Arauzo, Jesús

Garcia, L.

Oliva, M.

Ruiz, J.

Valiente, A.

English

Engineering Conferences International

HYDROGEN PRODUCTION BY AQUEOUS-PHASE REFORMING OF GLYCEROL FROM THE BIODIESEL MANUFACTURINGJ. Arauzo, A. Valiente, M.Oliva, J. Ruiz, L.García*Thermochemical Processes Group (GPT), Aragon Institute for Engineering Research (I3A), Zaragoza (Spain)* e-mail: jarauzo@unizar.es Bioenergy III:Present and New Perspectives on Biorefineries, Lanzarote (Spain),May 25th, 2011OUTLINE1. INTRODUCTION AND OBJECTIVES2. EXPERIMENTAL METHOD3. EXPERIMENTAL RESULTS• Effect of the feedstock and the glycerol content• Effect of the catalyst composition4. CONCLUSIONSBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011OUTLINE1. INTRODUCTION AND OBJECTIVES2. EXPERIMENTAL METHOD3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition4. CONCLUSIONSBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011EXPERIMENTAL METHOD RESULTS CONCLUSIONSTHERMOCHEMICAL CONVERSIONAQUEOUS PHASEREFORMING(APR)STEAMREFORMINGAUTOTHERMAL REFORMING SUPERCRITICALWATERREFORMING Reforming Air PARTIALOXIDATION 1. Introduction and objectivesH2/CO2airT ~ 227ºCP = 25-50 barPt-Ni/Al2O3Reforming +ShiftT ~ 500-850ºCP = 1 atmS/C=2-4Me/CeO2/Al2O3+ShiftT ~ 800-1000ºCC/O=0.43Pt/Al2O3+Reforming T ~ 374ºCP = 221 barNo catalystT ~ 500-800ºCC/O=0.3S/C=3Pd/Ni/Al2O3Adhikari et al. Ener. Conv. Management (2009) 2600-2604.Bioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 20111. Introduction and objectivesvaluable products+GlycerolR1TriacylglycerolCH OCO R1CH OCO R1Methanol+ 3 CH3 OHCH2 OHCH  OHCH2 OHAlkyl esterCO OCH33CH OCO R1H2USES:• CO + H2• fuel cellsBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 20111. Introduction and objectivesPure glycerol (chem)Glycerol from biodieselmanufacturing (co-prod):Average of organics:Synthesis of biodiesel in the laboratory:RAW MATERIALSEPARATIONT = 60 ºCReagents:Bioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011MeOH: 4%Acetic Acid: 38%Glycerol: 58%GLYCEROLBIODIESELREACTION : 3hNEUTRALIZATIONUSINGACETIC ACIDGLYCEROLMethanation and Fisher-Tropsch reactionWater-gas-shiftH2H-HO O-C-C-H*  *H2, CO 2H2, CO2-C-C-HO OH HH HCleavage C-CH2HO H-C-C-OH  *   *HHCleavage C-O1. Introduction and objectivesAlkanesH2, CO2, H2OH2Davda et al. App. Cata. B (2005) 171-186.-C-C-OHH OHOrganics acidsH2H2O2H2O-C-C-HH OH HAlcoholBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011 Experimental work with glycerol as a waste ofbiodiesel process at micro-scale reactor. Development of suitable catalysts for the process:OBJECTIVES Adequate catalytic activity and selectivitytowards H2.Resistance to deactivation.Bioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011OUTLINE1. INTRODUCTION AND OBJECTIVES2. EXPERIMENTAL METHOD3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition4. CONCLUSIONSBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 20112. Experimental methodExperimental conditions:• T = 500 K• P = 33 bar• Glycerol aqueous solution2-10 wt%• Liquid flow rate: 1 mL/min• WHSV = 3 (g glycerol/ gcatalyst h)• Run time: 5 hCharacteristics:• Micro-scale reactor test.• Fixed bed (sand + catalyst)particle sizes: 320-160 µm.• Upward flow.• Stainless steel reactor(9mm i.d).Bioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 20112. Experimental methodExperimental systemBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011Ni(NO3)2·6H2OAl(NO3)3·9H2ONH4OHT = 40ºCpH = 7.9CALCINATIONCALCINED PRECURSOR100 cm3/min T = 750ºC140 cm3/min airREDUCTIONCatalysts prepared by a coprecipitation method28 and 41% Ni/(Ni+Al)2. Experimental methodCOPRECIPITACIONHYDRATED PRECURSORFilteringDryingACTIVATED CATALYSTH21 hT=650 ºC3 hAl-Ubaid, A. and E.E. Wolf, Appl. Catal., 40 (1988), 73Bioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011OUTLINE1. INTRODUCTION AND OBJECTIVES2. EXPERIMENTAL METHOD3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition4. CONCLUSIONSBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 20110 50 100 150 200 250 30001020304050 Alkane selectivity (%)Time (min)01020304050   H2 selectuvity (%)0 50 100 150 200 250 3000,000,050,100,150,200,250,300,35  CO2 yield (g/g glycerol)Time (min)0,0000,0020,0040,0060,0080,0100,0120,0140,0160,018  H2 yield (g/g glycerol)Effect of the feedstock and the glycerol content:3. Results2% chem  (■) 2% co-prod  (□)5% chem (●)5% co-prod (○)10% chem  (▲) 10% co-prod (∆) Catalyst: 28% Ni Bioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011 The co-prod glycerol showed higher hydrogen selectivity and smaller alkane selectivity. Constant gas yield values were obtained with time, no deactivation was observed.  H2 and CO2 yields when the co-prod glycerol is fed.0102030405060708090100chemchemco-prodco-prodco-prodchem2 wt% 5 wt%  Organics conversion (%) 10 wt%50  Organic conversion is similar betweenboth feedstock. However, an improvementwas observed with the highest glycerolcontent.3. ResultsBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011010203040co-prodco-prodco-prodchemchemchem10 wt%5 wt%2 wt% Carbon conversion (%) Higher carbon conversion to gas isobtained in glycerol from chemicalreagent compared to co-product inbiodiesel manufacturing.2% chem2% co-prod5% chem5% co-prod10% chem10% co-prodYield(g chemical/g organics)MeOHEtOHAcetol0.05740.02130.13050.06170.02800.12500.02560.01810.08000.03820.02440.08730.01670.04820.05020.01800.00420.0480Effect of the feedstock and the glycerol content:3. ResultsBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011Acetic acid Propylene glycolEthylene glycol0.14350.05350.09510.41100.15290.05920.06180.09540.06150.60920.07110.04600.02890.14880.05800.28690.01180.0155 Product yields  when the glycerol content OUTLINE1. INTRODUCTION AND OBJECTIVES2. EXPERIMENTAL METHOD3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition4. CONCLUSIONS Bioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 20110 50 100 150 200 250 30001020304050 Alkane selectivity (%)Time (min)01020304050   H2 selectivity (%)0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 00 , 0 00 , 0 50 , 1 00 , 1 50 , 2 0T i m e  ( m i n )CO2 yield (g/g glycerol)0 , 0 0 00 , 0 0 10 , 0 0 20 , 0 0 30 , 0 0 40 , 0 0 50 , 0 0 60 , 0 0 70 , 0 0 8 H2 yield (g/g glycerol)3. ResultsEffect of the catalysts composition:Bioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 201128% Ni chem  (■) 28% Ni co-prod  (□)41% Ni chem (●)41% Ni co-prod (○) 41 wt% Ni catalyst tested showed a slightly deactivation in co-prod glycerol. Co-prod glycerol: H2 and CO2 yields are similar for both catalysts, after deactivation periodof 41 wt% Ni catalyst. Chemical glycerol: H2 and CO2 yields  when %Ni010203040506070809010041%Ni28%Ni5 wt%co-prodco-prodchemchem    Organics conversion (%)   The organic conversion is similarfor both feeds and catalysts exceptfor the 41% Ni catalyst and co-product feeding, that is higher.3. ResultsBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 20110102030405041%Ni28%Nichemchemco-prodco-prod5 wt%Carbon conversion (%)  Higher carbon conversion to gas isobtained in glycerol from chemicalreagent.28% Ni 5% chem28% Ni5% co-prod41% Ni5% chem41% Ni5% co-prodYield (g chemical/g organics):MeOHEtOHAcetolAcetic acid Propylene glycol0.02560.01810.08000.06180.09540.03820.02440.08730.60920.07110.02800.01400.06070.05910.08780.03160.00190.06720.29240.03903. ResultsEffect of the catalysts composition:Bioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011Ethylene glycol 0.0615 0.0460 0.0887 0.0408OUTLINE1. INTRODUCTION AND OBJECTIVES2. EXPERIMENTAL METHOD3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition4. CONCLUSIONSBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011 The co-prod glycerol showed higher hydrogen selectivity and smaller alkaneselectivity. Organic conversion is similar between both feedstock. However, an improvementwas observed with the highest glycerol content. Higher carbon conversion to gas is obtained in glycerol from chemical reagentcompared to co-product in biodiesel manufacturing.CONCLUSIONSBioenergy III: Present and New Perspectives on Biorefineries – Lanzarote, May 2011 Co-prod glycerol showed a slightly deactivation in 41 wt % Ni catalyst tested.FUTURE WORK Upgrade of waste biomass aqueous streams from several industrial processes;cheese whey and black liquor in a bench scale.HYDROGEN PRODUCTION BY AQUEOUS-PHASE REFORMING OF GLYCEROL FROM THE BIODIESEL MANUFACTURINGJ. Arauzo, A. Valiente, M.Oliva, J. Ruiz, L.García*Thermochemical Processes Group (GPT), Aragon Institute for Engineering Research (I3A), Zaragoza (Spain)* e-mail: jarauzo@unizar.es Bioenergy III:Present and New Perspectives on Biorefineries, Lanzarote (Spain),May 25th, 2011

Hydrogen Production by Aqueous-Phase Reforming of Glycerol from the Biodiesel Manufacturing

https://dc.engconfintl.org/cgi/viewcontent.cgi?article=1019&amp;context=bioenergy_iii

Hydrogen Production by Aqueous-Phase Reforming of Glycerol from the Biodiesel Manufacturing

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