HYDROGEN PRODUCTION BY AQUEOUS-PHASE REFORMING OF GLYCEROL FROM THE BIODIESEL MANUFACTURING

HYDROGEN PRODUCTION BY AQUEOUS-PHASE REFORMING OF GLYCEROL FROM THE BIODIESEL MANUFACTURING * J. Arauzo, A. Valiente, M.Oliva, J. Ruiz, L.García Thermoical 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

OUTLINE 1. INTRODUCTION AND OBJECTIVES 2. EXPERIMENTAL METHOD 3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition 4. CONCLUSIONS

EXPERIMENTAL METHOD RESULTS 1. Introduction and objectives CONCLUSIONS THERMOCHEMICAL CONVERSION STEAM REFORMING AUTOTHERMAL REFORMING AQUEOUS PHASE REFORMING (APR) SUPERCRITICAL WATER REFORMING PARTIAL OXIDATION Reforming + Shift T ~ 500-850ºC P = 1 atm S/C=2-4 Me/CeO 2 /Al 2 O 3 Air + Reforming + Shift Reforming T ~ 374ºC P = 221 bar No catalyst T ~ 500-800ºC C/O=0.3 S/C=3 Pd/Ni/Al 2 O 3 T ~ 227ºC P = 25-50 bar Pt-Ni/Al 2 O 3 air T ~ 800-1000ºC C/O=0.43 Pt/Al 2 O 3 H 2 /CO 2 Adhikari et al. Ener. Conv. Management (2009) 2600-2604.

1. Introduction and objectives CH OCO R 1 CH OCO R 1 CH OCO R 1 Triacylglycerol + 3 CH 3 OH Methanol CH 2 OH CH OH CH 2 OH Glycerol + 3 CO OCH 3 R 1 Alkyl ester valuable products H 2 USES: CO + H 2 fuel cells

Synthesis of biodiesel in the laboratory: 1. Introduction and objectives RAW MATERIAL GLYCEROL REACTION : BIODIESEL SEPARATION T = 60 ºC 3h NEUTRALIZATION USING ACETIC ACID Reagents: Pure glycerol () Glycerol from biodiesel manufacturing (co-prod): Average of organics: MeOH: 4% Acetic Acid: 38% Glycerol: 58% GLYCEROL

1. Introduction and objectives H H O O -C-C-H H H H 2 H 2 H 2 H 2 H-H O O -C-C-H * * H O H -C-C-O H * * H 2 O Cleavage C-C H 2 Cleavage C-O H 2 O Water-gas-shiftshift H 2, CO 2H 2, CO 2 H H O -C-C-H H H Alcohol Methanation and Fisher- Tropsch reaction H O -C-C-OH H Organics acids Alkanes H 2, CO 2, H 2 O Davda et al. App. Cata. B (2005) 171-186.

OBJECTIVES Experimental work with glycerol as a waste of biodiesel process at micro-scale reactor. Development of suitable catalysts for the process: Adequate catalytic activity and selectivity towards H 2. Resistance to deactivation.

OUTLINE 1. INTRODUCTION AND OBJECTIVES 2. EXPERIMENTAL METHOD 3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition 4. CONCLUSIONS

2. Experimental method Experimental conditions: T = 500 K P = 33 bar Glycerol aqueous solution 2-10 wt% Liquid flow rate: 1 ml/min WHSV = 3 (g glycerol/ g catalyst h) Run time: 5 h Characteristics: Micro-scale reactor test. Fixed bed (sand + catalyst) particle sizes: 320-160 µm. Upward flow. Stainless steel reactor (9mm i.d).

Experimental system 2. Experimental method

2. Experimental method Catalysts prepared by a coprecipitation method 28 and 41% Ni/(Ni+Al) Ni(NO 3 ) 2 6H 2 O Al(NO 3 ) 3 9H 2 O ph = 7.9 NH 4 OH CALCINATION CALCINED PRECURSOR T = 40ºC COPRECIPITACION T = 750ºC 140 cm 3 /min air 3 h HYDRATED PRECURSOR REDUCTION 100 cm 3 /min H 2 1 h T=650 ºC Filtering Drying ACTIVATED CATALYST Al-Ubaid, A. and E.E. Wolf, Appl. Catal., 40 (1988), 73

OUTLINE 1. INTRODUCTION AND OBJECTIVES 2. EXPERIMENTAL METHOD 3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition 4. CONCLUSIONS

Effect of the feedstock and the glycerol content: 3. Results H 2 selectuvity (%) Alkane selectivity (%) 50 40 30 20 10 0 50 40 30 20 10 0 0 50 100 150 200 250 300 Time (min) H 2 yield (g/g glycerol) CO 2 yield (g/g glycerol) 0,018 0,016 0,014 0,012 0,010 0,008 0,006 0,004 0,002 0,000 0,35 0,30 0,25 0,20 0,15 0,10 0,05 0,00 0 50 100 150 200 250 300 Time (min) 2% ( ) 2% co-prod ( ) 5% ( ) 5% co-prod ( ) 10% ( ) 10% co-prod ( ) Catalyst: 28% Ni The co-prod glycerol showed higher hydrogen selectivity and smaller alkane selectivity. Constant gas yield values were obtained with time, no deactivation was observed. H 2 and CO 2 yields when the co-prod glycerol is fed.

3. Results 100 Organics conversion (%) 90 80 70 60 50 40 30 20 co-prod co-prod co-prod Organic conversion is similar between both feedstock. However, an improvement was observed with the highest glycerol content. 10 0 2 wt% 5 wt% 10 wt% 50 Carbon conversion (%) 40 30 20 10 co-prod co-prod co-prod Higher carbon conversion to gas is obtained in glycerol from ical reagent compared to co-product in biodiesel manufacturing. 0 2 wt% 5 wt% 10 wt%

3. Results Effect of the feedstock and the glycerol content: 2% 2% co- prod 5% 5% co- prod 10% 10% co- prod Yield(g ical/g organics) MeOH EtOH Acetol Acetic acid Propylene glycol Ethylene glycol 0.0574 0.0213 0.1305 0.1435 0.0535 0.0951 0.0617 0.0280 0.1250 0.4110 0.1529 0.0592 0.0256 0.0181 0.0800 0.0618 0.0954 0.0615 0.0382 0.0244 0.0873 0.6092 0.0711 0.0460 0.0167 0.0482 0.0502 0.0289 0.1488 0.0580 0.0180 0.0042 0.0480 0.2869 0.0118 0.0155 Product yields when the glycerol content

OUTLINE 1. INTRODUCTION AND OBJECTIVES 2. EXPERIMENTAL METHOD 3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition 4. CONCLUSIONS

Effect of the catalysts composition: 3. Results 0, 0 0 8 H 2 selectivity (%) Alkane selectivity (%) 50 40 30 20 10 0 50 40 30 20 10 0 0 50 100 150 200 250 300 Time (min) CO yield (g/g glycerol) H yield (g/g glycerol) 2 2 0, 0 0 7 0, 0 0 6 0, 0 0 5 0, 0 0 4 0, 0 0 3 0, 0 0 2 0, 0 0 1 0, 0 0 0 0, 2 0 0, 1 5 0, 1 0 0, 0 5 0, 0 0 0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 T i m e ( m i n ) 28% Ni ( ) 28% Ni co-prod ( ) 41% Ni ( ) 41% Ni co-prod ( ) 41 wt% Ni catalyst tested showed a slightly deactivation in co-prod glycerol. Co-prod glycerol: H 2 and CO 2 yields are similar for both catalysts, after deactivation period of 41 wt% Ni catalyst. Chemical glycerol: H 2 and CO 2 yields when %Ni

3. Results 100 Organics conversion (%) 90 80 70 60 50 40 30 20 co-prod 5 wt% co-prod The organic conversion is similar for both feeds and catalysts except for the 41% Ni catalyst and coproduct feeding, that is higher. 10 0 28%Ni 41%Ni 50 Carbon conversion (%) 40 30 20 10 co-prod 5 wt% co-prod Higher carbon conversion to gas is obtained in glycerol from ical reagent. 0 28%Ni 41%Ni

Effect of the catalysts composition: 3. Results 28% Ni 28% Ni 41% Ni 41% Ni 5% 5% co-prod 5% 5% co-prod Yield (g ical/g organics): MeOH 0.0256 0.0382 0.0280 0.0316 EtOH 0.0181 0.0244 0.0140 0.0019 Acetol 0.0800 0.0873 0.0607 0.0672 Acetic acid 0.0618 0.6092 0.0591 0.2924 Propylene glycol 0.0954 0.0711 0.0878 0.0390 Ethylene glycol 0.0615 0.0460 0.0887 0.0408

OUTLINE 1. INTRODUCTION AND OBJECTIVES 2. EXPERIMENTAL METHOD 3. EXPERIMENTAL RESULTS Effect of the feedstock and the glycerol content Effect of the catalyst composition 4. CONCLUSIONS

CONCLUSIONS The co-prod glycerol showed higher hydrogen selectivity and smaller alkane selectivity. Organic conversion is similar between both feedstock. However, an improvement was observed with the highest glycerol content. Higher carbon conversion to gas is obtained in glycerol from ical reagent compared to co-product in biodiesel manufacturing. 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.