RE-CORD Renewable Energy COnsortium for R&D REVIEW OF CATALYTIC PYROLYSIS OF LIPIDS. EXPERIENCES FROM THE ITAKA PROJECT David Chiaramonti RE-CORD Renewable Energy Consortium for Research and Developmen Industrial Engineering Dpt., Univ.of Florence Florence, Italy 1
Scope of the work RE-CORD focused on investigation & testing of used cooking oils (such as fried cooking oil) as feedstock for alternative thermochemical process to commercial hydrotreating (WP leader Neste Oil). Bio-kerosene fraction Used cooking oil How? 2
Routes to green fuels Commercial hydrotreating of VOs Hydrogen, high cost catalysts, high energy input Hydrogen, noncondensable gases Additives, low energy input Deoxygenation Selective hydrogenation Fractionation High fraction recover UCO, vegetable oils, waste lipids Pre-treatment: cleaning, upgrading Low cost catalysts, medium energy input Water Hydrogen, noncondensable gases Medium fraction recover Renewable hydrocarbonsbased fuels Wastes Nitrogen Thermal catalytic conversion Separation and fractionation Water and oxygenated compounds RE-CORD cat-pyro process 3
Used Cooking Oil Highly contaminated feedstock Lipidic composition variable depending on region and time The same for contamination Potential estimated by us and various sources at around 1 Mt/y in the EU à Pyrolysis can quite well process such materials 4
Feedstock: VO vs filtered UCO vs FAs Parameter Unit Commercial Filtered UCO SO (1 µm) FAs Density kg/m 3 914 911 Kinematic Viscosity at 40 C mm 2 /s 26.0 38.15 18.03 Acid value mg KOH/g 1.06 2.63 201.7 Free Fatty Acid % 0.53 1.31 100.85 Iodine Number g Iodine/100g n.p. 93 Water content % 0.085 0.08 0.08 Ash % (m/m) 0.007 0.01 Total contamination mg/kg 209 256 68 Insoluble impurities % 0.01 0.05 Phosphorus mg/kg 0.11 10.1 C % 77.8 76.3 76.3 H % 11.9 11.7 12.2 N % 0.01 0.02 0.02 N mg/kg 116 137 O % 10.3 11.98 11.48 Calorific value, higher MJ/kg 39.5 38.9 39.4 Calorific value, lower MJ/kg 37.0 36.4 36.8 FAs %wt Capric 0.09 C10:0 Lauric 2.83 C12:0 Mystiric 1.43 C14:0 Palmitic 4.03 C16:0 Stearic 1.17 C18:0 Oleic 61.81 C18:1 Linoleic 13.47 C18:2 Linolenic 0.38 C18:3 Erucic 6.41 C22:1 Not ident. 8.38-5
Experimental setup ü Continuous catalytic multipurpose/feed pyrolysis unit processing to 1.5 kg/h; ü 400 550 C; RE-CORD/CREAR pyrolysis unit ü 15 kwth of power; ü Modular condensation line and bubbler (aerosols); ü T, p, measures. ü WHSV = 2.5 4 h -1 ü mass flow rate of the reactants - catalyst mass ration 6
Recent Publication (2016) 7
Catalysts: literature investigation Poster presentation: Buffi M, Rizzo AM, Chiaramonti D. A review on renewable jet fuel from thermo-chemical conversion of vegetable and cooking oil. Pyro2014. Ø Target: maximizing the yield and quality of bio-kerosene fraction. 8
Catalysts: literature investigation à 4 Catalysts selected: Activated Carbon (AC), Alumina, H-ZSM-5, Magnesium Oxide (MgO) à 2 WHSV 9
Experimental procedure Activity Description Feedstock Test N. Catalyst Temperature WHSV n - - n - C 1/h 1 Reference case UCO 1 none 500-2 First exp.campaign UCO 2 AC Cat #1 500 4 UCO 4 Alumina - Cat #2 500 4 UCO 5 H-Z-SM5 - Cat #3 500 4 UCO 6 MgO - Cat #4 500 4 3 Second exp.campaign UCO 7 AC - Reduced WHSV 2.5 4 FA 8 AC - Reduced WHSV 2.5 ü Focus on UCO conversion. Bio-oil quality vs temperature vs catalyst ü Best configuration tested again by increasing catalyst mass (WHSV). ü Best bio-oil distilled to identify bio-kerosene fractions. ü FA tested to examine deoxygenation performances of FA vs UCO 10
Results 11
Mass balance ü Process temperature 500 C ü Time on stream, 90 min In plant or process operations, the actual time that a unit is operating and producing product. ü WHSV = 4 h -1 Yield %wt 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% NO CAT CAT n.1 CAT n.2 CAT n.3 CAT n.4 NO CAT CAT n.1 CAT n.2 CAT n.3 CAT n.4 Liquid Yield 62,70% 63,64% 54,55% 33,74% 61,72% Non condensable gases Yield 22,30% 21,36% 30,45% 51,26% 23,28% Not converted fraction 15,00% 15,00% 15,00% 15,00% 15,00% 12
Bio-oil properties ü Selected process temperature: 500 C ü Time on stream: 90 min ü WHSV = 4 h -1 Catalytic tests Parameter Unit None CAT n.1 CAT n.2 CAT n.3 CAT n.4 Feedstock UCO UCO UCO UCO UCO WHSV 1/h 4 4 4 4 Process temperature C 500 500 500 500 500 Liquid yield wt% 62.70 63.64 54.55 33.74 61.72 C wt% 76.75 76.10 76.03 77.90 78.17 H wt% 11.45 11.10 11.65 10.10 11.48 N wt% 0.02 0.03 0.08 0.07 0.03 O wt% 11.98 12.77 12.25 11.93 10.33 Water content wt% 0.89 0.77 1.18 8.36 1.61 Density kg/liter 0.87 0.85 0.85 0.90 0.86 LHV MJ/kg 36.82 37.79 39.57 36.48 37.46 HHV MJ/kg 39.25 40.14 42.02 38.55 39.95 Acid value - 117.73 74.10 61.97 20.45 80.07 Kinematic viscosity (40 C) cst 4.47 2.24 3.36 1.19 5.68 13
Bio-oil composition ü The identification and quantification of chemical species were carried out by means of GC MS / GC FID (GC 2010 Plus Shimadzu) CAT n.1 CAT n.2 13% 5% Fatty Acids 12% 64% 8% Paraffins 8% Olefines 23 % HC Aromatics 75% 2% Ciclo-octene Undetected Species CAT n.4 18% CAT n.3 3% 1% 0% 92% 4% 0% 75% 3% 7% 1% 2% 1% 3% 1% 2% Ø Test with AC-CAT #1 @500 C selected as best case in terms of liquid yield and composition 14
Increasing catalyst mass Best configuration (CAT n.1) tested at 500 C, WHSV = 2.5 h -1 (CAT n.1*) 64% CAT n.1 13% 5% 8% 8% Fatty Acids Paraffins Olefines 35 % HC Aromatics 58% CAT n.1* 7% 15% 11% 2% Ciclo-octene Undetected Species 3% 6% Ø No significant changes in yield of liquid product (~ 63 %). Ø Increasing catalysts mass: ü higher aliphatic HCs content; ü lower aromatic HCs content; ü lower FFAs content. 15
FAs test ü Test CAT n.1* (UCO) was repeated feeding FAs @ 500 C and WHSV = 2.5 h -1 (CAT n.1**). CAT n.1** Fatty Acids 16% Paraffins 44% 20% Olefines Aromatics 40 % HC 2% 6% 12% Ciclo-octene Undetected Species Ø Slight liquid yield reduction (~ 49 %). Ø Higher overall HCs content Ø Higher Paraffins & Olefins content 16
UCO vs FA pyrolysis ü Oxygen removal is significantly higher Parameter Unit Commercial SO Filtered UCO (1 µm) Density kg/m 3 914 911 Kinematic Viscosity at 40 C mm 2 /s 26.0 38.15 18.03 Acid value mg KOH/g 1.06 2.63 201.7 Free Fatty Acid % 0.53 1.31 100.85 Iodine Number g Iodine/100g n.p. 93 Water content % 0.085 0.08 0.08 Ash % (m/m) 0.007 0.01 Total contamination mg/kg 209 256 68 Insoluble impurities % 0.01 0.05 Phosphorus mg/kg 0.11 10.1 C % 77.8 76.3 76.3 H % 11.9 11.7 12.2 N % 0.01 0.02 0.02 N mg/kg 116 137 O % 10.3 11.98 11.48 Calorific value, higher MJ/kg 39.5 38.9 39.4 Calorific value, lower MJ/kg 37.0 36.4 36.8 FAs Parameter Unit Norm CAT/1* CAT/1** Feedstock UCO FAs WHSV 1/h 2,5 2,5 Catalyst4Temp. C ) 500 500 Liquid4yield wt% ) 63,41 48,82 C wt% UNI5151045 76,295 83,53 H wt% UNI5151045 11,5 12,7 N wt% UNI5151045 0,04 0,04 O wt% calculated 12,165 3,73 Water4content wt% UNI58534 0,5375 0,17 Density kg/liter UNI53675 0,843 LHV MJ/kg calculated 38,897 40,0976 HHV MJ/kg DIN551900)25 41,335 42,79 Acid4value ) UNI514104 51,445 44,4 Kinematic4viscosity4(40 C) cst UNI531045 2,48 1,5 Fatty4Acids wt% wt% 7% 16% Paraffins wt% wt% 15% 20% Olefines wt% wt% 11% 12% Aromatics wt% wt% 6% 6% CicloJoctene wt% wt% 3% 2% Tot.4HCs wt% wt% 35% 40% SUM wt% wt% 42% 56% Undetected4Species wt% wt% 58% 44% 17
Recent (still unpublished) tests FA and STEARIC ACID, AC CAT #1* (@ 500 C, WHSV = 2.5 h -1 ). 18
Distillation test: procedure ü Distillation test (p_atm, CAT n.1*, 500 C, WHSV = 2.5 h -1 ) ü 3 fractions: A (<150 C); B (150-200 C); C (200-250 C) 250 150 Distillation test at RE-CORD laboratories Kerosene boiling range 19
Distillation test: UCO bio-oil CAT1* and CAT1** UCO bio-oil CAT1* UCO bio-oil CAT1** C Bio-intermediate in the range of kerosene fraction 48% (B + C), i.e. 30% of total feed B A 18% 34% A (<150 C) 24% B (150-200 C) Bio-intermediate fraction in the range of kerosene 51% (B + C) 24% C (200-250 C) Residual 9% 40% 19% A (<150 C) B (150-200 C) 32% C (200-250 C) Residuo differenza 20
Summary on PO of VO/UCO/FA Ø Catalytic conversion through pyrolysis of UCO was performed at 500 C with 4 different catalysts (WHSV = 4 1/h). Ø The best result (CAT n.1 test) gave 63.6 %wt of bio-oil, with lower Oxygen content, density, viscosity and higher HV than original feedstock. Ø Increasing catalyst mass, there were no significant changes in terms of bio-oil yield, but higher fractions of HCs classes were detected (from 24 to 35%wt). Ø Preliminary distillation tests were carried out Ø Further investigation concerned analytical issues in HC content quantification. This recent work concluded that more than 70% of collected liquid are HCs 21
Conferences/WS.. Publications & Communications ü ü ü ü ü ü ü ü ü EU Biomass Conf 2016-15-14 ICAE (Int Conf.on Applied Energy) ISAF (Int Conf.on Alcohol Fuels) 2016-15 Europefedlipid 2015 Biorefinery 2015 CORE-Jet meetings 2015-16 ATI conf (Italy) 2015 Pyro 2014 ISAFF (It.Forum on Alt.Fuels) 2014. Ø Book(among others): ü CRC Book on Biofuels RiaziChiaramonti ed.: chapter on Aviation Biofuels with prof L.Horta Nogueira Ø IEA Task 39 meetings ü Presentations of activities Ø EU BRISK R&D on biofuel combustion ü Cardiff Univ. 22
Thanks for your Attention! David Chiaramonti Contacts david.chiaramonti@re-cord.org david.chiaramonti@unifi.it 23