ntio

n tim

e (

s)

0

5

2


0 105

sig

na

l in

ten

sity (

mV

)

modulatednot

modulated

paraffins

(a) (b)

methane

propene

1.3-butadiene

ethene

indene

naphthalene

benzene

methyl-

naphthalenes

styrene

toluene



Reduced peak overlap

More straightforward peak identification More accurate quantification

Quantification of approximately 150 chemical components


20 5035

2n

d d

ime

nsio

n r

ete

ntio

n tim

e (

s)

0

5

8065

indene

naphthalene

acenapthylene

phenanthrene

pyrenetoluene

benzene ethyl-Bz

xylenes

styrenemethyl-naphthalenesvinyltoluene

anthracene

biphenyl

tri-methyl-Bz

methyl-indenes

acenapthene



35 5545

2n

d d

ime

nsio

n r

ete

ntio

n tim

e (

s)

0

1.8


35 452

nd

dim

en

sio

n r

ete

ntio

n tim

e (

s)

0

1.8

(a) (b)

C3 alkyl-

benzenes

nC14

nC10

nC14

nC10

C4 alkyl-

benzenes

C5 alkyl-

benzenes

C3 alkyl-

benzenes

C4 alkyl-

benzenes

C5 alkyl-

benzenes

vinyltoluene vinylstyrene vinyltoluene vinylstyrene


Reduced peak overlap

More straightforward peak identification

COT = 800 C COT = 840 C

More accurate quantification




COT = 800°C COT = 840°C COT = 800°C COT = 840°C

methane 8.736 12.718 indene 0.489 0.799

ethene 22.325 24.045 naphtalene 2.520 2.961

ethane 2.868 2.587 1-methyl-napthalene 2.401 2.126

propene 13.972 11.933 2-methyl-napthalene 1.919 1.673

propane 0.549 0.419 biphenyl 0.221 0.200

1.3-butadiene 4.657 4.520 2-ethyl-naphthalene 0.831 0.524

benzene 4.790 7.111 1.5-dimethyl-napthalene 0.343 0.252

toluene 3.051 3.656 1.6-dimethyl-napthalene 0.901 0.692

ethylbenzene 0.489 0.419 2-ethenyl-napthalene 0.230 0.491

m-xylene 0.759 0.874 1.4-dimethyl-napthalene 0.400 0.333

p-xylene 0.216 0.014 biphenylene 0.170 0.496

styrene 0.721 1.231 2-methyl-biphenyl 0.046 0.037

o-xylene 0.376 0.394 acenaphthylene 0.177 0.154

propylbenzene 0.066 0.019 phenanthrene 0.285 0.746

1-ethyl-2-methyl-benzene 0.369 0.313 anthracene 0.077 0.205

1.3.5-trimethyl-benzene 0.382 0.344 methyl-phenanthrene 0.187 0.285

1-methyl-indene 1.227 0.232 methyl-anthracene 0.035 0.329

2-methyl-indene 0.012 0.395 pyrene 0.107 0.233

Yields (wt%) Yields (wt%)



Renewable Naphtha Steam Cracking

0

5

10

15

20

25

30

35

10 11 12 13 14 15 16 17 18

Yie

ld (

wt%

)

Methane Yield (wt%)

ethylene propylene 1,3-butadiene 1-butene benzene pygas fuel oil

Effect of Coil Oulet Temperature

Detailed

feedstock

composition

continuity

equations

COILSIM1DDetailed

product

composition

Process

conditions

IDEAL

PLUG FLOWCRACKSIM

Symbols

Pilot Plant

Experiments

Lines

Simulated with

COILSIM1D


C18:1

C16:1

C20:1

Unconverted

FAME1-heptene

1-pentadecene

1-undecene1-nonene

1-heptadecene

1-tridecene

5

0100

C2 alkyl

benzene

C3 alkyl

benzene

C5 alkyl

benzene

C7 alkyl

benzene

C9 alkyl

benzene

FAME Pyrolysis

ON-LINE effluent analysis

600 C

3D view


benzene

toluene

styrene

naphthalene

1-pentene

1-heptene

1-pentadecene

1-undecene

Methyl-

propanoate

1-nonene

biphenyl

mono-

aromatics

di-aromatics

saturates &

olefins

5

1-tridecene

0100

FAME Pyrolysis

700 C

3D view

Ethylene : 25 wt%

Propylene : 12 wt%

CO + CO2 : 15 wt%

Benzene : 5 wt%

Toluene : 2.5 wt%


Conclusions

• Comprehensive 2D GC

Combination of FID and TOF-MS on one setup

• Molecular feedstock composition within reach

• Detailed on-line analysis of pilot plant product

Increasing our insight in occurring chemistry


Acknowledgement

• Prof. Wol

• Methusalem Funding

Thank you for

your attention!


Glossary

Pyrolysis : Thermal decomposition in the absence of air

FAME : Fatty Acid Methyl Esters

Modulator: High frequency sampling interface

COT: Coil Outlet Temperature


Documents

Thermal Conversion of - UGent Steven Pyl... · Thermal Conversion of Fossil and Renewable Feedstocks Steven P. Pyl ... • Kerosene steam cracking • Renewable naphtha steam cracking