Process for the Preparation of Low Molecular Weight Aromatics (BTX) and Biofuels from Biomass

Abstract

A process for the preparation of aromatic compounds from a feed stream containing biomass or mixtures of biomass, the process comprising: a) subjecting a feed stream containing biomass or mixtures of biomass to a process to afford a conversion product comprising aromatic compounds; b) recovering the aromatic compounds from said conversion product; c) separating a higher molecular weight fraction comprising polyaromatic hydrocarbons (PAH) from a lower molecular weight fraction comprising benzene, toluene and xylene (BTX) by distillation; d) reducing at least part of said higher molecular weight fraction to obtain a reduced fraction comprising polycyclic aliphatics (PCA); and e) subjecting the higher molecular weight fraction obtained in step c), the reduced fraction obtained in step d), or a mixture thereof, to a process to obtain lower molecular weight aromatics (BTX).

Claims

1. A process for the preparation of aromatic compounds from a feed stream containing biomass or mixtures of biomass, the process comprising: a) subjecting a feed stream containing biomass or mixtures of biomass to a process to afford a conversion product comprising aromatic compounds; b) recovering the aromatic compounds from said conversion product; c) separating a higher molecular weight fraction comprising polyaromatic hydrocarbons (PAH) from a lower molecular weight fraction comprising benzene, toluene and xylene (BTX) by distillation; d) reducing at least part of said higher molecular weight fraction to obtain a reduced fraction comprising polycyclic aliphatics (PCA); and e) subjecting the higher molecular weight fraction obtained in step c), the reduced fraction obtained in step d), or a mixture thereof, to a process to obtain lower molecular weight aromatics (BTX).

2. Process according to claim 1, wherein step a) comprises subjecting the biomass feed stream to in situ or ex situ pyrolysis, or to a vaporization process.

3. Process according to claim 2, wherein step a) comprises pyrolysis of the biomass feed, preferably using a cheap cracking catalyst, followed by subsequently subjecting the vapors thus obtained to an ex situ catalytic aromatization step.

4. Process according to claim 1, wherein said feed stream containing biomass or mixtures of biomass comprises one or more of selected from the group consisting of agricultural waste, plants, wood, preferably wherein the feed stream comprises organic material such as, glucose, maltose, starch, cellobiose, cellulose, hemi-cellulose, other polysaccharides, lignin, sugar cane bagasse, lignocellulosic materials (e.g., wood chips or shavings, lignocellulosic biomass, etc.), glycerol, fatty acids, fatty acid methyl esters, triglycerides, food waste, animal waste, manure, corn stover, partially decayed vegetation, such as peat or lignite, or any combination thereof.

5. Process according to claim 1, wherein step a) comprises adding at least one further reactant to the feed stream, the reactant being selected from the group consisting of olefins, alcohols, aldehydes, ketones, acids and combinations thereof.

6. Process according to claim 5, wherein the further reactant comprises 1 to 6 carbon atoms, preferably wherein the further reactant is selected from the group consisting of ethene, propene, butene, isobutene, pentenes, hexenes, methanol, ethanol, propanol, isopropanol, hexanol, formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, formic acid and acetic acid.

7. Process according to claim 1, wherein step d) comprises catalytic hydrogenation, preferably using a catalyst selected from the group consisting of Ru/C, Ni/C, Pd/C, Pt/C, MoS.sub.2, WS.sub.2, CoMoS/Al.sub.2O.sub.3, NiMoS/Al.sub.2O.sub.3, NiWS/Al.sub.2O.sub.3, CoMo/Al.sub.2O.sub.3 or homogeneous catalysts such as the Wilkinson catalyst and the Crabtree catalyst.

8. Process according to claim 7, wherein said catalytic hydrogenation is performed without the addition of a solvent.

9. Process according to claim 1, wherein step e) comprises mixing the higher molecular weight fraction obtained in step c) or the reduced fraction obtained in step d) with a biomass feedstream and subjecting the resulting mixture to pyrolysis or vaporization.

10. Process according to claim 9, wherein step e) comprises a catalytic pyrolysis treatment.

11. Process according to claim 9, comprising mixing the higher molecular weight fraction obtained in step c) or the reduced fraction obtained in step d) with the biomass feedstream of step a).

12. A composition comprising higher molecular weight polyaromatic hydrocarbons (PAH) obtainable by steps a) through c) of claim 1.

13. A composition comprising higher molecular weight polycyclic aliphatics (PCA) obtainable by steps a) through d) of claim 1.

14. Composition according to claim 13, comprising up to 10 wt % of monocyclic compounds.

15. Composition according to claim 13, wherein said composition comprises a mixture of polycyclic aliphatics (PCA) and polyaromatic hydrocarbons (PAH).

16. Composition according to claim 1, wherein said composition comprises compounds having a molecular weight in the range of about 100 to 500 Dalton, preferably about 120 to 300 Dalton.

17. Composition according to claim 12, wherein said composition comprises compounds having about 9 to 20 C-atoms and multiple aromatic rings.

18. Composition according to claim 12, being a biofuel.

19. Composition according to claim 13, being a jet fuel additive.

20. (canceled)

Description

LEGEND TO THE FIGURES

[0034] FIG. 1 is a flow diagram of an embodiment of the method according to the invention for improving the yield of BTX from biomass. The aromatic fraction obtained in the catalytic aromatization treatment is subjected to distillation in order to separate the BTX fraction from a high molecular weight polyaromatic hydrocarbon (PAH) fraction. At least part of the latter fraction is first reduced to a polycyclic aliphatic fraction, which can be co-feeded with the biomass in order to achieve a recycling of higher aromatics towards BTX. Alternatively, the high molecular weight fraction (reduced or not) is used for other applications.

[0035] FIG. 2 displays the chemistry for the preparation of additional BTX from a polyaromatic fraction by reduction/hydrogenation and subsequent catalytic aromatization.

[0036] FIGS. 3 and 4 show the .sup.1H-NMR of the polyaromatic fraction and the .sup.1H-NMR of the reduced fraction, obtained by catalytic hydrogenation (ex situ upgrading) of glycerol (PAH-1). It clearly displays that the amount of aromatic protons present between 6.5-8.0 ppm are less in intensity and mostly converted to aliphatic (cyclic) hydrocarbons.

[0037] FIG. 5 GC Chromatograms of polyaromatic hydrocarbons (from glycerol), polycyclic alkanes/polyaromatic hydrocarbons (PCA/PAH-1), obtained by catalytic hydrogenation (Ru/C) and PCA/PAH-1 aromatized over an H-ZSM-5 (23) catalyst. It is observed that the PCA/PHA fraction is converted by the catalyst toward a mixture of BTX and higher aromatics.

[0038] FIG. 6 and FIG. 7 display the MALDI-TOF spectra of the polyaromatic fraction and the reduced fraction and confirm the transformation of aromatics towards aliphatics.

[0039] FIG. 8 is a flow diagram of an embodiment of the method according to the Integrated Cascading Catalytic Pyrolysis (N. J. Schenk, A. Biesbroek, A. Heeres, H. J. Heeres, WO 2015/047085 A1).

[0040] FIG. 9 Ex situ pyrolysis of polyaromatic hydrocarbons (PAH-2, obtained from glycerol, after distillation of BTX)), polycyclic alkanes/polyaromatic hydrocarbons (PCAG2; obtained by catalytic hydrogenation (Ru/C) of PAH-2)(((T=560 C, H-ZSM-5 (23), zeolite:biomass 3:1) and an Integrated Cascading Catalytic Pyrolysis Process of PCAG-2 with different cracking catalysts ((T=560 C, H-ZSM-5 (23), zeolite:biomass 3:1, cracking catalyst:biomass=0.5-1.0:1), yields of BTX (see examples 6-19)

[0041] It can be concluded that [0042] the reduced polycyclic and polyaromatic hydrocarbon fraction afford higher yields of BTX as compared to the non-reduced polyaromatic fraction [0043] both the PAH and PCA fraction suffer from ageing and lowers yields of BTX were obtained if both fractions were stored for several months at room temperature. [0044] under the conditions used the Integrated Cascading Catalytic Pyrolysis, using a cracking catalyst afforded higher amounts of BTX for fresh produced PCA. [0045] an ex situ pyrolysis of a fresh PCA fraction with a mix of a cracking catalyst and a aromatization catalyst (H-ZSM-5 (23) (layered) results in higher formation of BTX.

[0046] FIG. 10. Mass balances for the ex situ pyrolysis of polyaromatic hydrocarbons (PAH-2, obtained from glycerol, after distillation of BTX)), polycyclic alkanes/polyaromatic hydrocarbons (PCAG2; obtained by catalytic hydrogenation (Ru/C) of PAH-2)(((T=560 C, H-ZSM-5 (23), zeolite:biomass 3:1) and an Integrated Cascading Catalytic Pyrolysis Process of PCAG-2 with different cracking catalysts ((T=560 C, H-ZSM-5 (23), zeolite:biomass 3:1, cracking catalyst:biomass=0.5-1.0:1 (see examples 6-19).

[0047] It can be concluded that minor amounts of char, gas and water are being formed and the majority of the PAH and PCA is transformed into a bio-oil, consisting of BTX and substituted higher aromatics (GC). The bio-oil obtained can be subjected to distillation in order to isolate BTX and the remaining fraction can be reutilized in the pyrolysis treatment.

[0048] FIG. 11. displays the BTX yields of the ex-situ pyrolysis of several biomass feedstocks co-feeded with a polyaromatic hydrocarbon fraction (PAH-2, obtained from glycerol) (see examples 1, 6 and 20-22).

[0049] FIG. 12. shows the yields of BTX for the ex-situ pyrolysis of several biomass feedstocks co-feeded with a reduced polycyclic and polyaromatic hydrocarbon fraction (PCA, obtained from glycerol). It can be concluded that co-feeding of biomass with an already pyrolyzed fraction results in additional yields of BTX. Furthermore, in most cases a synergistic effect is observed as reflected by a higher yield of BTX from the mixtures than the sum of the yields from the individual feedstocks (see examples 7, 20 and 24-30)

[0050] FIG. 13. The amount of BTX present in the bio-oil obtained after the ex-situ pyrolysis of several biomass feedstocks co-feeded with a reduced polycyclic and polyaromatic hydrocarbon fraction (PCA, obtained from glycerol) (see examples 7, 20 and 24-30).

TABLE-US-00001 TABLE 1 Products observed in the GC Chromatograms of polyaromatic hydrocarbons (from glycerol), polycyclic alkanes/polyaromatic hydrocarbons (PCA/PAH-1), obtained by catalytic hydrogenation (Ru/C) and PCA/PAH-1 aromatized over an H-ZSM-5 (23) catalyst Glycerol over PCA over RT Quality H-ZSM-5 (23) PAH PCA H-ZSM-5 (23) 6.06 94 Benzene Benzene 8.3 90 Cyclohexane, 1,2- dimethyl-, tra 9.87 91 Toluene Toluene 11.54 94 Cyclohexane, 1,3,5-trimethyl-, 12.86 91 Cyclohexane, 1,2,4-trimethyl- 13.03 96 Cyclohexane, Cyclohexane, 1,2,4-trimethyl- 1,2,4-trimethyl- 13.17 94 Cyclohexane, 1,2,4-trimethyl- 13.39 95 cis-1-Ethyl-3- methyl-cyclohexan 13.49 90 Cyclohexane, 1-ethyl-4-methyl-, 14.47 93 Ethylbenzene Ethylbenzene 14.94 97 p-Xylene Benzene, 1,3- dimethyl- 15.72 91 Cyclohexane, 1-ethyl-2-methyl-, 16.43 97 Benzene, 1,2- Benzene, 1,2- dimethyl- dimethyl- 17.37 96 1H-Indene, 1H-Indene, octahydro-, trans- octahydro-, trans- 18.42 90 Cyclohexane, 1- methyl-2-propyl- 19.02 95 Decane Decane 19.11 91 Cyclohexane, diethyl- 19.3 98 1H-Indene, 1H-Indene, octahydro-, cis- octahydro-, cis- 19.8 91 Benzene, 1- ethyl-2-methyl- 19.82 90 Benzene, 1-ethyl- Benzene, 1-ethyl- 3-methyl- 3-methyl- 19.87 90 Benzene, 1-ethyl- 2-methyl- 20.2 90 Benzene, 1-ethyl- 3-methyl- 20.21 96 1,2,4- Trimethylbenzene 20.61 95 Cyclohexane, 1-methyl-2-propyl- 21 91 Benzene, 1,3,5- trimethyl- 21.12 90 Cyclohexane, butyl- 21.72 94 Benzene, 1,2,3- trimethyl- 21.77 97 1,2,4- 1,2,4- 1,2,4- Trimethylbenzene Trimethylbenzene Trimethylbenzene 21.92 98 1H-Indene, 1H-Indene, octahydro-5-methyl- octahydro-5-methyl- 22.75 99 Naphthalene, Naphthalene, decahydro-, trans- decahydro-, trans- 23.37 98 1H-Indene, 1H-Indene, octahydro- octahydro-5-methyl- 5-methyl- 23.54 93 1,2,4- Benzene, 1,2,3- Benzene, 1,2,3- Trimethylbenzene trimethyl- trimethyl- 24.22 93 Indane Indane 24.26 95 Undecane 24.86 95 Benzene, 4-ethyl- 1,2-dimethyl- 25.25 99 Naphthalene, Naphthalene, decahydro- decahydro- 25.55 95 Naphthalene, decahydro-2-methy 25.67 94 Indene 25.98 95 Benzene, 4-ethyl-1,2- dimethyl- 26.08 91 Benzene, 1-methyl-4- (1-methylet 26.35 94 Benzene, 2-ethenyl- 1,4-dimethyl 26.36 93 Benzene, 1-methyl- 2-(2-propenyl)- 26.43 90 Benzene, 1-ethyl- Benzene, 1-ethyl-2,3- 2,3-dimethyl- dimethyl- 26.44 90 Benzene, 4-ethyl- 1,2-dimethyl- 26.67 90 2,3-Dihydro-1- methylindene 27.65 94 Naphthalene, decahydro- 2-methyl 27.92 94 Naphthalene, decahydro- 2-methyl 28.15 93 Benzene, 1,2,4,5- Benzene, 1,2,4,5- tetramethyl- tetramethyl- 28.16 91 Benzene, 4-ethyl- 1,2-dimethyl- 28.4 91 Benzene, 1,2,3,5- Benzene, 1,2,3,5- Benzene, 1,2,4,5- tetramethyl- tetramethyl- tetramethyl- 29.18 95 Dodecane Dodecane 29.38 93 2,3-Dihydro-1- methylindene 29.39 91 Benzene, 2- ethenyl-1,4-dimethyl 30.14 96 Benzene, 2-ethenyl- 1,4-dimethyl 30.15 93 2,3-Dihydro-1- methylindene 30.73 96 1H-Indene, 1-methyl- 30.77 96 Naphthalene, Naphthalene, 1,2,3,4-tetrahydro 1,2,3,4-tetrahydro 30.85 96 1H-Indene, 1-methyl- 31.28 92 Benzene, 2-ethenyl- 1,3,5-trimet 31.29 95 1H-Indene, 2,3- dihydro-4,7-dime 31.41 93 Benzene, (1-methyl- 2-cyclopropen-l 31.47 94 Benzene, (1-methyl- 2-cyclopropen-1 31.54 91 Naphthalene, 1,2,3,4-tetrahydro 31.54 94 Benzene, (2-methyl- 1-butenyl)- 31.8 95 1H-Indene, 2,3- 1H-Indene, 2,3- dihydro-1,6-dime dihydro-4,7-dime 32.01 91 1H-Indene, 2,3- dihydro-1,2-dime 32.24 94 Benzene, (2-methyl- 1-butenyl)- 32.25 91 1H-Indene, 2,3- dihydro-1,6-dime 33.24 96 Naphthalene, Naphthalene, 1,2,3,4-tetrahydro 1,2,3,4-tetrahydro 33.52 94 Naphthalene 33.55 94 Azulene Azulene 33.64 94 Naphthalene, 1,2,3,4-tetrahydro 33.79 91 Benzene, 1-(1-methylethenyl)-3- 33.83 95 Tridecane Tridecane 34.3 90 1H-Indene, 2,3-dihydro-1,5,7-tr 34.72 96 1H-Indene, 2,3-dihydro-4,7-dime 34.73 90 1H-Indene, 2,3- dihydro-1,3-dime 35.53 94 Naphthalene, Naphthalene, 1,2,3,4-tetrahydro 1,2,3,4-tetrahydro 36.18 91 Naphthalene, 1,2,3,4-tetrahydro 36.25 90 Benzene, Benzene, pentamethyl- pentamethyl- 36.54 90 1H-Indene, 2,3- dihydro-4,5,7-tr 36.66 93 1H-Indene, 1,1- dimethyl- 37.07 92 Naphthalene, Naphthalene, 1,2,3,4-tetrahydro 1,2,3,4-tetrahydro 37.79 93 Naphthalene, Naphthalene, 1,2,3,4-tetrahydro 1,2,3,4-tetrahydro 38.13 90 Naphthalene, 1,2,3,4-tetrahydro 38.22 95 Tetradecane 38.57 91 Naphthalene, 1-methyl- 38.62 94 Naphthalene, 1- Naphthalene, methyl- 1-methyl- 39.11 94 l,4-Dimethyl- 1,4-Dimethyl- 1,2,3,4-tetrahydro 1,2,3,4-tetrahydro 39.23 95 1,4-Dimethyl- 1,2,3,4-tetrahydro 39.38 94 Naphtalene, Naphthalene, 1- Naphthalene, 1-methyl methyl- 1-methyl- 39.56 94 Naphthalene, Naphthalene, 6-ethyl-1,2,3,4-te 6-ethyl-1,2,3,4-te 39.67 90 Naphthalene, 1,2,3,4-tetrahydro 40.9 90 3-Ethyl-3-phenyl-1- pentene 41.09 90 Benzene, 1,3,5- trimethyl-2- (1,2-pr 41.24 96 Naphthalene, Naphthalene, 1,2,3,4-tetrahydro 1,2,3,4-tetrahydro 42.36 96 Pentadecane Pentadecane 42.76 97 Naphthalene, 1- ethyl- 43.21 95 Naphthalene, Naphthalene, 1,2,3,4-tetrahydro 1,2,3,4-tetrahydro 43.26 94 Naphthalene, 1,7-dimethyl- 43.3 98 Naphthalene, 2,6- dimethyl- 43.3 96 Naphthalene, 1,7-dimethyl- 43.31 91 Naphthalene, 1,2,3,4-tetrahydro 43.91 93 Naphthalene, 1,7-dimethyl- 43.95 98 Naphthalene, 1,8- dimethyl- 43.95 98 Naphthalene, 2,6-dimethyl- 44.04 91 Naphthalene, 2,6-dimethyl- 44.08 97 Naphthalene, 2,6- Naphthalene, dimethyl- 2,6-dimethyl- 44.98 96 Naphthalene, 1,3- Naphthalene, dimethyl- 1,3-dimethyl- 45.58 90 Naphthalene, 1,2-dimethyl- 47.17 91 Naphthalene, Naphthalene, 1,4,6-trimethyl- 1,4,6-trimethyl- 48.14 93 Naphthalene, Naphthalene, 1,6,7-trimethyl- 1,6,7-trimethyl- 48.3 95 Naphthalene, Naphthalene, 1,6,7-trimethyl- 1,6,7-trimethyl- 48.95 96 Naphthalene, 1,4,5-trimethyl- 48.97 93 Naphthalene, 1,6,7-trimethyl- 49.28 96 Naphthalene, 1,6,7-trimethyl- 49.28 97 Naphthalene, 1,4,6-trimethyl- 49.72 93 Naphthalene, 1,4,6-trimethyl- 49.88 96 Naphthalene, 1,6,7-trimethyl- 49.88 95 Naphthalene, 2,3,6-trimethyl- 50.41 95 Naphthalene, 1,4,6-trimethyl- 53.73 91 Azulene, 7-ethyl- 1,4-dimethyl- 54.24 94 Azulene, 7-ethyl- 1,4-dimethyl- 54.43 98 Phenanthrene, 1,2,3,4,5,6,7,8-o 55.15 91 4,4-Dimethylbiphenyl 55.4 93 4,4-Dimethylbiphenyl 55.48 91 4,4-Dimethylbiphenyl 56.54 91 Tricyclo[4.4.1.02, 5]undeca-1(10 67.31 91 Phenanthrene, 2,5-dimethyl-

[0051] The invention is further illustrated by means of the following non-limiting examples.

EXPERIMENTAL SECTION

Example 1: Catalytic Aromatization of Glycerol (Ex Situ Upgrading, Gram Scale)

[0052] Crude glycerol was obtained from a biodiesel production process. The crude glycerol was first pyrolysed and subsequently in situ up-graded using a bench-scale reactor set up comprising a pyrolysis- and an up-grading unit, connected with each other. A constant stream of N.sub.2 of about 11 min/ml was used as a gas flow in order to maintain an inert atmosphere. The pyrolysis unit was filled with crude glycerol (0.94 g) and the upgrading unit was filled with the catalyst (H-ZSM-5 (23), 3.18 g). The up-grading unit of the bench-scale reactor set up, including the catalyst, was first placed in a fluidized sand bed (T=550 C.) and after reaching T=550 C. the pyrolysis unit, comprising the crude glycerol, was placed in the fluidizing bed to start the vaporization/pyrolysis. The pyrolysis took about 5-15 min to finish (constant N.sub.2 flow). The obtained glycerol liquor gas is subsequently converted in the upgrading unit via the catalytic treatment. The converted glycerol liquor gas was subsequently condensed by cooling the vapour phase to a temperature of 40 C. The amount of condensables was determined by weight. The cooling unit was then washed with small amounts of THF, the amount of water was determined using Karl Fischer titration and the organic fraction was subsequently calculated by difference.

Example 2: Catalytic Aromatization of Glycerol (Ex Situ Upgrading, >100 Gram Scale)

[0053] Crude glycerol was evaporated/pyrolyzed/aromatized in a demo reactor comprising a evaporation/pyrolysis unit (reactor 1, T=520 C.), a fixed bed containing the aromatization catalyst (reactor 2, H-ZSM-5 (23)/bentonite 60:40, 200 gram, 1-2 mm particles, T=536 C.) and a condenser zone (T=20 C.). The glycerol was heated to T=70 C. and fed (850 gram, 3.8 g/min) to the first reactor using a N.sub.2 flow (1.5 L/min). Layer separation of the condensed fraction (organics/water) afforded an aromatic oil (163.2 g; about 70 g BTX, based on GC)) and water (215.45 g).

Example 3: Distillation of the Aromatic Oil

[0054] Combined crude aromatic bio-oils (3.5 liter) from example 2 were transferred to a separating funnel and the phases were allowed to settle over the weekend. The phases were separated and the crude bio-oil was dried over Na.sub.2SO.sub.4 and subsequently filtered by suction over a glass-filter. The filtered oil (2941 g) was subjected to a coarse distillation under reduced pressure (1000 mbar 50 mbar and 40 C. 110 C. using a simple distilling setup and a 3-4 L distilling flask, affording a mixture of benzene, toluene and xylenes (1193 g) and a residual oil (1748 g) consisting of higher molecular weight aromatics (polyaromatic hydrocarbons)

Example 4: Catalytic Hydrogenation of Substituted Polyaromatic Hydrocarbons (PAH-1)

[0055] A polyaromatic hydrocarbon fraction, obtained according to Example 3 (PAHG1; 15.02 g), and 5% Ru/C (0.76 g; Sigma-Aldrich) were put under hydrogen pressure (101.5 bar) in a Parr apparatus and heated to 305 C. (external temperature, P=119.1 bar). A gradual pressure drop in H.sub.2 pressure was observed. After stirring for 2 hrs the reaction was cooled to room temperature and the reaction product was filtered over cotton wool (3) and Na.sub.2SO.sub.4 (1), affording an orange oil (5 g).

Example 5: Catalytic Hydrogenation of Substituted Polyaromatic Hydrocarbons (PAH-2))

[0056] A polyaromatic hydrocarbon fraction, obtained according to Example 3 (PAHG2; 18.01 g), and 5% Ru/C (0.92 g) were put under hydrogen pressure (134.1 bar) in a Parr apparatus and heated to 305 C. (external temperature, P=119.1 bar). A gradual pressure drop in H.sub.2 pressure was observed. After stirring for 3.25 hrs the reaction was cooled to room temperature and the reaction product was filtered over Whatman syringe filters (0.2 m) affording an orange oil (11.6 g).

Example 6: Catalytic Aromatization of Substituted Polyaromatic Hydrocarbons (Ex Situ Upgrading, PAH2, Gram Scale)

[0057] Under identical conditions as described in Example 1 a substituted polyaromatic fraction (prepared according to Example 3, 1.05 gram) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.04 g).

Example 7: Catalytic Aromatization of Substituted Polycyclic Aliphatic Hydrocarbons/Polyaromatic Hydrocarbons (Ex Situ Upgrading, PCA-2, Gram Scale)

[0058] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (PCAG2, prepared according to Example 5, 0.87 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.01 g).

Example 8: Integrated Cascading Catalytic Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2) with Bentonite (Ex Situ Upgrading, Gram Scale)

[0059] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (PCAG2, according to Example 5, 0.52 g) mixed with bentonite (0.54 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (1.55 g).

Example 9: Integrated Cascading Catalytic Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2) with Hydrotalcite (Ex Situ Upgrading, Gram Scale)

[0060] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (PCAG2, according to Example 5, 0.57 g) mixed with hydrotalcite (0.48 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (2.09 g).

Example 10: Integrated Cascading Catalytic Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2) with Phosphotungstic Acid Hydrate (Ex Situ Upgrading, Gram Scale)

[0061] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (PCAG2, according to Example 5, 0.52 g) mixed with phosphotungstic acid hydrate (0.25 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (1.59 g).

Example 11: Integrated Cascading Catalytic Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2) with MnO.SUB.2 .(Ex Situ Upgrading, Gram Scale)

[0062] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (PCAG2, according to Example 5, 0.51 g) mixed with MnO.sub.2 (0.27 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (1.64 g).

Example 12: Integrated Cascading Catalytic Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2) with FeO (Ex Situ Upgrading, Gram Scale)

[0063] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (PCAG2, according to Example 5, 0.48 g) mixed with FeO (0.28 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (1.87 g).

Example 13: Integrated Cascading Catalytic Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2) with Silicotungstic Acid (Ex Situ Upgrading, Gram Scale)

[0064] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (PCAG2, according to Example 5, 0.47 g) mixed with silicotungstic acid (0.33 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (1.71 g).

Example 14: Integrated Cascading Catalytic Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2) with ASA1/Siral 40 (Ex Situ Upgrading, Gram Scale)

[0065] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (PCAG2, according to Example 5, 0.45 g) mixed with ASA1/Siral 40 (0.49 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (1.74 g).

Example 15: Catalytic Aromatization of Substituted Polycyclic Aliphatic Hydrocarbons/Polyaromatic Hydrocarbons (Ex Situ Upgrading, PCA-2, Gram Scale, Fresh Material)

[0066] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (PCAG2, fresh material, prepared according to Example 5, 0.99 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.05 g).

Example 16: Integrated Cascading Catalytic Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2, Fresh Material)) with FeO (Ex Situ Upgrading, Gram Scale)

[0067] Under identical conditions as described in Example 1 a polyaromatic hydrocarbon fraction (according to Example 5, Inouk 0.87 g) mixed with FeO (0.35 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.03 g).

Example 17: Ex Situ Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction with FeO.SUB.2./H-ZSM-5 (23), Layered

[0068] Under identical conditions as described in Example 1 a polyaromatic hydrocarbon fraction (according to Example 5, 0.86 g) was pyrolyzed and catalytically aromatized with a catalyst consisting of FeO (first layer, 0.71 g) and H-ZSM-5 (23) (second layer, 3.15 g)

Example 18: Integrated Cascading Catalytic Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2, Fresh Material) with ASA1/Siral 40 (Ex Situ Upgrading, Gram Scale)

[0069] Under identical conditions as described in Example 1 a polyaromatic hydrocarbon fraction (according to Example 5, 1.10 g) mixed with ASA1/Siral 40 (Inouk 0.77 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.63 g).

Example 19: Ex Situ Pyrolysis of a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2, Fresh Material) with ASA1/Siral 40/H-ZSM-5 (23), Layered

[0070] Under identical conditions as described in Example 1 a polyaromatic hydrocarbon fraction (according to Example 5, 1.02 g) was pyrolyzed and catalytically aromatized with a catalyst consisting of ASA1/Siral 40 (first layer, 0.70 g) and H-ZSM-5 (23) (second layer, 3.40 g)

Example 20: Catalytic Aromatization of Wood (Ex Situ Upgrading, Gram Scale)

[0071] Under identical conditions as described in Example 1 pinewood (0.85 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (2.63 g).

Example 21: Catalytic Aromatization of a Mixture of Pinewood and Substituted Polyaromatic Hydrocarbons (Hydrocarbons (PAH-2), Ratio 1:1 (Ex Situ Upgrading, Gram Scale)

[0072] Under identical conditions as described in Example 1 a polyaromatic hydrocarbon fraction (PAH-2, according to Example 3, 0.62 g) mixed with pinewood (0.56 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.64 g).

Example 22: Catalytic Aromatization of a Mixture of Glycerol and Substituted Polyaromatic Hydrocarbons (Hydrocarbons (PAH-2), Ratio 1:1 (Ex Situ Upgrading, Gram Scale)

[0073] Under identical conditions as described in Example 1 a polyaromatic hydrocarbon fraction (according to Example 3, 0.57 g) mixed with glycerol (0.40 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.29 g).

Example 23: Catalytic Aromatization of a Mixture of Glycerol and a Reduced Polyaromatic Hydrocarbon Fraction (Hydrocarbons (PCAG-2), Ratio 1:1 (Ex Situ Upgrading, Gram Scale)

[0074] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (according to Example 5, 0.43 g) mixed with glycerol (0.40 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.17 g).

Example 24: Catalytic Aromatization of a Mixture of Wood and a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2), Ratio 1:1 (Ex Situ Upgrading, Gram Scale)

[0075] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (prepared according to Example 5, 0.61 g) mixed with wood (0.50 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.33 g).

Example 25: Catalytic Aromatization of Kraft Lignin (Ex Situ Upgrading, Gram Scale)

[0076] Under identical conditions as described in Example 1 Kraft lignin (1.00 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.37 g).

Example 26: Catalytic Aromatization of a Mixture of Kraft Lignin and a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2), Ratio 1:1 (Ex Situ Upgrading, Gram Scale)

[0077] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (prepared according to Example 5, 0.55 g) mixed with Kraft lignin (0.51 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.29 g).

Example 27: Catalytic Aromatization of Cellulose (Ex Situ Upgrading, Gram Scale)

[0078] Under identical conditions as described in Example 1 cellulose (1.00 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (2.96 g).

Example 28: Catalytic Aromatization of a Mixture of Cellulose and a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2), Ratio 1:1 (Ex Situ Upgrading, Gram Scale)

[0079] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (prepared according to Example 5, 0.53 g) mixed with cellulose (0.53 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.79 g).

Example 29: Catalytic Aromatization of Jatropha Oil (In Situ Upgrading, Gram Scale)

[0080] Under identical conditions as described in Example 1 Jatropha oil (1.28 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.87 g).

Example 30: Catalytic Aromatization of a Mixture of Jatropha Oil and a Reduced Polyaromatic Hydrocarbon Fraction (PCAG2), Ratio 1:1 (Ex Situ Upgrading, Gram Scale)

[0081] Under identical conditions as described in Example 1 a reduced polyaromatic hydrocarbon fraction (prepared according to Example 5, 0.51 g) mixed with Jatropha oil (0.52 g) was ex-situ pyrolyzed with a H-ZSM-5 (23) catalyst (3.79 g).