Thermal Conversion of Fossil and Renewable Feedstocks Steven P. Pyl - - PowerPoint PPT Presentation

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Thermal Conversion of Fossil and Renewable Feedstocks Steven P. Pyl - - PowerPoint PPT Presentation

Dec 28, 2022 32 likes •264 views

Thermal Conversion of Fossil and Renewable Feedstocks Steven P. Pyl Advisors prof. dr. Marie-Franoise Reyniers prof. dr. ir. Guy B. Marin Laboratory for Chemical Technology Methusalem Advisory Board, 28/06/2010 The Need for Detail

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SLIDE 1

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
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SLIDE 2

Feedstock molecular composition

continuity equations

Fundamental model Product molecular composition

Process conditions Advanced analytical techniques

Complex feedstock Complex product

Advanced analytical techniques Physical 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

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SLIDE 3

Outline

Feedstock analyses

  • Kerosene
  • Renewable Naphtha
  • Bio-diesel

Pilot Plant Experiments

  • Kerosene steam cracking
  • Renewable naphtha steam cracking
  • Bio-diesel pyrolysis

Methusalem Advisory Board, 28/06/2010

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SLIDE 4

GC GC setup

TOF-MS GC×GC Heated Transfer- line

Methusalem Advisory Board, 28/06/2010

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SLIDE 5

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

Methusalem Advisory Board, 28/06/2010

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SLIDE 6

Kerosene

10 50 30 4 C9 C16 Di-aromatics naphthenes Di-naphthenes Mono- aromatics Naphtheno- aromatics paraffins 10 50 30 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 quatification 3D view

Methusalem Advisory Board, 28/06/2010

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SLIDE 7

10 40 20 4 benzene 30 toluene ethyl- benzene n-C13 n-C12 n-C11 n-C10 n-C9 n-C8 n-C7 n-C6 propyl- benzene butyl- benzene

Hydrodeoxygenation Hydrocracking

Renewable Naphtha

GC×GC-FID analysis

n-Paraffins 32.4% iso-Paraffins 59.9% Olefins 0.4% Naphthenes 6.5% Aromatics 0.8%

Naphtha Kerosene

Methusalem Advisory Board, 28/06/2010

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SLIDE 8

Bio-diesel

C16:0 C18:0 C18:1 C18:2 C18:3 C20:1 C22:1 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

Methusalem Advisory Board, 28/06/2010

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SLIDE 9

Outline

Feedstock analyses

  • Kerosene
  • Renewable Naphtha
  • Bio-diesel

Pilot Plant Experiments

  • Kerosene steam cracking
  • Renewable naphtha steam cracking
  • Bio-diesel pyrolysis

Methusalem Advisory Board, 28/06/2010

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SLIDE 10

Pilot Plant

Furnace + Reactor Online Analysis Section

Methusalem Advisory Board, 28/06/2010

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SLIDE 11

Pilot Plant

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

  • il

flare DHA FURNACE & REACTOR ONLINE ANALYSIS FEED preheating & mixing reactor zone P P P P P

condensate

GC×GC

(4) (5) (9) (1) (1) (6) (2) (3)

× × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × × ×

N2 IR-GA RGA PGA

(10) (11) (8) (12) (7)

Methusalem Advisory Board, 28/06/2010

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SLIDE 12
  • il

flare DHA ONLINE ANALYSIS P

condensate

GC×GC

(4) (5) (9) (6)

N2 IR-GA RGA PGA

(10) (11) (8) (12) (7)

Pilot Plant: On-line Effluent Sampling

Heated transfer lines 300°C GCGC DHA

Methusalem Advisory Board, 28/06/2010

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SLIDE 13

RGA (TCD) RGA (FID) PGA (TCD) DHA (FID) GC×GC (FID) H2 CO2 C2H4 C2H6 C2H2 CH4 CO N2 C2 C3 C4 CH4 CO2 C2H4 C2H6 C2H2 CO CH4 C2 C3 C4 CH4 C5 C6 ... N2 ... CH4

check

C16 C25

  • il

flare DHA ONLINE ANALYSIS P

condensate

GC×GC

(4) (5) (9) (6)

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

Methusalem Advisory Board, 28/06/2010

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SLIDE 14

1st dimension retention time (min) 50 25 2nd dimension retention time (s) 5 2 modulated not modulated paraffins (a) indene naphthalene benzene methyl- naphthalenes styrene toluene

Kerosene Steam Cracking

GCGC chromatogram  two parts

  • 1. Conventional 1D part

 C4-

  • 2. Comprehensive 2D part

 C5+

1st dimension retention time (min) 10 5 signal intensity (mV) (b) methane propene 1.3-butadiene ethene

Methusalem Advisory Board, 28/06/2010

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SLIDE 15

Kerosene Steam Cracking

Reduced peak overlap More straightforward peak identification  More accurate quantification  Quantification of approximately 150 chemical components

1st dimension retention time (min) 20 50 35 5 80 65 indene naphthalene acenapthylene phenanthrene pyrene toluene benzene ethyl-Bz xylenes styrene methyl-naphthalenes vinyltoluene anthracene biphenyl tri-methyl-Bz methyl-indenes acenapthene Methusalem Advisory Board, 28/06/2010

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SLIDE 16

1st dimension retention time (min) 35 55 45 2nd dimension retention time (s) 1.8 1st dimension retention time (min) 35 45 2nd dimension retention time (s) 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

Kerosene Steam Cracking

Reduced peak overlap More straightforward peak identification COT = 800 C COT = 840 C  More accurate quantification  Quantification of approximately 150 chemical components

Methusalem Advisory Board, 28/06/2010

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SLIDE 17

Kerosene Steam Cracking

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

  • -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%)

 Quantification of approximately 150 chemical components

Methusalem Advisory Board, 28/06/2010

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SLIDE 18

Renewable Naphtha Steam Cracking

5 10 15 20 25 30 35 10 11 12 13 14 15 16 17 18

Yield (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

COILSIM1D

Detailed product composition

Process conditions

IDEAL PLUG FLOW CRACKSIM

Symbols Pilot Plant Experiments Lines Simulated with COILSIM1D

Methusalem Advisory Board, 28/06/2010

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SLIDE 19

C18:1 C16:1 C20:1 Unconverted FAME 1-heptene 1-pentadecene 1-undecene 1-nonene 1-heptadecene 1-tridecene 5 100 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

Methusalem Advisory Board, 28/06/2010

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SLIDE 20

benzene toluene styrene naphthalene 1-pentene 1-heptene 1-pentadecene 1-undecene Methyl- propanoate 1-nonene biphenyl mono- aromatics di-aromatics saturates &

  • lefins

5 1-tridecene 100

FAME Pyrolysis 700 C

3D view

Ethylene : 25 wt% Propylene : 12 wt% CO + CO2 : 15 wt% Benzene : 5 wt% Toluene : 2.5 wt%

Methusalem Advisory Board, 28/06/2010

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SLIDE 21

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

Methusalem Advisory Board, 28/06/2010

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SLIDE 22

Acknowledgement

  • Prof. Wol
  • Methusalem Funding

Thank you for your attention!

Methusalem Advisory Board, 28/06/2010

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SLIDE 23

Glossary

Pyrolysis : Thermal decomposition in the absence of air FAME : Fatty Acid Methyl Esters Modulator: High frequency sampling interface COT: Coil Outlet Temperature

Methusalem Advisory Board, 28/06/2010