Thermal Conversion of Fossil and Renewable Feedstocks Steven P. Pyl Advisors prof. dr. Marie-Françoise Reyniers prof. dr. ir. Guy B. Marin Laboratory for Chemical Technology
The Need for Detail Fundamental Process Modeling = Molecule-based Modeling Accurate experimental data is crucial! Process conditions Complex feedstock Advanced analytical techniques Feedstock molecular composition Microkinetic model Fundamental model continuity equations Product molecular composition Physical transport phenomena Advanced analytical techniques Complex product
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 Heated Transferline GCGC
GC GC setup injector (2) (1) modulator BPX-50 (3) FID He (7) TOF-MS FID Quantitative results TOF-MS Peak identification (6) (4) OVEN Rtx-1 PONA (5) BPX-50 (3) Liquid CO 2 Initial objective Maximal agreement between FID and TOF-MS chromatograms Van Geem, Pyl, et al. J. Chrom. A. 2010
Kerosene GC GC-FID Di-aromatics KEROSENE 4 Monoaromatics Naphthenoaromatics Naphthenoaromatics Identification and quantification of 300 components C9 10 30 50 1st dimension retention time (min) Confident peak indentification Accurate quatification 3D view 2nd dimension retention time (s) Di-naphthenes 0 naphthenes C16 paraffins C9 Di-aromatics Monoaromatics Di-naphthenes naphthenes C16 paraffins GC GC-(TOF-MS)
Renewable Naphtha Hydrodeoxygenation Naphtha Olefins 0.4% Naphthenes 6.5% Aromatics 0.8% 4 Hydrocracking Kerosene n-paraffins 32.4% toluene ethylbenzene propylbenzene butylbenzene iso-paraffins 59.9% benzene n-c7 n-c12 n-c13 n-c11 n-c9 n-c10 n-c8 GCGC-FID analysis n-c6 0 10 20 30 40
Bio-diesel Transestrification Glycerol FAME C18:1 C18:3 C18:1 C18:2 C16:0 C18:0 C20:1 C22:1C24:1 GCGC-FID O O C14:0 C16:1 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
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 FEED FURNACE & REACTOR ONLINE ANALYSIS P P P P P (4) (5) GCGC DHA oil (6) N 2 (9) (3) (8) (1) (7) (10) condensate IR-GA (12) (11) (2) (1) cell 1 cell 2 cell 3 cell 4 cell 5 cell 6 cell 7 preheating & mixing reactor zone RGA PGA flare
Pilot Plant: On-line Effluent Sampling FEED FURNACE & REACTOR ONLINE ANALYSIS P P P P P Heated transfer lines 300 C (4) (5) GCGC DHA (3) GC GC DHA (6) oil N 2 (9) (8) (1) (7) (10) condensate IR-GA (12) (11) (2) (1) cell 1 cell 2 cell 3 cell 4 cell 5 cell 6 cell 7 preheating & mixing reactor zone RGA PGA flare
Pilot Plant: On-line Quantification Approach FEED FURNACE & REACTOR P Nitrogen = Internal Standard P P P P Methane = Reference Component ONLINE ANALYSIS (4) (5) GCGC DHA oil RGA (TCD) H 2 CO 2 C 2 H 4 C 2 H 6 C 2 H 2 N 2 CH 4 CO (6) N 2 (9) (3) RGA (FID) (1) CH 4 C 2 C 3 C 4 check (7) (8) (10) PGA (TCD) CO 2 C 2 H 4 C 2 H 6 C 2 H 2 N 2 CO CH 4 condensate IR-GA DHA (FID) CH 4 C 2 C 3 C 4 C 5 C 6... C 16 (12) (11) (2) GCGC (1) (FID) CH 4... C cell 1 cell 2 cell 25 3 cell 4 cell 5 cell 6 cell 7 preheating & mixing reactor zone RGA PGA DHA and GCGC temperature program: -40 C 300 C flare
Kerosene Steam Cracking GC GC chromatogram two parts 2nd dimension retention time (s) 5 2 not modulated modulated styrene benzene toluene methylnaphthalenes naphthalene indene signal intensity (mv) ethene methane propene 1.3-butadiene 0 paraffins 0 25 50 1st dimension retention time (min) (a) 0 5 10 1st dimension retention time (min) (b) 1. Conventional 1D part C 4-2. Comprehensive 2D part C 5+
5 Kerosene Steam Cracking phenanthrene acenapthene anthracene acenapthylene naphthalene biphenyl methyl-indenes benzene styrene ethyl-bz indene vinyltoluene methyl-naphthalenes toluene xylenes tri-methyl-bz pyrene 0 20 35 50 1st dimension retention time (min) 65 80 Reduced peak overlap More straightforward peak identification More accurate quantification Quantification of approximately 150 chemical components
Kerosene Steam Cracking COT = 800 C COT = 840 C 1.8 vinyltoluene vinylstyrene 1.8 vinyltoluene vinylstyrene 2nd dimension retention time (s) C3 alkylbenzenes C4 alkylbenzenes C5 alkylbenzenes nc14 2nd dimension retention time (s) C3 alkylbenzenes C4 alkylbenzenes C5 alkylbenzenes nc14 nc10 0 35 45 55 1st dimension retention time (min) (a) Reduced peak overlap More straightforward peak identification nc10 0 35 45 1st dimension retention time (min) (b) More accurate quantification Quantification of approximately 150 chemical components
Kerosene Steam Cracking Quantification of approximately 150 chemical components Yields (wt%) Yields (wt%) 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
Yield (wt%) Renewable Naphtha Steam Cracking Effect of Coil Oulet Temperature ethylene propylene 1,3-butadiene 1-butene benzene pygas fuel oil 35 30 25 20 15 10 5 Symbols Pilot Plant Experiments Lines Simulated with COILSIM1D 0 10 11 12 13 14 15 16 17 18 Methane Yield (wt%) Process conditions Detailed feedstock composition COILSIM1D Detailed product composition CRACKSIM continuity equations IDEAL PLUG FLOW
FAME Pyrolysis 3D view ON-LINE effluent analysis 5 600 C C9 alkyl benzene C2 alkyl benzene C3 alkyl benzene C5 alkyl benzene C7 alkyl benzene 1-heptadecene C20:1 C18:1 1-pentadecene 1-heptene 1-tridecene 1-undecene 1-nonene C16:1 Unconverted FAME 0 100
5 FAME Pyrolysis 3D view Ethylene : 25 wt% Propylene : 12 wt% naphthalene biphenyl CO + CO2 : 15 wt% Benzene : 5 wt% Toluene : 2.5 wt% 700 C di-aromatics benzene styrene Methylpropanoate toluene monoaromatics 0 1-pentene 1-heptene 1-pentadecene 1-tridecene 1-undecene 1-nonene saturates & olefins 100
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 : FAME : Modulator: COT: Thermal decomposition in the absence of air Fatty Acid Methyl Esters High frequency sampling interface Coil Outlet Temperature