Engineering Conferences International ECI Digital Archives BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals Proceedings Spring 6-12-2013 Integrating Pyrolysis and Anaerobic Digestion in a Novel Biorefinery Concept Matthew Smith Washington State University Manuel Garcia Perez Washington State University Follow this and additional works at: http://dc.engconfintl.org/bioenergy_iv Part of the Chemical Engineering Commons Recommended Citation Matthew Smith and Manuel Garcia Perez, "Integrating Pyrolysis and Anaerobic Digestion in a Novel Biorefinery Concept" in "BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals", Manuel Garcia-Perez,Washington State University, USA Dietrich Meier, Thünen Institute of Wood Research, Germany Raffaella Ocone, Heriot-Watt University, United Kingdom Paul de Wild, Biomass & Energy Efficiency, ECN, The Netherlands Eds, ECI Symposium Series, (2013). http://dc.engconfintl.org/bioenergy_iv/31 This Conference Proceeding is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion in BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals by an authorized administrator of ECI Digital Archives. For more information, please contact franco@bepress.com.
Integrating Pyrolysis and Anaerobic Digestion in a Novel Biorefinery Concept Matthew Smith, Manuel Garcia-Perez Bioenergy IV June 12 th, Otranto Italy
Motivation for Integration Adoption of anaerobic digestion is currently proceeding at a slower than desired pace in the United States Adoption is hindered by currently marginal economics of operations Pyrolysis offers an effective means to treat recalcitrant fiber remaining after digestion and develop potentially valuable co-products Fields surrounding numerous dairy and CAFOs are overloaded with N and P (36% and 55%). Char based filters may be effective in reducing effluent concentrations and limiting further over application
Desired Design Properties Pyrolysis unit should be able to operate with little maintenance using AD fiber Char modification should not require an abundance of purchased chemicals or generate significant waste water Filter media should be able to reduce phosphates and ammonium to near zero levels in the effluent Filter media should not contaminate the treated effluent stream
Combustion Gases Steam turbine Electricity Low Pressure steam Aqueous phase rich in acetic acid from fast pyrolysis and torrefaction Combustion Vapor Steam Water Dairy manure Anaerobic digester Biogas Pyrolysis Precipitation of AAEMs Solids Solids Separation fuel and heat char Liquid rich in N and P Char Oxidation Lagoon Storage High CEC char Ion Exchange Filtration Clean water N & P loaded char
Phosphorous Removal Exploratory Study Results Char produced from unaltered AD fiber has relatively poor phosphate adsorption characteristics. Post-pyrolysis calcium addition was effective at reducing phosphates but resulted in higher metal leaching Post-pyrolysis iron addition was not effective at reducing phosphate in solution Addition of Calcium to the fiber to pyrolysis is an effective method to phosphate adsorption. This treatment was selected for further studies.
Phosphorous Removal Pre-pyrolysis CaCl 2 modification of AD fiber Experimental AD fiber was acid washed in 2% nitric acid and impregnated with calcium by immersion in a CaCl 2 solution followed by ph adjustment to 6, 8, 9.35, 11 and 12 Modified fiber samples were then dried and pyrolized at 500 o C for 30 minutes using a spoon reactor Spoon Reactor Spoon Reactor Diagram
Phosphorous Removal Pre-pyrolysis CaCl 2 modification of AD fiber Elemental Analysis C H N Ash O AD1 39.8 4.4 3.3 25.5 27.0 AD1AW 43.1 4.7 3.5 18.9 29.8 AD1AWC 42.8 2.2 2.9 40.2 11.8 ph6 43.6 2.6 2.9 38.4 12.5 ph8 42.5 2.5 2.8 37.3 14.8 ph9.35 42.2 2.5 2.8 39.8 12.7 ph11 39.1 2.4 2.6 41.3 14.6
Phosphorous Removal Calcium Concentration (mg / g fiber) Char fraction (%) Pre-pyrolysis CaCl 2 modification of AD fiber 70 60 50 40 57 56 55 54 30 53 20 Raw Fiber 52 10 51 0 4 6 8 10 12 Final ph of CaCl2 Solution 50 40 50 60 70 80 Total AAEM fraction mg / g fiber
Phosphorous Removal Na, Ca, K show possible metal leaching, other metals showed no significant loss Metal leaching, mg X / g char. Error ± 0.1 Sample Na Ca K Raw 0.07 0.38 0.00 ph 6 0.01 0.02 0.06 ph 8 0.00 0.02 0.01 ph 9.35 0.01 0.01 0.01 ph 11 0.01 0.02 0.01 ph 12 0.06 0.02 0.13
Phosphorous Removal Phosphate Adsorption (mg PO4/g) 16 14 12 ph 12 ph 11 10 8 6 ph 9.35 ph 8 ph 6 4 2 0 Raw 0 10 20 30 40 Contact time (hours)
Phosphorous Removal Phosphate adsorbed mg/g Phosphate Adsorption Sample ph 9.35 phosphate adsorption compared to first order model 14 12 10 8 6 4 2 0 0 10 20 30 40 Contact time (hours) dq dt = k q e q dq dt = change in concentration k = 1st order rate constant q e = equilibrium constant q = concentration at time t
Phosphorous Removal Phosphate adsorbed mg/g Phosphate Adsorption Sample ph 9.35 phosphate adsorption compared to first order model 14 12 10 8 6 4 2 0 Plateau, followed by increase after 24 hours suggests multilayer adsorption or slow mineralization is occurring 0 10 20 30 40 Contact time (hours) dq dt = k q e q dq dt = change in concentration k = 1st order rate constant q e = equilibrium constant q = concentration at time t
Phosphorous Removal Equilibrium Adsorption mmol/g 1st order rate constant (1/hr) Phosphate Adsorption 0.5 0.4 0.3 Raw 0.2 0.1 0.0 Raw 1 1.5 2 2.5 3 Calcium Concentration (mmol/g)
Phosphorous Removal Equilibrium Adsorption mmol/g 1st order rate constant (1/hr) Phosphate Adsorption 0.5 0.4 0.3 Raw 0.2 0.1 Raw Y =.0765x -.0886 0.0 1 mol PO 4 3- adsorbed per 13 mol Ca + Mg 1.5 2 2.5 3 3.5 Calcium + Magnesium Concentration (mmol/g)
Phosphorous Removal Conclusions Contacting fiber with a CaCl 2 solutions prior to pyrolysis significantly increased the adsorption capacity of resulting chars. Increasing the equilibrium ph of solutions during contacting further increased both the rate and equilibrium adsorption capacity of the char. Chars prepared from fiber equilibrated at ph 9.35 effectively removed more than 50% of ionic phosphate after 7.5 hours and 80% after 36 hours. Minerals of both calcium and magnesium are involved in the adsorption of phosphates Chars modified with calcium did not show high levels of leaching during the adsorption tests, indicating that the mineral matter was converted to a stable form.
Oxidation for Nitrogen Removal Experimental Equipment Ozone Cold Plasma Air Oxidation ~ Spoon Reactor
Oxidation for Nitrogen Removal Experimental Untreated AD fiber was pyrolized at 500 o C for 30 minutes to generate all char samples studied, Pine wood and bark chars were produced in an auger reactor at 500 o C Untreated fiber char was oxidized by three different mechanisms 1) Ozone at 70 mg/l (4%) at 2 SLPM for 30 minutes 2) Cold plasma using a 4.2 kv RMS arc potential for 20 minutes 3) Air at elevated temperature for 1.5-2 hours The change in functional groups were evaluated by Boehm titration
Oxidation for Nitrogen Removal Ozone Studies using ozone showed to it be an excellent oxidizing agent for activated carbons and chars from Douglas Fir Bark( DFBC) but had limited effect on Douglas Fir Wood Char (DFWC) Activated Carbon DF Bark Char DF Wood Char Surface groups ( mol/g) 600 500 400 300 200 100 Carboxylic Lactonic Phenolic AC Surface groups ( mol/g) 600 500 400 300 200 100 DFBC Surface groups ( mol/g) 500 400 300 200 100 DFWC 0 0 10 20 30 40 50 60 Ozonation Time (min) 0 0 10 20 30 40 50 60 Ozonation Time (min) 0 0 10 20 30 40 50 60 Oxidation Time (min) Strong ozonation effect
Oxidation for Nitrogen Removal Mass percent reamining Mass loss due to oxidation 100 80 60 325C 300C 40 275C 250C 225C 20 200C 0 0 0.5 1 1.5 2 2.5 3 3.5 4 Oxidation time at final temperature (hours)
Oxidation for Nitrogen Removal Carboxylic Group Formation Cold Plasma
Oxidation for Nitrogen Removal Changes in soluble matter due to oxidation
Oxidation for Nitrogen Removal Changes in soluble matter (ph 8-9) due to oxidation Raw AW O3 CP O 2 treated 275-350 o C
Oxidation for Nitrogen Removal Changes in soluble matter (ph ~ 12) due to oxidation Raw AW O3 CP O 2 treated 275-350 o C
Oxidation for Nitrogen Removal Correlation between Ammonium Adsorption and Carboxylic groups (acid washed chars) 500 400 NH4-N adsorption ph 6.3 (umol/g) 300 200 100 y = 0.9782x R² = 0.811 0 0 100 200 300 400 500 Total Carboxylic Groups
Oxidation for Nitrogen Removal Conclusions All oxidation methods tested resulted in varying degrees of acid group formation and carbon gasification. Air at temperatures of 250-300 o C was effective at generating carboxylic acid groups, at 350 o C carboxylic groups were not detected. This process can be easily integrated to a pyrolysis units during bio-char cooling.. Increasing the number of carboxylic groups on various char surfaces was found to have a near 1:1 correlation with CEC and ammonium adsorption Oxidation by air results in the formation of a significant fraction of small molecules and particles soluble in basic solutions that require further study Shorter oxidation times and possibly lower oxygen concentration are required to mitigate destruction of the surface
Acknowledgements We would like to thank the funding agencies supporting our Research Program WASHINGTON STATE UNIVERSITY AGRICULTURAL RESEARCH CENTER WASHINGTON STATE DEPARTMENT OF ECOLOGY WASHINGTON STATE DEPARTMENT OF AGRICULTURE SUN GRANT INITIATIVE, U.S. DEPARTMENT OF TRANSPORTATION, USDA U.S. NATIONAL SCIENCE FOUNDATION U.S. DEPARTMENT OF ENERGY
QUESTIONS?