Selective Pyrolysis of Lignocellulosic Materials and Novel Refining Concepts to Produce Second Generation Bio-fuels, Bio-chemicals and Engineered Bio-chars.

SELECTIVE PYROLYSIS OF LIGNOCELLULOSIC MATERIALS AND NOVEL REFINING CONCEPTS TO PRODUCE SECOND GENERATION BIO-FUELS, BIO-CHEMICALS AND ENGINEERED BIO-CHARS.

Sponsoring Institution

National Institute of Food and Agriculture

Project Status

TERMINATED

Funding Source

HATCH

Reporting Frequency

Annual

Accession No.

0214389

Grant No.

(N/A)

Project No.

WNP00701

Proposal No.

(N/A)

Multistate No.

(N/A)

Program Code

(N/A)

Project Start Date

Jan 1, 2013

Project End Date

Dec 31, 2017

Grant Year

(N/A)

Project Director
Garcia-Perez, M.

Recipient Organization
WASHINGTON STATE UNIVERSITY
240 FRENCH ADMINISTRATION BLDG
PULLMAN,WA 99164-0001

Performing Department
Biological Systems Engineering

Non Technical Summary
This research effort will be devoted to advance the science and technology required to implement a new model of a biomass economy, formed by distributed pyrolysis units, rural refineries and centralized refineries. The pyrolysis units located near biomass resources will produce crude bio-oil and bio-char. The crude bio-oil is then transported to rural refineries to be converted into stabilized bio-oil, fuels and chemicals (ethanol, lipids, biogas, bio-plastic). Finally, centralized refineries are envisioned to convert stabilized bio-oils into drop-in transportation fuels. The pyrolysis units could have a function in this new biomass economy similar to the role of petroleum wells in our current petroleum based economy. To implement this concept, additional research in several areas is necessary to: (1) conduct fundamental studies of thermo-chemical reactions to better understand the relationship between biomass composition and its thermal degradation mechanisms to enhance the production of levoglucosan (2) develop and tests new types of selective fast pyrolysis reactors and their mathematical modeling, (3) develop new analytical methods to characterize the chemical composition of bio-oils, (4) develop bio-chars for environmental services (5) evaluate several new concepts for rural bio-oil refineries, (6) study the feasibility of processing of stabilized bio-oil fractions in existing petroleum refineries, and (7) develop and test second generation bio-fuels and chemicals from bio-oils. Our project targets the conversion of at least 30 mass % of the initial biomass into transportation fuels and high value chemicals. The production of engineered bio-chars for environmental services will contribute to sequester carbon, reduce the content of phosphorous and nitrogen from liquid effluents of anaerobic digesters and enhance soil fertility.

Animal Health Component

Research Effort Categories

Basic

25%

Applied

50%

Developmental

25%

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
511	0699	2020	100%

Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
0699 - Trees, forests, and forest products, general;

Field Of Science
2020 - Engineering;

Keywords

Goals / Objectives
a) Conduct fundamental studies on the kinetics of biomass thermo-chemical reactions to better understand the relationship between the structure of biomass constituents (cellulose, hemicelluloses and lignin) and their degradation mechanisms. b) Develop and test new types of pyrolysis reactors with mathematical modeling of proposed concepts. c) Develop new analytical methods to characterize the chemical composition of bio-oils. d) Develop and test engineered bio-chars for environmental services. e) Test new bio-oil based refinery concepts at laboratory scale. f) Develop of new transportation fuels and chemicals from bio-oil fractions.

Project Methods
(1)Fundamental studies of biomass thermo-chemical reactions: This study will be carried out using TG, DSC, a spoon reactor, a wire mesh reactor, a hot stage and Py-GC/MS techniques. This project will target strategies to maximize levoglucosan production. (2) Development and testing of new types of pyrolysis reactors, with mathematical modeling of proposed concepts: We currently have a 1 kg/h Auger pyrolysis reactor operational and plan to build a 500 g/h bubbling fluidized bed pyrolysis reactor. This project proposes the development and validation of mathematical models to describe the yield and composition of bio-oils produced. (3) Development of new methods to characterize the chemical and physical structure of bio-oils: New hybrid analytical approaches based on GC/MS, GC-FID, UV-Fluorescence, HPLC, LC-MS, TG-FTIR, Py-GC/MS, GPC, NMR, Karl Fischer titration, solvent extraction and precipitation techniques will be proposed to quantify the chemical composition of the different chemical families present in bio-oils. (4) Development of Engineered Bio-chars for Environmental Services: We will evaluate new approaches to produce high surface area biochars doped with Ca(OH)2, and Ferric sulphate/oxide to enhance phosphate retentions in liquid effluents. We will also study the potential of low temperature oxidation to generate acidic functional groups on bio-char surfaces. Changes in proximate and bulk elemental composition, surface area, surface pH, surface acidic groups, cation exchange capacity, and the capacity to absorb ammonium will be determined for each sample. The capacity of the developed bio-chars to remove nitrogen and phosphorous species from the aqueous effluents of anaerobic digesters will be evaluated. (5)Testing of new bio-oil refinery concepts: New bio-refinery concepts will be tested at laboratory scale to transform crude bio-oils into new transportation fuels. The proposed concepts will target the production of ethanol, lipids and butanol from the fermentation of pyrolytic sugars, biogas from the anaerobic digestion of C1-C4 pyrolytic molecules and drop-in fuels from the hydrotreatment of whole bio-oils and the lignin-derived fractions. Genetically modified microorganisms able to directly use levoglucosan as carbon source for ethanol, lipid and butanol production will be developed. A new hydrotreatment unit will be built to produce drop in fuels from biomass pyrolysis intermediates. Co-Mo catalysts for bio-oil hydrotreatment will be synthesized and their properties will be systematically varied by manipulating the synthesis parameters such as the ratio of Mo and Co precursors, the pore structures of the Al2O3 support and calcination temperature and time. The performance of these catalysts during bio-oil hydrotreatment will be evaluated. (6) Development of new transportation fuels from bio-oils, and construction of a new bio-fuel lab at WSU: The fuel properties of fractions derived from bio-oils will be tested at a new fuel laboratory to be built at WSU. The refined bio-oil fractions will be used as fuel additives for Otto and Diesel engines.

Progress 01/01/13 to 12/31/17

Outputs
Target Audience:Our targeted audiences have been our peers at the biomass thermochemical conversion, environmental engineering and biochar scientific communities. We have also presented our work to farmers, energy and engineering companies. Between 2016 and December 2018 we graduated five PhD students in this area (Filip Stankovikj, Micheal Brennan Pecha, Matthew Smith, Jorge Ivan Montoya, Geraldo Ferreira David). In 2017 we made five presentations at national and international conferences and more than 20 papers were published in peer reviewed journals. Our work has been thoroughly communicated to peers, policy makers, engineering companies, students, and the public in general. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?PARTICIPANTS: Eleven PhD students (Mathew Smith, Micheal Brennan Pecha, Filip Stankovikj, Tanzil Abid Hossain, Yinglei Han, Michael Ayania, Evan Terrel,.Lina Martinez, Sohrab Haghighi, Anamaria Paiva and Iva Tews), two MSc student (Alexander Dunsmoor, Mainali Kalidas), three Post-doctoral fellow (Martin Gamarra, Waled Suliman, and Ian Dalmeyer) and five undergraduate students. How have the results been disseminated to communities of interest?The results obtained were presented to policy makers, the industry, graduate and undergraduate students. The results have been disseminated through peer reviewed papers, presentation and posters in national and international conferences. We also wrote several technical reviews to support the development of the biomass pyrolysis industry. What do you plan to do during the next reporting period to accomplish the goals?This is the last quarter of our project .This is our final report. The goals stated in the original proposal were achieved.

Impacts
What was accomplished under these goals? Last year we published two literature reviews. The first one was a review on the historical developments of pyrolysis reactors. The second review in collaboration with VTT (Finland) was on the multiphase behavior and phase stability of pyrolysis oils. During the last two years we made progresses in the following 4 areas: (1) Fundamental studies of biomass thermo-chemical reactions to better understand the relationship between the structure of biomass constituents (cellulose, hemicelluloses and lignin) and their degradation mechanisms with five papers in this area authored by Michael Pecha and Jorge Montoya (2) New analytical methods to characterize the chemical composition of bio-oils with three papers authored in this area by Stankovikj (3) Engineered bio-chars for environmental services with five papers authored in this area by Smith and Suliman (4) New bio-oil based refinery concepts at laboratory scale with two papers authored in this area by Stankovikj and Han. The fundamental studies of biomass thermochemical reactions were divided in studies to understand cellulose and lignin reactions. This year we focused on the secondary reactions happening in the liquid intermediate formed by oligomeric primary products of cellulose and lignin decomposition and the microexplosion phenomenon responsible for aerosols formation during biomass pyrolysis. Pyrolysis experiments using cellulose were performed under near-vacuum conditions (3.5 mbar) and at near-atmospheric pressure (950 mbar) to gain insight into the effect of pressure on pyrolysis. A computer simulation of these experiments including heat, mass and momentum transfer was developed. Known molecule products were identified and quantified by gas chromatography (GC), GC/MS and high performance liquid chromatography, and yields were calculated. Vacuum allowed the evaporation of cellobiosan and promote the release of heavy oligosaccharides by thermal ejection (cellotriosan, ...) reducing in this way the residence time of the oligomeric products in the liquid intermediate and consequently their secondary reactions. The unknown heavy fractions in the oil were studied in more details by high-resolution mass spectrometry using positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The results illustrated a dominant dehydration reaction pathway in the liquid intermediate to form distinct parent molecules from which fragmentation reactions occur. Furthermore, as the pressure increased, cross-linking and polyaromatic ring formation in the liquid intermediate was enhanced. A new cellulose pyrolysis reaction scheme stressing the secondary reactions in the liquid intermediate was proposed. We also made important progressed understanding the formation of liquid intermediates and their thermal ejection. A new methodology has been proposed to describe of the dynamics of bubble formation during pyrolysis of Organosolv lignin and sucrose (surrogates for biomass) using fast speed visualization (125fps) with mathematical modeling. Last year we made important progresses in the development of new deconvolution methods for the characterization of biochar XPS, Raman and 13C-NMR. These new analytical strategies were used to study biochar formation reactions. The role of biochar porosity and surface functionality in augmenting the hydrologic properties of a sandy soil were also studied. The biochars studied were produced from pine wood (PW), hybrid poplar wood (HP), and pine bark (PB) at temperatures of 350C and 600 °C. The resulting materials were then oxidized under air at 250 °C to generate oxygenated functional groups on the surface. All biochar were thoroughly characterized (surface and bulk properties) and their hydrological properties measured in blends with Quincy sand. We prepared 39 microcosms for this study to examine the effect of biochar functionalities and porosity on the hydro-physical properties of Quincy sand. The field capacity, wilting point, and total available soil moisture of the bio-char/Quincy sand mixtures were measured for both dry and wet ranges. Our results indicated that the amount of oxygenated functional groups on the surface of biochars clearly differentiated the biochars in terms of hydrophilicity, with the oxidized biochars being superior, followed by the low-temperature biochars, while the high temperature biochars possessed lowest hydrophilicity. As a result, oxidized biochars exhibited better wettability compared to unoxidized biochars, regardless their feedstock source. Significant correlation occurred between the total acidic functional groups on biochar surface and water contents at different matric potentials. Over a wide range of soil water potentials, oxidized biochar-soil mixtures held more water than the unoxidized biochar-soil mixtures. Our group also conducted quantitative studied of the effect of biochar oxidation and pyrolysis temperature on the transport of pathogens and nonpathogenic E.coli in biochar Amendment sand columns. We studied the transport of Escherichia coli pathogenic O157:H7 and nonpathogenic K12 strains in water-saturated Our results showed that the addition of oxidized bio-char into QS columns enhanced the transport of E. Coli O157:H7 by 3.1 fold compared with the unoxidized contraparts, likely because of increase in the repulsive forces due to their higher negative charge densities. Last year we also made very important contributions to the understanding of bio-oil chemical make-up. More specifically with the identification of two oligomeric fractions not reported before (the pyrolytic humins and the hybrid oligomers). The carbonyl groups are almost equally distributed between the volatile and the oligomeric fractions. Between 85 and 95 % of the phenols in bio-oil are in the form of oligomers. Between 52 and 66 % of the carboxylic acids are GC/MS detectable and the rest is in the oligomeric fraction. These results confirm that the GC/MS detectable fraction, although it only represents around 30 wt. % of the whole oil - contains more than half of the very reactive carbonyl and carboxyl functional groups. As an average 56 % of all the oxygen derived from the carbohydrate fraction that is collected in the oil is in the form of water. Around 20 % is in the form of carbonyl groups, close to 12 % is in the form of carboxylic groups, and only 17 % is in the form of OH in aliphatic chains. This result clearly show the importance of dehydration reactions (close to 70 % of the oxygen in the oil is in the form of carbonyl or water). The oils were studied by FT-ICR-MS. The heavy fraction is composed of oligomeric materials. The data was plotted in the Van Krevelen plot showing for the first time the formation of heavy unknown water soluble oligomers produced by the gradual dehydration of cellulose primary depolymerization products. This fraction was called by our group as "pyrolytic humin". The behavior of these oils and the evolution of their functional groups during stabilization was also studied last year. Our studies were conducted with pyrolysis oils from BTG and Amaron in a batch reactor over Ru/C catalyst for reaction time of 4 h. The contents of carbonyl, hydroxyl and carboxyl groups in the volatiles GC/MS detectable fraction decreased (80, 65 and 70 % respectively), while the behavior in the total oil and hence in the nonvolatile fraction was more complex. The carbonyl groups initially decreased having a minimum at 125 - 150 oC and then increased while the hydroxyl groups had a reverse trend. The deconvolution of the IR bands around 1050 and 1260 cm-1 corresponded very well with the changes in the 31 P-NMR silent O groups (likely ethers). Most of the H2O formation can be explained from the significant reduction of these silent O groups (from 12 % in the fresh oils, to 6 to 2 % in the stabilized oils) most probably belonging to the ethers.

Publications

Progress 10/01/16 to 09/30/17

Outputs
Target Audience:Our targeted audiences have been our peers at the biomass thermochemical conversion, environmental engineering and biochar scientific communities. We have also presented our work to farmers, energy and engineering companies. Between 2016 and 2017 we graduated five PhD students in this area (Filip Stankovikj, Micheal Brennan Pecha, Matthew Smith, Jorge Ivan Montoya, Geraldo Ferreira David). Our work was presented at sixnational and international conferences. More than 20 papers were published last year. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Eleven PhD students (Mathew Smith, Micheal Brennan Pecha, Filip Stankovikj, Tanzil Abid Hossain, Yinglei Han, Michael Ayania, Evan Terrel,.Lina Martinez, Sohrab Haghighi, Anamaria Paiva and Iva Tews), two MSc student (Alexander Dunsmoor, Mainali Kalidas), three Post-doctoral fellow (Martin Gamarra, Waled Suliman, and Ian Dalmeyer) and five undergraduate students. How have the results been disseminated to communities of interest?The results obtained were presented to policy makers, the industry, graduate and undergraduate students. The results have been disseminated through peer reviewed papers, presentation and posters in national and international conferences. We also wrote several technical reviews to support the development of the biomass pyrolysis industry. What do you plan to do during the next reporting period to accomplish the goals?This is the last year of our project. During the timeremaining we will write and submit several manuscripts to peer reviewed journals.

Impacts
What was accomplished under these goals? Last year we published two literature reviews. The first one was a review on the historical developments of pyrolysis reactors. The second review in collaboration with VTT (Finland) was on the multiphase behavior and phase stability of pyrolysis oils. During 2016 we made progresses in the following 4 areas: (1) Fundamental studies of biomass thermo-chemical reactions to better understand the relationship between the structure of biomass constituents (cellulose, hemicelluloses and lignin) and their degradation mechanisms with five papers in this area authored by Michael Pecha and Jorge Montoya (2) New analytical methods to characterize the chemical composition of bio-oils with three papers authored in this area by Stankovikj (3) Engineered bio-chars for environmental services with five papers authored in this area by Smith and Suliman (4) New bio-oil based refinery concepts at laboratory scale with two papers authored in this area by Stankovikj and Han. The fundamental studies of biomass thermochemical reactions were divided in studies to understand cellulose and lignin reactions. This year we focused on the secondary reactions happening in the liquid intermediate formed by oligomeric primary products of cellulose and lignin decomposition and the microexplosion phenomenon responsible for aerosols formation during biomass pyrolysis. Pyrolysis experiments using cellulose were performed under near-vacuum conditions (3.5 mbar) and at near-atmospheric pressure (950 mbar) to gain insight into the effect of pressure on pyrolysis. A computer simulation of these experiments including heat, mass and momentum transfer was developed. Known molecule products were identified and quantified by gas chromatography (GC), GC/MS and high performance liquid chromatography, and yields were calculated. Vacuum allowed the evaporation of cellobiosan and promote the release of heavy oligosaccharides by thermal ejection (cellotriosan, ...) reducing in this way the residence time of the oligomeric products in the liquid intermediate and consequently their secondary reactions. The unknown heavy fractions in the oil were studied in more details by high-resolution mass spectrometry using positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The results illustrated a dominant dehydration reaction pathway in the liquid intermediate to form distinct parent molecules from which fragmentation reactions occur. Furthermore, as the pressure increased, cross-linking and polyaromatic ring formation in the liquid intermediate was enhanced. A new cellulose pyrolysis reaction scheme stressing the secondary reactions in the liquid intermediate was proposed. We also made important progressed understanding the formation of liquid intermediates and their thermal ejection. A new methodology has been proposed to describe of the dynamics of bubble formation during pyrolysis of Organosolv lignin and sucrose (surrogates for biomass) using fast speed visualization (125fps) with mathematical modeling. Last year we made important progresses in the development of new deconvolution methods for the characterization of biochar XPS, Raman and 13C-NMR. These new analytical strategies were used to study biochar formation reactions. The role of biochar porosity and surface functionality in augmenting the hydrologic properties of a sandy soil were also studied. The biochars studied were produced from pine wood (PW), hybrid poplar wood (HP), and pine bark (PB) at temperatures of 350C and 600 °C. The resulting materials were then oxidized under air at 250 °C to generate oxygenated functional groups on the surface. All biochar were thoroughly characterized (surface and bulk properties) and their hydrological properties measured in blends with Quincy sand. We prepared 39 microcosms for this study to examine the effect of biochar functionalities and porosity on the hydro-physical properties of Quincy sand. The field capacity, wilting point, and total available soil moisture of the bio-char/Quincy sand mixtures were measured for both dry and wet ranges. Our results indicated that the amount of oxygenated functional groups on the surface of biochars clearly differentiated the biochars in terms of hydrophilicity, with the oxidized biochars being superior, followed by the low-temperature biochars, while the high temperature biochars possessed lowest hydrophilicity. As a result, oxidized biochars exhibited better wettability compared to unoxidized biochars, regardless their feedstock source. Significant correlation occurred between the total acidic functional groups on biochar surface and water contents at different matric potentials. Over a wide range of soil water potentials, oxidized biochar-soil mixtures held more water than the unoxidized biochar-soil mixtures. Our group also conducted quantitative studied of the effect of biochar oxidation and pyrolysis temperature on the transport of pathogens and nonpathogenic E.coli in biochar Amendment sand columns. We studied the transport of Escherichia coli pathogenic O157:H7 and nonpathogenic K12 strains in water-saturated Our results showed that the addition of oxidized bio-char into QS columns enhanced the transport of E. Coli O157:H7 by 3.1 fold compared with the unoxidized contraparts, likely because of increase in the repulsive forces due to their higher negative charge densities. Last year we also made very important contributions to the understanding of bio-oil chemical make-up. More specifically with the identification of two oligomeric fractions not reported before (the pyrolytic humins and the hybrid oligomers). The carbonyl groups are almost equally distributed between the volatile and the oligomeric fractions. Between 85 and 95 % of the phenols in bio-oil are in the form of oligomers. Between 52 and 66 % of the carboxylic acids are GC/MS detectable and the rest is in the oligomeric fraction. These results confirm that the GC/MS detectable fraction, although it only represents around 30 wt. % of the whole oil - contains more than half of the very reactive carbonyl and carboxyl functional groups. As an average 56 % of all the oxygen derived from the carbohydrate fraction that is collected in the oil is in the form of water. Around 20 % is in the form of carbonyl groups, close to 12 % is in the form of carboxylic groups, and only 17 % is in the form of OH in aliphatic chains. This result clearly show the importance of dehydration reactions (close to 70 % of the oxygen in the oil is in the form of carbonyl or water). The oils were studied by FT-ICR-MS. The heavy fraction is composed of oligomeric materials. The data was plotted in the Van Krevelen plot showing for the first time the formation of heavy unknown water soluble oligomers produced by the gradual dehydration of cellulose primary depolymerization products. This fraction was called by our group as "pyrolytic humin". The behavior of these oils and the evolution of their functional groups during stabilization was also studied last year. Our studies were conducted with pyrolysis oils from BTG and Amaron in a batch reactor over Ru/C catalyst for reaction time of 4 h. The contents of carbonyl, hydroxyl and carboxyl groups in the volatiles GC/MS detectable fraction decreased (80, 65 and 70 % respectively), while the behavior in the total oil and hence in the nonvolatile fraction was more complex. The carbonyl groups initially decreased having a minimum at 125 - 150 oC and then increased while the hydroxyl groups had a reverse trend. The deconvolution of the IR bands around 1050 and 1260 cm-1 corresponded very well with the changes in the 31 P-NMR silent O groups (likely ethers). Most of the H2O formation can be explained from the significant reduction of these silent O groups (from 12 % in the fresh oils, to 6 to 2 % in the stabilized oils) most probably belonging to the ethers.

Publications

Type: Journal Articles Status: Published Year Published: 2017 Citation: Pecha B, Terrell E, Montoya JI, Stankovikj F, Chejne F, Garcia-Perez M: Effect of Pressure on Pyrolysis of Milled Wood Lignin and Acid Washed Hybrid Poplar Wood. Industrial and Engineering Chemistry Research, 2017, 56 (32), 9079-9089
Type: Journal Articles Status: Published Year Published: 2017 Citation: Stankovikj F, Tran C-C, Kaliaguine S, Olarte M, Garcia-Perez M: Evolution of Functional Groups During Pyrolysis Oil Upgrading. Energy & Fuels, 2017, 32 (8), 8300-8316
Type: Journal Articles Status: Published Year Published: 2017 Citation: Smith M, Pecha M, Helms G, Scudiero L, Garcia-Perez M: Chemical and Morphological Evaluation of Chars produced from Primary biomass constituents: Cellulose, Xylan and Lignin. Biomass and Bioenergy, 2017, 104, 17-35
Type: Journal Articles Status: Published Year Published: 2017 Citation: Garcia-Nunez JA, Pelaez-Samaniego MR, Garcia-Perez ME, Fonts I, Abrego J, Westerhof RJM, Garcia-Perez M: Historical Developments of Pyrolysis Reactors: A Review. Energy & Fuels, 2017, 31 (6), 5751-5775
Type: Journal Articles Status: Published Year Published: 2017 Citation: Pecha B, Montoya JI, Ivory C, Chejne F, Garcia-Perez M: Modified Pyroprobe Captive Sample Reactor: Characterization of Reactor and Cellulose Pyrolysis at Vacuum and Atmospheric Pressures. Industrial and Engineering Chemistry Research, 2017, 56 (18), 5185-5200.
Type: Journal Articles Status: Published Year Published: 2017 Citation: Suliman W, Harsh J, Fortuna A, Garcia-Perez M, Abu-Lail N: Quantitative Effects of Biochar Oxidation and Pyrolysis Temperature on the Transport of Pathogens and Nonpathogenic E. coli in Biochar-Amended Sand Columns Environmental Science and Technology Journal, 2017, 51 (9), 5071-5081
Type: Journal Articles Status: Published Year Published: 2017 Citation: Pecha B, Montoya JI, Chejne F, Garcia-Perez M: Effect of Vacuum on the Fast Pyrolysis of Cellulose: Nature of secondary reactions in Liquid Intermediate. Industrial and Engineering Chemistry Research, 2017, 56 (15), 4288-4301
Type: Journal Articles Status: Published Year Published: 2017 Citation: Montoya J, Pecha B, Chejne-Janna F, Garcia-Perez M: Single Particle Single particle model for biomass pyrolysis with bubble formation dynamics inside the liquid intermediate and its contribution to aerosol formation by thermal ejection. Journal of Analytical and Applied Pyrolysis, 2017, 124, 204-218
Type: Journal Articles Status: Published Year Published: 2017 Citation: Han Y, Stankovikj F, Garcia-Perez M: Co-hydrotreatment of Tire Pyrolysis Oil and Vegetable Oil for the production of Transportation Fuels. Fuel Processing Technology, 2017, 159, 328-339
Type: Journal Articles Status: Published Year Published: 2017 Citation: Smith M, Helms G, McEwen J-S, Garcia-Perez M: Effect of Pyrolysis Temperature on Aromatic Cluster Size of cellulose char by quantitative Multi Cross-Polarization 13C NMR with Long Range Dipolar Dephasing. Carbon, 2017, 116, 210-222
Type: Journal Articles Status: Published Year Published: 2017 Citation: Stankovikj F, Garcia-Perez M: TG-FTIR Method for the Characterization of Bio-oils in Chemical Families. Energy and Fuels, 2017, 31, 1689-1701
Type: Journal Articles Status: Published Year Published: 2017 Citation: Stankovikj F, McDonald A, Helms GL, Olarte MV, Garcia-Perez M: Characterization of the Water Soluble Fraction of Woody Biomass Pyrolysis Oils. Energy Fuels, 31, 2017, 1650-1664
Type: Journal Articles Status: Published Year Published: 2017 Citation: Suliman W, Harsh JB, Abu-Lail NI, Fortuna AM, Garcia-Perez M: The role of Biochar Porosity and surface functionality in augmenting hydrologic properties of a sandy soil. Science of the Total Environment, 574, 2017, 139-147
Type: Journal Articles Status: Published Year Published: 2017 Citation: Montoya J, Pecha B, Roman D, Chejne-Janna F, Garcia-Perez M: Effect of temperature and Heating Rate Effects on product Distribution from the Fast Pyrolysis of Sugarcane Bagasse in a Hot Plate Reactor Journal of Analytical and Applied Pyrolysis, 2017, 123, pp. 347-363
Type: Journal Articles Status: Published Year Published: 2016 Citation: Smith M, Scudiero L, Espinal J, McEwen J-S, Garcia-Perez M: Improving the Deconvolution and Interpretation of XPS Spectra from Chars by ab Initio Calculations Carbon, 2016, 110, 155-171
Type: Journal Articles Status: Published Year Published: 2016 Citation: Montoya J, Pecha B, Chejne-Janna F, Garcia-Perez M: Micro-explosion of liquid intermediates during the fast pyrolysis of sucrose and organosolv lignin. Journal of Analytical and Applied Pyrolysis, 2016, 122, 106-121
Type: Journal Articles Status: Published Year Published: 2016 Citation: Stankovikj F, McDonald A, Helms GL, Garcia-Perez M: Quantification of Bio-oil Functional Groups and Evidence of the Presence of Pyrolytic Humins Energy & Fuels, 2016, 30, 6505-6524
Type: Journal Articles Status: Published Year Published: 2016 Citation: Oasmaa A, Fonts I, Linfors C, Pelaez Samaniego MR, Garcia-Perez ME, Garcia-Perez M: Pyrolysis oil Multiphase Behavior and Phase Stability: A Review Energy Fuels, 2016, 30, 6179-6200

Progress 10/01/15 to 09/30/16

Outputs
Target Audience:The results obtained were presented to policy makers, the industry, graduate and undergraduate students as well as to other members of the scientific community. Changes/Problems:Nothing significant to report during this reporting period. What opportunities for training and professional development has the project provided?PARTICIPANTS: Nineteen graduate students: (1) Mathew Smith, (2) Jesus A. Garcia, (3) Zhouhong Wang, (4) Shuai Zhou, (5) Shi-Shen Liaw, (6) Brennan Pecha, (7) Amir Sahaf, (8) Waled Suliman, (9) Jieni Lian, (10) Filip Stankovikj, (11) Daniel Howe, (12) Iva Tews, (13) Evan Terrell, (14) Yinglei Han, (15) Lina Martinez, (16) Michael Ayania, (17) Alex Dunsmor, (18) Sohrab Haghighi, (19) Mainali Kalidas and five undergraduate students. How have the results been disseminated to communities of interest?The results obtained were presented to policy makers, the industry, graduate and undergraduate students through peer reviewed papers, presentations, and posters in national and international conferences. We also wrote several technical reviews to support the development of the biomass pyrolysis industry. What do you plan to do during the next reporting period to accomplish the goals?During the next reporting period we will continue working in each of the tasks listed in the proposal approved. More specifically, we will continue working to better understand cellulose and lignin primary and secondary reactions and the thermal ejection mechanism. Our goal is to increase the yield of anhydrosugars. Our group will also continue advancing our understanding of bio-oil chemistry and studying strategies to separate bio-oils in fractions that can then be used for the development of bio-products. Early in 2017 we will defend two PhD dissertations in this area. Our group will continue working on the development or new strategies for biochar characterization and new adsorbents for environmental services.

Impacts
What was accomplished under these goals? The overall goal of this project is to advance the science and technology required to implement a novel biomass economy, formed by distributed selective pyrolysis units, rural refineries, and centralized refineries for the production of bio-fuels and bio-chemicals from waste lignocellulosic materials. During 2016 we made progress in the following 7 areas: (1) Fundamental studies of biomass thermo-chemical reactions to better understand the relationship between the structure of biomass constituents (cellulose, hemicelluloses and lignin) and their degradation mechanisms; (2) Testing of new types of analytical pyrolysis reactors with mathematical modeling of their concepts; (3) New analytical methods to characterize the chemical composition of bio-oils; (4) Engineering bio-chars for environmental services; (6) Developing new bio-oil based refinery concepts at the laboratory scale; (7) Strategizing new transportation fuels and chemicals from bio-oil fractions. The fundamental studies of biomass thermochemical reactions focused on understanding cellulose and lignin reactions. Studies on cellulose primary reactions under vacuum were conducted at Twente University. These studies revealed that the primary products of cellulose pyrolysis are mainly levoglucosan, cellobiosan and cellotriosan. Levoglucosan is very volatile so under fast heating rates conditions it does not contributes much to the formation of secondary products. Cellobiosan on the other hand has boiling point close to 580 oC so it can only be evaporated under deep vacuum. If not removed from the liquid intermediate, it will be subjected to dehydration and fragmentation secondary reactions leading to the formation of water, volatile molecules, highly modified oligomeric products and char. In 2016 we continue modifying our Py-GC/MS to conduct fundamental studies of biomass pyrolysis reactions under vacuum. Perhaps our major contribution in 2016 year was our study of the nature of the secondary reactions in the liquid intermediate through the analysis of the oil collected by ICR-MS with Van Krevelen plots. These plots clearly allowed us to visualize the existence of important depolymerization and fragmentation reactions happening in the liquid intermediate. Our visualization studies with fast speed cameras confirm that the oligomeric products are removed from the liquid intermediate in the form of aerosols by thermal ejection. This year we published a paper with the statistical analysis of bubbling birth and death phenomena that is helping to explain the mechanisms of aerosol formation. We have submitted other two papers to the Journal of Analytical and Applied Pyrolysis with these results. These studies support the findings published in the last years suggesting that cellulose and lignin oligomeric products are produced by the primary reactions and that they are thermally ejected by the bubbles formed by volatile products. In 2016 we focused on the development of strategies to describe bio-oil chemical composition in terms of functional groups and chemical families. Both strategies proved to be extremely useful to formalize bio-oil chemical composition in terms relevant to engineers. For the first time, we identified the presence of highly modified dehydrated sugars soluble in water and heavy lignin oligomers soluble in water. Our group also made important contributions to understand how bio-char composition and morphological properties are affected by the composition of the feedstock and the production conditions. Eighteen biochar samples were produced from the pyrolysis of Douglas fir wood (DFW), Douglas fir bark (DFB), and hybrid poplar wood (HP) at different temperatures in a lab scale spoon reactor. Changes in the bulk composition of the biochar produced were examined by elemental and proximate analyses. Surface properties of all the biochars produced (SEM morphology, CO2 and N2 adsorption, XPS analysis, Boehm titration, cation exchange capacity (CEC) and ζ-potential) were also studied. The XPS and Boehm titration confirmed that most oxygenated surface functional groups (presence of carbonyl, carboxyl and hydroxyl groups) are gradually removed as pyrolysis temperature increases. The changes in surface charge were studied by ζ-potential measurements and were found to vary directly with the content of oxygenated functional groups. Properties that depend on both surface area and the surface oxygenated functional groups, such as the cation exchange capacity, showed a more complex behavior. The composition of the ash and associated properties such as pH and electric conductivity (EC) were also measured. Last year we also studied the potential relationships between porosity and surface functionality of biochar and soil water retention characteristics. The hydrological properties of these materials were measured in blends with Quincy sand. The complex heterogeneous nature of chars has confounded the complete analysis of the Raman spectra of these materials. The additional shoulders observed on the defect (D)-band and high intensity valley between the D and graphitic (G)-bands represent the primary regions of uncertainty. In 2016 we studied the effects of various vacancy and substitution defects in a coronene parent molecule using density functional theory (DFT). The impacts of these defects are best understood in terms of a reduced symmetry as compared to a "parent" coronene molecule. Based on simulation results, a total of ten potential bands were assigned between 1000 cm−1and 1800 cm−1. These bands have been used to deconvolute a thermoseries of cellulose chars produced by pyrolysis at 300-700 oC. The shoulder observed in chars near 1200 cm−1 was assigned to the symmetric breathing mode of various small polyaromatic hydrocarbons (PAH) as well as rings containing seven or more carbons. Intensity between 1400 cm−1 and 1550 cm−1 results from a range of coupled vibrational modes from various defect structures. The deconvolution of cellulose derived chars shows consistent growth of PAH clusters, loss of oxygen, and development of non-hexoganal ring systems as pyrolysis temperature increased. Likewise, the interpretation of C1s XPS spectra from disordered oxygenated carbons remains uncertain despite a variety of schemes reported in the literature. A thermoseries of cellulose chars was studied to evaluate six published deconvolution schemes; however, none were capable of correctly identifying the oxygen content determined by the O1s spectrum. To improve the self-consistency of the XPS interpretation a method was proposed based on a 7 peak C1s deconvolution. To improve assignments, various functional groups and carbon structures were examined via DFT using an initial state approximation. DFT calculations of model compounds were compared with experimental results to confirm the validity of the calculation method used. The DFT calculations identified several defect structures that justify the use of 3 peaks for deconvolution of the C-C region of C1s XPS spectra. The deconvolution method proposed provides C:O ratios in good agreement (within 5%) of those obtained from total C1s and O1s peaks.

Publications

Type: Journal Articles Status: Published Year Published: 2016 Citation: Smith MW, Dallmeyer I, Johnson TJ, Brauer CS, McEwen JS, Espinal JF, Garcia-Perez M: Structural Analysis of Char by Raman Spectroscopy: Improving band Assignments through First Principle Computational Calculations, Carbon, Volume 100, 2016, pp 678-692.
Type: Journal Articles Status: Published Year Published: 2017 Citation: Suliman W, Harsh JB, Abu-Lail NI, Fortuna AM, Garcia-Perez M: Understanding the Role of Biochar Porous Structure and Surface Chemistry in Augmenting Hydrologic Properties of a Sandy Soil Journal of the Total Environment, 574, 2017, 139-147
Type: Journal Articles Status: Published Year Published: 2016 Citation: Montoya J, Pecha B, Roman D, Chejne-Janna F, Garcia-Perez M: Effect of temperature and Heating Rate Effects on product Distribution from the Fast Pyrolysis of Sugarcane Bagasse in a Hot Plate Reactor Accepted in the Journal of Analytical and Applied Pyrolysis, 2016, DOI: 10.1016/jaap.2016.11.008
Type: Journal Articles Status: Published Year Published: 2016 Citation: Smith M, Scudiero L, Espinal J, McEwen J-S, Garcia-Perez M: Improving the Deconvolution and Interpretation of XPS Spectra from Chars by ab Initio Calculations Carbon, 2016, 110, 155-171
Type: Journal Articles Status: Published Year Published: 2016 Citation: Montoya J, Pecha B, Chejne-Janna F, Garcia-Perez M: Micro-explosion of liquid intermediates during the fast pyrolysis of sucrose and organosolv lignin. Journal of Analytical and Applied Pyrolysis, 2016, 122, 106-121
Type: Journal Articles Status: Published Year Published: 2016 Citation: Stankovikj F, McDonald A, Helms GL, Garcia-Perez M: Quantification of Bio-oil Functional Groups and Evidence of the Presence of Pyrolytic Humins Energy & Fuels, 2016, 30, 6505-6524
Type: Journal Articles Status: Published Year Published: 2016 Citation: Oasmaa A, Fonts I, Linfors C, Pelaez Samaniego MR, Garcia-Perez ME, Garcia-Perez M: Pyrolysis oil Multiphase Behavior and Phase Stability: A Review Energy Fuels, 2016, 30, 6179-6200
Type: Journal Articles Status: Published Year Published: 2016 Citation: Garcia-Nunez JA, Tatiana Rodriguez D, Andres-Fontanilla C, Elizabeth Ramirez N, Silva-Lora EE, Frear CS, Stockle C, Amonette J, Garcia-Perez M: Evaluation of alternatives for the Evolution of Palm Oil Mills into Biorefineries. Biomass and Bioenergy, 2016, 95, 310-329.
Type: Journal Articles Status: Published Year Published: 2016 Citation: Garcia-Nunez JA, Ramirez-Contreras NE, Rodriguez DT, Silva-Lora E, Frear CS, Stockle C, Garcia-Perez M: Evolution of Palm Oil Mills into Bio-refineries: Literature Review on Current and Potential Uses of Residual Biomass and Effluents. Resources Conservation & Recycling, Vol. 110, 2016, 99-114
Type: Journal Articles Status: Published Year Published: 2016 Citation: Suliman W, Harsh JB, Abu-Lail NI, Fortuna A-M, Dallmeyer I, Garcia-Perez M: Modification of Biochar Surface by Air Oxidation: Role of Pyrolysis Temperature. Biomass and Bioenergy, Vol.85, February 2016, pp 1-11.
Type: Journal Articles Status: Published Year Published: 2016 Citation: Suliman WSO, Harsh J,Abu-Lail N, Fortuna A-M, Dallmeyer I, Garcia-Perez M: Influence of Feedstock Source and Pyrolysis Temperature on Biochar Bulk and Surface Properties. Biomass and Bioenergy, Volume 84, 2016, pp 37-48

Progress 10/01/14 to 09/30/15

Outputs
Target Audience:Graduate student, professionals, thermochemical engineers, general public Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Eighteenstudents and our partners participated in this project: 9 PhD students (Matthew Smith, Jesus A Garcia, Brennan Pecha, Waled Suliman, Filip Stankovikj, Daniel Howe, Iva Tews, Yinglei Han, Abid Hossain Tanzil) 3 MSc students (Anamaria Paiva, Alex W Dunsmoor, Gabriela Pereira Ferraz), 2 research associates (Ian Dellmayer, Jonathan Pulgarin Leon), 4 undergraduate students (Tyler Enslow, Kisten N Ford, Kelly Welsch, Marisol Contreras) and our partners participated in this project. How have the results been disseminated to communities of interest?Results have been disseminated through publications and presentations in international conference (six conferences this year). What do you plan to do during the next reporting period to accomplish the goals?We will continue working on all the objectives of this project, our plan is to publish at least 10 peer reviewed manuscripts next year and to obtain competitive grants to support and expand our program.

Impacts
What was accomplished under these goals? The overall goal of this project is to address the scientific and technical hurdles to build a biomass economy formed by selective pyrolysis units where lignocellulosic materials are converted into bio-oil and biochar and upgrading and refining facilities to obtain added value fuels, chemicals and adsorbents from them. During 2015 we made progress in the following 6 areas : (1) Fundamental studies of biomass thermochemical reactions to better understand the relationship between te structure of biomass constituents (cellulose, hemicellulose and lignin) and their degradation mechanisms (2) Testing new technologies for our Auger pyrolysis reactor (3) New analytical methods to characterize the chemical composition of bio-oils (4) Engineering bio-chars for environmental services (5) Testing of new bio-oil based refinery concepts at laboratory scale (6) Strategizing new transportation fuels and chemicals from bio-oil fractions. An important result this year was the modification of a commercial pyroprobe that is allowing the group to easily study thermochemical reactions. This year we continue our fundamental biomass thermochemical reactions studies focusing on the mechanisms of cellulose and lignin thermochemical reactions and their interactions with three papers published in this area. The first paper published report findings on the cellulose-lignin interactions during slow and fast pyrolysis. The second paper report results on the impact of combined acid washing and acid impregnation on the pyrolysis of Douglas fir wood. These two papers were published in the Journal of Analytical and Applied Pyrolysis. The last paper focusses on the abundance and characteristics of lignin liquid intermediates in Wood (Pinus ponderosa Dougl. Ex Laws.) formed during thermochemical reactions. This paper was published in biomass and bioenergy. A manuscript was published with VTT (Finland) shedding light on the phenomena controlling biooil phase Stability. This paper reports new biooil phase diagrams and a new stability index to predict the condictions under which separate phase will be produced. 2015 was a very product year on the production, characterization and evaluation of engineered bio-chars with six papers submitted for review (5 has been published). We published two papers in Biomass and Bioenergy and one paper in the Journal of Analytical and Applied Pyrolysis on the production and characterization of biochars form lignocellulosic materials and from bacterial biomass. These papers established direct correlations between the biomass composition and production conditions and the bulk and surface properities of these chars. Two papers were published on the oxidation of biochar surfaces with ozone and oxygen. Both manuscripts were published in Biomass and Bioenergy. The oxidation of these chars is important to increase their cation exchange capacity which is one of the parameters directly linked with soil fertility. A paper on the effect of biochar on leaching of Organic Carbon, Nitrogen and Phosphorous from Compost in Bioretention System was published in the journal of Science of the Total Environment. The group is currently working on three papers combining computational and experimental studies to improve the Raman, XPS and NMR methods used for the characterization of biochars. One of these papers was submitted to Carbon we are now working on the other three manuscripts. Our group is also working very hard on the development of new methods for the characterization of bio-oils which should be reported in two manuscripts to be submitted in 2015.

Publications

Type: Books Status: Published Year Published: 2015 Citation: Pelaez-Samaniego MR, Garcia-Perez M, Barriga A, Marti-Herrero, Moreno Izquierdo J, Mayer FD, Garcia-Nunez JA: Estado de uso de la biomasa para la producci�n de bioenerg�a, biocombustibles and bioproductos en Ecuador. In: Energ�as Renovables en el Ecuador. Situacion Actual, Tendencias y Perspectivas. Editores: Pelaez-Samaniego RM and Espinosa-Abad JL: Cuenca Ecuador, 2015
Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Smith M, dallmeyer I, Johnson T, Brauer C, Mc-Ewen J-S, Garcia-Perez M: Raman Spectroscopy of Char: Improved Band Assigments through Ab Initio Modeling. TCS Biomass 2015, Chicago.
Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Garcia-Nunez JA, Garcia-Perez ML Evolution of Palm Oil mills into bio-refineries: technical and environmental assessment of six bio-refinery options. Biorefinery I: Chemicals and Materials from Thermo-Chemical Biomass Conversion and Related Processes. September 27-October 2, 2015
Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Garcia-Perez M, The Challenges of Studying Solid and Solid-Gas Thermochemical Reaction with Carbonaceous Materials: A New Experimental and Theoretical Approaches, CONICCA 2015, August 18-20, Medellin Colombia
Type: Journal Articles Status: Published Year Published: 2015 Citation: Suliman W, Harsh JB, Abu-Lail NI, Fortuna A-M, Dallmeyer I, Garcia-Perez M: Modification of Biochar Surface by Air Oxidation: Role of Pyrolysis Temperature. Biomass and Bioenergy, Vol.85, February 2016, pp 1-11.
Type: Journal Articles Status: Published Year Published: 2015 Citation: Suliman WSO, Harsh J,Abu-Lail N, Fortuna A-M, Dallmeyer I, Garcia-Perez M: Influence of Feedstock Source and Pyrolysis Temperature on Biochar Bulk and Surface Properties. Biomass and Bioenergy, Volume 84, 2016, pp 37-48
Type: Journal Articles Status: Published Year Published: 2015 Citation: Miao C, Gao D, Dong T, Wang Y, Garcia-Perez M, Chen S: Hydrothermal catalytic deoxygenation of palmitic acid over nickel catalyst. Fuel, 2016, Volume 166, pp 302-308
Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Brennan M, Garcia-Perez M, Walter J, Coal supercritical CO2 liquefaction. CONICCA 2015, August 18-20, Medellin, Colombia
Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Garcia-Nunez JA,Garcia-Perez M, Stockle C, Amonette J, Frear C: evolution of Palm Oil Mill into Biorefineries. ASABE International Meeting, New Orleans, July 29, 2015.
Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Suliman W, Abu-Lail N,Fortuna A-M, Harsh J, Garcia-Perez M: Effect of Pyrolysis Temperature and Post-Pyrolysis Oxidation on the Physico-Chemical Properties of Biochars. ASABE International Meeting, New Orleans July 26-29, 2015
Type: Journal Articles Status: Published Year Published: 2015 Citation: Hassani-Ghezelchi M, Garcia-Perez M, Wu H: Bioslurry as a Fuel. 7: Spray Characteristics of Bio-oil and Bioslurry via Twin-Fluid Atomiers. Energy and Fuels, 2015, 29 (12), pp 8058-8065
Type: Journal Articles Status: Published Year Published: 2015 Citation: Howe D, Taasevigen D, Gerber M, Gray M, Fernandez C, Saraf L, Garcia-Perez M, Wolcott M: Bed Agglomeration During the Steam Gasification of a High Lignin Corn Stover Simultaneous Saccharification and Fermentation (SSF) Digester Residue. Energy and Fuels, 2015, 29 (12), pp 8035-8046
Type: Journal Articles Status: Published Year Published: 2015 Citation: Montoya JI, Chejne-Janna F, Garcia-Perez M: Fast Pyrolysis: A review of relevant aspects: Part I: Parametric study. Dyna, 2015, 82, 192 pp 239-248
Type: Journal Articles Status: Published Year Published: 2015 Citation: Dong T, Gao D, Miao C, Yu X, Degan Ch, Garcia-Perez M, Rasco B, Sablani SS, Chen S: Two-step microalgal biodiesel production using acid catalysts generated from pyrolysis derived bio-char. Energy Conversion and Management. 2015, vol. 105, pp 1389-1396.
Type: Journal Articles Status: Published Year Published: 2015 Citation: Wei L,Liang S, Guho NM, Hanson AJ, Smith M, Garcia-Perez M, McDonald A: Production and characterization of bio-oil and bio-char from the pyrolysis of residual bacterial biomass from a polyhydroxyalkanoate production process. Journal of Analytical and Applied Pyrolysis, 2015, September, pp. 268-278
Type: Journal Articles Status: Published Year Published: 2015 Citation: Smith M, Ha S, Amonette JE, Garcia-Perez M: Enhancing Cation Exchange Capacity of Carbonaceous Materials through ozonation. Biomass and Bioenergy, 81, 2015, 304-314
Type: Journal Articles Status: Published Year Published: 2015 Citation: Bhattarai S, Bottenus D, Ivory CF, Gao A H, Bule M, Garcia-Perez M, Chen S: Simulation of the Ozone Pretreatment of Wheat Straw. Bio-resource Technology, 2015, Vol. 196, pp. 78-87
Type: Journal Articles Status: Published Year Published: 2015 Citation: Pelaez-Samaniego MR, Yadama V, Garcia-Perez M, Lowell E: Abundance and Characteristics of Lignin Liquid Internediates in Wood (Pinus ponderosa Dougl. Ex Laws.) during Hot Water Extraction. Biomass and Bioenergy, Vol. 81, 2015, pp. 117-128
Type: Journal Articles Status: Published Year Published: 2015 Citation: Oasmaa A, Sundqvist T, Kuoppala E, Garcia-Perez M, Solantausta Y, Lindfors C: Controlling Phase Stability of Biomass Fast Pyrolysis Bio-oils. (Accepted in Energy and Fuels, 2015, 29 (7), pp 43734381
Type: Journal Articles Status: Published Year Published: 2015 Citation: Hilberts T, Wang Z, Pecha MB, Kersten SRA, Pelaez-Samaniego RM, Garcia-Perez M: Cellulose-Lignin Interactions during slow and fast pyrolysis. Journal of Analytical and Applied Pyrolysis, Vol. 114, 2015, pp. 197-207
Type: Journal Articles Status: Published Year Published: 2015 Citation: Pecha B, Arauzo P, Garcia-Perez M: Impact of combined acid washing and acid impregnation on the pyrolysis of Douglas fir wood. Journal of Analytic and Applied Pyrolysis, Volume 114, 2015, 127-137
Type: Journal Articles Status: Published Year Published: 2015 Citation: Pelaez-Samaniego MR, Yadama V, Garcia-Perez M, Lowell E, Zhu R, Englund K: Interrelationship between lignin-rich dichloromethane extracts of hot water treated wood fibers and high density polyethylene (HDPE) in wood plastic composite (WPC) production. Holzforschung, DOI: 10.1515/hf-2014-0309, 2015.
Type: Journal Articles Status: Published Year Published: 2015 Citation: Cuba-Torres C, Marin-Flores O, Owen C, Wang Z, Garcia-Perez M, Norton G, Ha S: Catalytic partial oxidation of biodiesel surrogate over molybdenum dioxide. Fuel, 146, 2015, 132-137
Type: Theses/Dissertations Status: Published Year Published: 2015 Citation: Suliman W: Toward an understanding of the role of biochar as an agro-envirometal tool: Potential for Control water release, bacterial retention and greenhouse gases. PhD thesis. Department of Crop and Soil Sciences, 2015
Type: Theses/Dissertations Status: Published Year Published: 2015 Citation: Garcia-Nunez Jesus A: Evolution of Palm Oil Mills into Biorefineries. PhD thesis. Biological Systems Engineering, 2015
Type: Theses/Dissertations Status: Published Year Published: 2015 Citation: Daniel Howe: Thermal Pretreatment of a High Lignin and High Ash Fermentation Residue for Gasification. PhD thesis, Chemical Engineering, 2015
Type: Journal Articles Status: Published Year Published: 2015 Citation: Iqbal H, Garcia-Perez M, Flury M: Effect of Biochar on Leaching of Organic Carbon, Nitrogen, and Phosphorous from Compost in Bioretention System. Sci. Total Environ, Volumes 521-522, 2015, pages 37-45

Progress 10/01/13 to 09/30/14

Outputs
Target Audience: Graduate student, professionals, thermochemical engineers, general public. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? 8 PhD students (Mathew Smith, Jesus A. Garcia, Shi-Shen Liaw, Brennan Pecha, Waled Suliman, Filip Stankovikj, Daniel Howe, and Iva Tews), one MSc student (Sergio Baravalle), one visiting scholar (Electo Silva), one research associate (Ian Dellmeyer) five undergraduate students, and our partners participated in this project. How have the results been disseminated to communities of interest? Through publications and presentations in international conferences (Five conferences this year). What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? The overall goal of this project is to advance the science and technology required to implement a novel biomass economy, formed by distributed selective pyrolysis units, rural refineries, and centralized refineries for the production of bio-fuels and bio-chemicals from waste lingo-cellulosic materials. During 2014 we made progress in the following 7 areas: (1) Fundamental studies of biomass thermo-chemical reactions to better understand the relationship between the structure of biomass constituents (cellulose, hemicelluloses and lignin) and their degradation mechanisms; (2) Testing of new technologies for our Auger pyrolysis reactor; (3) New analytical methods to characterize the chemical composition of bio-oils; (4) Engineering bio-chars for environmental services; (6) Developing new bio-oil based refinery concepts at the laboratory scale; (7) Strategizing new transportation fuels and chemicals from bio-oil fractions. The fundamental studies of biomass thermochemical reactions continue focusing on studies to understand cellulose and lignin reactions, and their interactions. In total 10 peer reviewed papers were published. Two of these papers focused on the effect of crystallinity, temperature and sulfuric acid on the formation of primary and secondary products during the pyrolysis of cellulose. The first paper on cellulose pyrolysis reports changes in solid phase composition when samples of Avicel cellulose and ball-milled cellulose were subjected to pyrolysis in a spoon reactor. Solid state chemistry evolution was examined. The formation of C=O and C=C groups was accelerated by the presence of liquid intermediates derived from the amorphous cellulose. The content of cross-linked cellulose was quantified for the first time by the combined use of acid hydrolysis and 13C NMR. A new reaction mechanism to describe the changes in the solid residue composition at different reaction conditions was proposed. The goal of the second paper on cellulose pyrolysis was to better understand important reactions responsible for the suppression of anhydro-sugars during the pyrolysis of cellulose. Our results proved that cellobiosan is an important intermediate for char formation during cellulose pyrolysis. When sulfuric acid was added in small quantities, the yield of levoglucosan increased for the Douglas Firs but decreased for the Avicel. In 2014 we published two papers reporting the results on lignin thermal degradation mechanisms. In the first paper published in Biomass and Bioenergy, the formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. In the second paper, published in Fuels, the effect of particle size on the yield and composition of lignin derived oligomers in a fluidized bed reactor was reported. Comparing the milled particles to the cylinders with equal length (equal vapor outflow distance) but varied diameter, the effect on the yield of PL seems to be mainly due to the impact of thermally ejected oligomers on internal cell walls of biomass particles (mass transfer limitations). A parametric study using principal components analysis was conducted to evaluate the effect of biomass composition and pyrolysis temperature on the distribution of products during pyrolysis. Our results showed that the yield of most of the pyrolytic products can be explained in the five groups or families proposed. Three papers were published on the torrefaction of lignocellulosic materials. The first one (published in Transactions of ASABE) reports experimental results on the effect of torrefaction temperatures (as pretreatment step) for the pyrolysis process. The objective of the second paper, published in Applied Bioenergy, was to evaluate the carbon implications of using torrefied Arundo Donax as a coal replacement. The assessment encompasses the carbon impacts of transportation, agriculture, torrefaction and combustion. The third paper published in the Journal of Analytical and Applied Pyrolysis studied the effect of torrefaction conditions on the formation of lignin liquid intermediates. Results suggest that it is possible to control the thermal pretreatment conditions to increase or reduce the amount of lignin-rich material on fiber surfaces as required for downstream processes (e.g., fuel pellets or wood composites manufacture). During 2014, we continue our evaluation of the potential of Auger pyrolysis for the selective production of bio-oils enriched in high value intermediates and bio-char. Our work focused on the use of a fractional condensation system for the separation of a heavy oil rich in bio-fuel precursors and an aqueous phase rich in C1-C4 molecules. A paper was published on the use of the anaerobic digestion of this fraction. This paper reports the anaerobic digestion (AD) of the aqueous phase rich in C1-C4 oxygenated organic compounds derived from the torrefaction of six lignocellulosic materials in an Auger reactor. A linear correlation was obtained between the optimal concentration at which a torrefaction aqueous phase can be AD and the content of HAA phenols.

Publications

Type: Book Chapters Status: Accepted Year Published: 2014 Citation: Garcia-Perez M, Garcia-Nunez JA, Pelaez-Samaniego MR, Kruger C, Fuchs MR, Flora G. 2014. Sustainability, Business Models and Techno-economic Analysis of Biomass Pyrolysis Technologies. In: Innovative Solutions and Fluid-Particle Systems and Renewable energy Management. Editor: Katia Tannous (Unicamp Brazil), 2014
Type: Conference Papers and Presentations Status: Accepted Year Published: 2014 Citation: Zhou S, Westerhof R, Garcia-Perez M: Understanding Lignin Pyrolysis Reactions on the Formation of Mono-phenols and Pyrolytic Lignin from Ligno-cellulosic Materials. TCS 2014, Denver, September 4th, 2014
Type: Journal Articles Status: Submitted Year Published: 2014 Citation: Cuba-Torres C, Marin-Flores O, Owen C, Wang Z, Garcia-Perez M, Norton G, Ha S: Catalytic partial oxidation of biodiesel surrogate over molybdenum dioxide. (Submitted to Fuel 2014)
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Liaw S-S, Frear C, Lei W, Zhag S, Garcia-Perez M: Anaerobic Digestion of C1-C4 light oxygenated organic compounds (aqueous phase) derived from the torrefaction of lignocellulosic materials. Fuel Processing Technology, 131, 2014, pp. 150-158.
Type: Theses/Dissertations Status: Published Year Published: 2014 Citation: Liaw S-S: Understanding the Formation and Separation of C1-C4 during the pyrolysis and torrefaction of ligno-cellulosic materials.
Type: Book Chapters Status: Accepted Year Published: 2014 Citation: Zhou S, Westerhof R, Pelaez-Samaniego R, Pecha B, Garcia-Perez M: Lignin Pyrolysis for the production of Fuels and Chemicals. XXIV Congreso Iberoamericano de Catalisis, Medellin, Colombia, September 15-19, 2014
Type: Book Chapters Status: Accepted Year Published: 2014 Citation: Brown R, del Campo B, Boateng AA, Garcia-Perez M, Masek O: Chapter 3: Fundamentals of Biochar production. In: Biochar for Enviornmental Management. Edited by Lehman.
Type: Book Chapters Status: Accepted Year Published: 2014 Citation: Boateng AA, Garcia-Perez M, Ondrej M, Brown R, del Campo B: Chapter 4: Biochar Production Technology. In: Biochar for Enviornmental Management. Edited by Lehman 2013.
Type: Conference Papers and Presentations Status: Accepted Year Published: 2014 Citation: Garcia-Perez M: Pyrolysis of Lignocellulosic Materials for the Production of Bio-fuels, Bio-chemicals and Bio-char. Northwest Wood based Biofuels Co-products Conference. Seattle, April 28-30, 2014
Type: Journal Articles Status: Submitted Year Published: 2014 Citation: Kadarwati S, Oudenhoven SRG, Garcia-Perez M, Kersten SRA, Li C-Z, Westerhof RJM: Polymerization, Hydrogenation and Hydrocracking of biomass derived bio-oil and Pyrolytic Lignin. (Submitted to Fuel Processing Technology, 2014)
Type: Journal Articles Status: Submitted Year Published: 2014 Citation: Garcia-Nunez JA, Elizabeth-Ramirez N, Rodriguez DT, Garcia-Perez M: Evolution of Palm Oil Mills into Bio-refineries. Part 1: Literature Review on Current and Potential Uses of biomass from Palm Oil Mills and Oil Palm Plantations (Submitted to Biomass and Bioenegry, 2014).
Type: Journal Articles Status: Submitted Year Published: 2014 Citation: Pelaez-Samaniego R, Garcia-Perez M, Zhu R, Englund K, Lowell E, Yadama V: Contribution of Lignin to the Rheology of Wood Plastic Composites Produced with Hot Water Extracted Wood. (Submitted to Composites Science and Technology, 2014)
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Zhou S, Liaw S-S, Garcia-Perez M: Py-GC/MS Studies to Evaluate the Effect of Torrefaction Temperature on Douglas fir and Hybrid Poplar Wood Pyrolysis Products. Transaction of ASABE, 57, 6, 2014
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Wang Z, Zhou S, Pecha B, Westerhof RJM, Kersten SRA, Garcia-Perez M: Effect of Pyrolysis Temperature and Sulfuric Acid on the Formation of Anhydrosugars during the Fast Pyrolysis of cellulose in a Wire Mesh Reactor at atmospheric pressure. Energy and Fuels, 28, 8, 2014, pp. 5167-5177
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Bass R, Garcia-Perez M, Horneck D, Lewis M, Pan B, Peters T, Stevens B, Wysocki D: Carbon Implications of Converting a Coal-Fired Power Plant to Combustion of Torrefied Arundo Donax. Applied Bio-energy, 1, 1, 2014 (On line journal)
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Liaw S-S, Haber-Perez V, Zhou S, Garcia-Perez M, Py-GC/MS Studies and Principal Components Analysis to Evaluate the Effect of Biomass Composition and Pyrolysis Temperature on the Distribution of Products during Fast Pyrolysis. Journal of Analytical and Applied Pyrolysis, 109, 2014, 140-151.
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Pelaez-Samaniego MR, Garcia-Perez M, Lowell E, McDonald A: Effect of temperature during wood torrefaction on the formation of lignin liquid intermediates. Journal of Analytical and Applied Pyrolysis, 109, 2014, 222-233
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Zhou S, Pecha B, van Kuppevelt M, McDonald A, Garcia-Perez M: Slow and Fast Pyrolysis of Douglas Fir Lignin: Importance of Liquid Intermediates Formation on Products Distribution. Biomass and Bioenergy, 66, 2014, 398-409
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Wang Z, Pecha B, Westerhof R.J.M., Kersten S.R.A., Li C-Z, Garcia-Perez M, McDonald AG: Effect of Cellulose Crystallinity on Solid/Liquid Phase Reactions Responsible for the Formation of Carbonaceous residues during Slow Pyrolysis. Industrial and Engineering Chemistry Research, 53, 2014, 2940-2955
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Zhou S, Garcia-Perez M, Pecha B, McDonald AG, Kersten SRA, Westerhof RJM: Effect of Particle Size on the Composition of Lignin Derived Oligomers Obtained by Fast Pyrolysis of Beech Wood Fuels, 125, 2014, 15-19
Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Wu, L, Hu X, Mourant D, Wang Y, Kelly C, Garcia-Perez M, He M, Li C-Z: Quantification of strong and weak acidities in bio-oil via non-aqueous potentiometric titration Fuel, Volume 115, January 2014, 652-657

Progress 01/01/13 to 09/30/13

Outputs
Target Audience: The results obtained were presented to policy makers, the industry, graduate and undergraduate students as well as to other members of the scientific community. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? PARTICIPANTS: Twelve PhD students (Mathew Smith, Jesus A. Garcia, Zhouhong Wang, Shuai Zhou, Shi-Shen Liaw, Brennan Pecha, Amir Sahaf, Waled Suliman, Jieni Lian, Filip Stankovikj, Daniel Howe, and Iva Tews), one MSc student (Sergio Baravalle), two Post-doctoral fellows (Victor Haber-Perez, Oselys Rodriguez Justo), five undergraduate students, and our partners participated in the research tasks How have the results been disseminated to communities of interest? The results obtained were presented to policy makers, the industry, graduate and undergraduate students through peer reviewed papers, presentations, and postersat national and international conferences. We also wrote several technical reviews to support the development of the biomass pyrolysis industry. What do you plan to do during the next reporting period to accomplish the goals? During the next reporting period we will continue working in each of the tasks listed in the proposal. More specifically, we will continue working to better understand cellulose and lignin primary and secondary reactions. Several proposals will be submitted in this area. We also plan to work on the validation of the mathematical models developed for our Auger pyrolysis reactor and will focus on the installation and operation of a new 20 lb/h Auger pyrolysis reactor we purchased last year. We plan to complete one or two PhD theses on the development and testing of engineered bio-chars for environmental papers. This year we plan to start our bio-oil hydrotreatment studies with the new set up built last year and will advance the characterization of the fuel properties of the resulting fuels. We will continue our studies on the development of hybrid concepts (e.g., bio-chemical and thermo-chemical) to refine bio-oils and on the development of methodologies to evaluate bio-refinery concepts for existing biomass processing industries.

Impacts
What was accomplished under these goals? The overall goal of this project is to advance the science and technology required to implement a novel biomass economy, formed by distributed selective pyrolysis units, rural refineries, and centralized refineries for the production of bio-fuels and bio-chemicals from waste lignocellulosic materials. Last year a literature review was published with Prof. Kersten at Twente University (Netherlands) on the current status of the technologies for this model of biomass economy. During 2013 we made progress in the following 7 areas: (1) Fundamental studies of biomass thermo-chemical reactions to better understand the relationship between the structure of biomass constituents (e.g., cellulose, hemicelluloses and lignin) and their degradation mechanisms; (2) Testing of new types of pyrolysis reactors with mathematical modeling of their concepts; (3) New analytical methods to characterize the chemical composition of bio-oils; (4) Engineering bio-chars for environmental services; (6) Developing new bio-oil based refinery concepts at the laboratory scale; and (7) Strategizing new transportation fuels and chemicals from bio-oil fractions. The fundamental studies of biomass thermochemical reactions focused on understanding cellulose reactions, lignin reactions, and interactions between the two. Vacuum pyrolysis studies on cellulose primary reactions were conductedat Twente University. These studies revealed that both crystalline and amorphous cellulose primary reactions under very fast heating rate conditions are very selective toward the formation of liquid intermediates rich in hydrolysable sugars especially larger oligomers. The Py-GC/MS at WSU was modified in 2013 to work under vacuum. We are currently workingon the design of a vacuum wire mesh reactor to study cellulose primary reactions. Studies conducted at atmospheric pressure suggest that under these conditions the oligosugars cannot evaporate, so they further crack to form levoglucosan or are dehydrated and cross-link to form larger molecules that are charcoal precursors. Some of these oligosugars can be removed in the form of aerosols by thermal ejection. We are currently writing two manuscripts reporting these results. Under slow heating rate conditions while crystalline cellulose remains as a fiber, amorphous cellulose cracks and forms a liquid intermediate. A paper with these results was published in 2013 and a paper with a detailed study of the solid phase reactions is currently under review by Industrial and Engineering Chemistry Research. The studies on lignin pyrolysis focused on the formation of oligomeric intermediates and their secondary reactions. In 2013 we published two papers in Energy and Fuels describing the formation of lignin oligomers in the primary reactions and their secondary reactions in the vapor phase. An additional paper describing how biomass structure affects the release or capture of lignin oligomeric products was accepted in Fuel. A paper with additional evidence on the critical role of lignin oligomers during pyrolysis is ready to be submitted to Biomass and Bioenergy. Studies to understand potential interactions between cellulose and lignin were conducted with blends of these two bio-polymers. Py-GC/MS results reveal that under certain cellulose-lignin ratios the production of levoglucosan is enhanced; this is likely due to the enhancement of thermal ejection when lignin was present. The fourth part of a review on pyrolysis technologies and the use of its products was also published this year. During 2013 we continued our evaluation of the potential of Auger pyrolysis for the selective production of bio-oils enriched in high value intermediates and bio-char. Our work focused on the design and construction of a fractional condensation system for the separation of a heavy oil, rich in bio-fuel precursors and an aqueous phase rich in C1-C4 molecules. We also advanced the development of a microscopic mathematical model to describe the behavior of single particles and a plug flow model to describe the behavior of the reactor. Two strategies were studied to improve the selectivity of this reactor towards the production of transportation fuels. The first strategy (thermal pretreatment also called step-wise pyrolysis) did not result in an important improvement of selectivity. However, our studies did show that certain benefits could be obtained if the biomass was first torrefied at temperatures below 300 oC. One paper with these findings was published in Fuel and we are currently working on a second manuscript reporting the outcome of Py-GC/MS studies. The second strategy studied is the use of sulfuric acid as an additive. Three papers were published (two in Fuel and one in the Journal of Analytical and Applied Pyrolysis) describing the findings of our studies. In materials containing natural catalysts in the ash (Na, K, Mg, Ca), sulfuric acid seems to passivate their catalytic effect on fragmentation reactions and consequently enhance the production of levoglucosan. The new finding of our group is that the use of sulfuric acid on acid wash materials also enhances levoglucosan production mainly because of its effect on poorly known cellulose-lignin interactions. A paper with these results was published in the Journal of Analytical and Applied Pyrolysis. Our group continued working on the development of new analytical methods to characterize the chemical composition of bio-oils. A new method for the quantification of strong and weak acids in bio-oil was developed in collaboration with Prof. Chun-Zhu Li from Curtin University. A paper with the method was published in Fuel. Our group continued designing engineered bio-chars for environmental services. This year we focused on several bio-chars for P and N removal. We also studied the interactions between bio-char and micro-organisms. Three papers will be submitted in 2014 with the results of these studies. A 20 lb/h pyrolysis reactor was purchased for the production of large quantities of engineered bio-char for field studies. Several studies were conducted to study novel concepts to refine bio-oils. One of the strategies studied is the fermentation of levoglucosan for the production of lipids and ethanol. A paper was published on Bio-resources technology on the fermentation of this pyrolytic sugar with Oleaginous Yeasts. We are currently working on other two manuscripts. In the first one, we will report our findings on the over-expression of lgk gene in Yeat Yarrowia for enhanced lipid production. The second paper on which we are workingreports the engineering ofthelevoglucosan metabolic Pathway in Rhodococcus jostii RHA1 for lipid production. The phenolic rich fraction has been studied for the production of tunable thermoplastics. A paper with the results obtained was published in Biomacromolecules. Finally, last year we completed the construction of a 250 mL batch hydrotreatment unit for the conversion of bio-oils in transportation fuels.

Publications

Type: Journal Articles Status: Published Year Published: 2013 Citation: Zhou S, Osman N, Li H, McDonald A, Mourant D, Li C-Z, Garcia-Perez M : Effect of Sulfuric Acid Addition on the Yield and Composition of Lignin Derived Oligomers Obtained by the Auger and Fluidized bed Pyrolysis of Douglas Fir Wood Fuel, Volume 103, January 2013, 512-523
Type: Journal Articles Status: Published Year Published: 2013 Citation: Liaw S-S, Zhou S, Wu H, Garcia-Perez: Effect of Pretreatment Temperature on the Yield and Properties of Bio-Oils obtained from the Auger Pyrolysis of Douglas Fir Wood. Fuel, Vol. 103, January 2013, 672-682
Type: Journal Articles Status: Published Year Published: 2013 Citation: Wang Z, McDonald A, Cuba-Torres C, Ha S, Westerhof R, Kersten S, Pecha B ,Garcia-Perez M: Effect of Cellulose Crystallinity on the Formation of a Liquid Intermediate and on Product Distribution During Pyrolysis, Journal of Analytical and Applied Pyrolysis, Volume 100, March 2013, 56-66
Type: Journal Articles Status: Published Year Published: 2013 Citation: Usman-Rahim M, Gao X, Garcia-Perez M, Li Y, Wu H: Release of Chlorine during Mallee Bark Pyrolysis. Energy and Fuels, 2013, 27 (1), 310-317
Type: Journal Articles Status: Published Year Published: 2013 Citation: Lian J, Garcia-Perez M, Chen S: Fermentation of Levoglucosan with Oleaginous Yests for Lipid Production. Bio-resources Technology, Volume 133, 2013, 183-189
Type: Journal Articles Status: Published Year Published: 2013 Citation: Zhou S, Pecha B, Westerhof R, Garcia-Perez M, McDonald A, Kersten S: Secondary Vapor Phase Reactions of Lignin Derived Oligomers Obtained by fast Pyrolysis of Pine Wood. Energy and Fuels, 2013, 27 (3), pp 1428-1438
Type: Journal Articles Status: Published Year Published: 2013 Citation: Kersten SRA, Garcia-Perez M: Recent Developments in Fast Pyrolysis of Lignocellulosic Materials. Current Opinion in Biotechnology, Volume 24, Issue 3, 2013, pp. 414-420)
Type: Journal Articles Status: Published Year Published: 2013 Citation: Zhou S, Garcia-Perez M, Pecha B, McDonald A, Kersten SRA, Westerhof RJM: Effect of the Fast Pyrolysis Temperature on the Primary and Secondary Products of Lignin. Energy and Fuels, 2013, 27 (10), pp 5867-5877)
Type: Journal Articles Status: Published Year Published: 2013 Citation: Zhou S, Wang Z, Liaw S-S, Li C-Z, Garcia-Perez M: Effect of Sulfuric Acid on the Pyrolysis of Douglas Fir and Hybrid Poplar Wood: Py-GC/MS and TG Studies. Journal of Analytical and Applied Pyrolysis, Volume 104, November 2013 pp 117-130
Type: Book Chapters Status: Published Year Published: 2013 Citation: Brown R, del Campo B, Boateng AA, Garcia-Perez M, Masek O: Chapter 3 : Fundamentals of Biochar production. In : Biochar for Enviornmental Management. Edited by Lehman 2013.
Type: Book Chapters Status: Published Year Published: 2013 Citation: Boateng AA, Garcia-Perez M, Ondrej M, Brown R, del Campo B: Chapter 4 : Biochar Production Technology. In : Biochar for Enviornmental Management. Edited by Lehman 2013.
Type: Book Chapters Status: Published Year Published: 2013 Citation: Garcia-Perez M. Chapter 23 Pyrolysis. In: Bioenergy: Principles and Applications. Editors: Yebo Li, Samir Kumar Khanal 2013
Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Lian J: Biological Conversion of Pyrolytic Products to Lipids and Ethanol. PhD Thesis, WSU, May 2013
Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Wang Z: Understanding cellulose primary and secondary pyrolysis reactions to enhance the production of anhydrosaccharides and ti better predict the composition of carbonaceous residues. PhD Thesis, WSU August 2013
Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Zhou S: Understanding Lignin pyrolysis reactions on the formation of mono-phenols and pyrolytic lignin from lignocellulosic materials. PhD Thesis, WSU, July 2013

Progress 01/01/12 to 12/31/12

Outputs
OUTPUTS: This project aims to advance the science and technology needed to implement a new model of biomass economy formed by pyrolysis units located close to biomass resources to produce crude bio-oil and bio-char, to support rural and centralized refineries for the production of fuels and chemicals from bio-oils. The experimental results obtained last year contribute to a much clearer view of the mechanisms of cellulose thermochemical reactions and how to control the reactions (through pretreatment and through the use of additives) to enhance the production of anhydrosugars. We have measured the chemical changes occurring in solid phase and have proposed a new model explaining the formation of crosslinked sugars and char. The cross-linked sugars are important intermediates during cellulose pyrolysis and define the yield of charcoal produced. Our experimental results have proven the importance of cellulose crystallinity on the formation of liquid intermediates and show that these liquid intermediates are responsible for the thermal ejection of oligomeric products and for dehydration and poly-condensation reactions leading to the formation of water and char. Our collaborative work with the University of Twente proves that the composition of bio-oil can be controlled by changing the condensation conditions employed. This result is very important because by controlling the condensation conditions it is possible to separate the light organic molecules (C1-C4) and the water (undesirable molecules) from the heavier molecules (more than 5 carbon atoms) which are precursors for the production of transportation fuels. We have also proven that the structural and chemical modifications occurring in cellulose structure at temperature below 300 oC do not affect the yield of pyrolysis products when the thermally pretreated biomass is subjected to pyrolysis between 500 and 530 oC. This study found that the formation of "active cellulose" is not a critical intermediate, as initially thought, in determining the outcome of the pyrolysis reactions happening at high temperatures (500 oC). Our results also confirmed that depending of the pyrolysis reactor, there are certain sulfuric acid concentrations at which the production of levoglucosan is maximized. The increase in the yield of levoglucosan seems to be associated with the passivation of the catalytic effect of alkalines. Although the production of small amounts of sulfuric acid seems to be a positive strategy to maximize the production of anhydrosugars, it has a detrimental impact in the production of aromatic compounds from lignin. The production of lipids with Cryptococcus curvatus from the carboxylic acids present in the pyrolytic aqueous phase (kindly provided by Coates Engineering) was also studied. The capacity of three oleaginous yeasts: Cryptococcus curvatus, Rhodotorula glutinis, Lipomyces starkeyi, to ferment acetate, formate, hydroxyacataldehyde, phenol and acetol (as model compounds of pyrolytic aqueous phase compounds) was tested. PARTICIPANTS: Eight graduate students (Mathew Smith, Jesus A. Garcia, Zhouhong Wang, Shuai Zhou, Shi-shen Liaw, Waled Suliman, Jieni Lian, Filip Stankovikj) and our partners participated in the research tasks TARGET AUDIENCES: The results obtained were presented to policy makers, the industry, graduate and undergraduate students. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Last year our team finished the construction of a wire mesh reactor. This type of reactor has two important features: (1) An inert gas flows through the system which rapidly sweeps any volatile product formed from the hot reaction zone and (2) Heating rates from as low as 0.01 and up to 200 oC/s may be programmed for peak temperatures between 100 and 1200 oC. An infrared sensor measures the temperature of the mesh. We synchronized a fast speed camera to visualize on real time the changes on the biomass structure occurring under very high heating rates. The construction of a two-step condensation system for our pyrolysis reactor was completed by Bill's Welding & Machine Shop (Pullman, WA). New cells were added to the batch respirometer in our department. This respirometer has been used to study the anaerobic digestion of pyrolytic C1-C4 molecules. In 2012, we established a new kinetic model that considers the formation of aromatic rings in three consecutive steps for the amorphous cellulose (depolymerization and formation of a liquid intermediate, dehydration/crosslinking and formation of aromatics) was proposed. The kinetic constants (Activation energy and pre-exponential factor) of each of these steps were obtained. Studies in the atmospheric wire mesh reactor prove that very high yields of levoglucosan (over 60 %) can be obtained from cellulose at 350 oC. Most of the oligomeric sugars formed are non hydrolysable, suggesting that they are undergoing dehydration and cross-linking in the liquid intermediate. One paper published in the Journal of Analytical and Applied Pyrolysis reported results on the effect of pyrolysis temperature on the yield and properties of pyrolysis products from the auger pyrolysis of Douglas Fir wood. Bio-oil yields were close (maximum yield: 59 mass%) to those reported for fluidized bed reactors (more than 60 mass%). The results obtained confirm that the auger reactor is able to achieve good yields of both bio-oil and bio-char. A paper was published in Energy and Fuel on the effect of thermal pretreatment conditions on the outcome of the pyrolysis process. The temperature of the first step (pretreatment) was varied between 260 oC and 360 oC. After the first step, the solid residue was cooled to ambient temperature and pyrolyzed again at 530 oC. If the first step temperature was below 290 oC, the cumulated yields (the sum of step 1 and 2) were identical to yields of the single-step experiment at 530 oC. The paper authored by Liaw at el. (2012) also investigates the effect of thermal pretreatment temperatures between 200 and 370 oC on the yield and composition of products (bio-char, gas, water and organics) obtained when Douglas-fir wood was subsequently pyrolyzed in an auger reactor at 500 oC. The effect of sulfuric acid (H2SO4) additives on the yield and composition of pyrolysis products in an auger and fluidized bed reactor was reported in two papers authored by Zhou et al. (2013). The concentration of sulfuric acid in the feedstock was varied between 0 and 0.6 mass%.

Publications

Lian J., M.Garcia-Perez, R.Coates, H.Wu, S.Chen 2012. Yeast Fermentation of Carboxylic Acids obtained from Pyrolytic Aqueous Phases for Lipid Production. Bioresource Technology 118:177-186.
Zhou S., N.Osman, H.Li, A.McDonald, D.Mourant, C.Li, M.Garcia-Perez 2012. Effect of Sulfuric Acid Addition on the Yield and Composition of Lignin Derived Oligomers Obtained by the Auger and Fluidized bed Pyrolysis of Douglas Fir Wood. Fuel. 103:512-523.
Liaw S., S.Zhou, H.Wu, M.Garcia-Perez 2012. Effect of Pretreatment Temperature on the Yield and Properties of Bio-Oils obtained from the auger Pyrolysis of Douglas Fir Wood. Fuel. 103:672-682.
Hu X., D.Mourant, Y.Wang, L.Wu, W.Chaiwat, C.Li, R.Gunawan, M.Gholizadeh, C.Lievens, M.Garcia-Perez 2012. Acid-catalysed treatment of the mallee leaf of bio-oil with methanol: Effects of molecular structure of carboxylic acids and esters on their conversion. Fuel Processing Technology 106:569-576.
Westerhof R., W.Brilman, M.Garcia-Perez, Z.Wang, W.Van Swaaij, S.Kersten 2012. Stepwise Fast Pyrolysis of Pine Wood. Energy & Fuels : An American Chemical Society Journal. 26(12):7263-7273.
Zhou S., D.Mourant, C.Lievens, Y.Wang, C.Li, M.Garcia-Perez 2012. Effect of Sulfuric Acid Concentration on the Yield and Properties of the Bio-oils Obatined from the Auger and Fast Pyrolysis of Douglas Fir. Fuel. 104:536-546.
Gao X., M.Garcia-Perez, H.Wu 2012. Roles of Inherent Fine Included Mineral Particles in the Emission of PM10 during Pulverized Coal Combustion. Energy & Fuels : An American Chemical Society Journal. 26(11):6783-6791.

Progress 01/01/11 to 12/31/11

Outputs
OUTPUTS: The main goal of this project is to advance the science and technology needed to implement a new model of biomass economy formed by pyrolysis units located close to biomass resources that can produce crude bio-oils and bio-char, rural refineries where these oils will be converted into high value products and stabilized bio-oils compatible with existing refineries where drop-in fuels will be produced. To implement this new concept of biomass economy it is necessary: (1) To better understand thermochemical reactions of cellulose hemicelluloses and lignin (2) to design new concepts for slow and fast pyrolysis units able to convert biomass into bio-oil and bio-char, (3) to evaluate new concepts for rural bio-oil refineries, and (4) to develop and test second generation bio-fuels and chemicals from bio-oils and bio-chars. During the last year our team has evaluated two strategies to enhance the production of hydrolysable sugars from lignocellulosic materials. The strategies evaluated were: thermal pretreatment to increase the production of "active cellulose" and use of additives (NH4H2PO4, a hydrogen donor (tetralin), and H2SO4). These studies were conducted in the auger pyrolysis reactor and in a fluidized bed reactor. The results obtained proved that although mild torrefaction (between 270 and 300 oC) is a valuable approach to reduce the energy consumed to grind the biomass, the effect on the yield of anhydrosugars obtained was modest. Torrefaction, at temperatures over 300 oC, results in drastic reductions in bio-oil yield. A paper reporting these results has been submitted with our collaborators from Twente University to Industrial and Engineering Chemistry Research. Because of the limited effect observed with the thermal pretreatment, we decided to conduct studies with additives (NH4H2PO4, H2SO4, and tetralin) to enhance the production of anhydrosugars (levoglucosan). The addition of 0.3 mass % of NH4H2PO4 increases the yield of anhydrosugars, but induced a drastic reduction in the yield of pyrolytic lignin. The effect of a hydrogen donor (tetralin) concentration was also evaluated, but its impact on the yield of anhydrosugars was modest without drastically impacting the yield of lignin oligomers. The effect of sulfuric acid concentration on the yield of anhydrosugars obtained in an auger and fluidized bed reactor was studied in collaboration with our partners at Curtin University (Australia). Our group reported, for the first time that, although a good strategy to enhance the production of anhydrosugars, the addition of sulfuric acid dramatically reduced the yield of lignin oligomers. A paper with these results was submitted to Fuel. Lignin oligomers are also considered precursors for the production of transportation fuels. Our team also developed a method to hydrolyze, detoxify and ferment pyrolytic anhydrosugars to produce ethanol and lipids. It was proven that the hydrolysable pyrolytic sugars produced can be fully converted into ethanol or lipids. Last year we studied the direct fermentation of pyrolytic sugars (levoglucosan) into lipids (without hydrolyzing it into glucose first). PARTICIPANTS: Eight graduate students (Matthew Smith, Jesus A. Garcia, Zhouhong Wang, Shuai Zhou, Shi-Shen Liaw, Waled Suliman, Jieni Lian, Filip Stankovikj) and our WSU domestic and international collaborators (Prof. Shulin Chen, Prof. Su Ha, Prof. Chun-Zhu Li, Prof. Sascha Kersten, Dr. Craig Frear, Dr. Roel Westerhof) participated in the research tasks. TARGET AUDIENCES: The results obtained were presented to policy makers, the industry, graduate and undergraduate students. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
The results of this project have advanced our understanding of the mechanisms responsible for the production of anhydrosugars and the possibility of passivating the catalytic effect of the alkalines present in biomass. Our results also point out the importance of cellulose-alkaline-lignin interactions. Our studies confirm that the use of small quantities of the additives sulfuric acid (H2SO4), ammonium phosphate (NH4H2PO4), and hydrogen donors (tetralin) has a positive effect on the yield of levoglucosan. The effect of H2SO4 seems to be associated to the passivation of the alkalines. Higher yields of levoglucosan are needed to enhance the economic viability of this concept. The yield of products obtained in the fluidized bed and auger pyrolysis reactors were similar. The pyrolytic sugars can be separated, hydrolyzed, detoxified and fermented to produce ethanol and lipids. We have identified micro-organisms containing levoglucosan kinase that are able to produce lipids directly from levoglucosan. Cheaper methods to detoxify the fermented aqueous phase need to be developed. A mathematical model to describe the behavior of single particle was developed. Our results were published in seven peer reviewed journals and were presented in posters and presentations in six conferences. A literature review on pyrolysis reactors was also published.

Publications

Streubel, J.D., Collins, H.P, Garcia-Perez, M., Tarara, J., Granatstein, D., and Kruger, C.E. 2011. Influence of contrasting biochar types on five soils at increasing rates of application. Soil Sci Soc Am J. 75(4):1402-1413.
Westerhof, R. J.M., Brilman, D.W.F., Garcia-Perez, M., Wang, Z., Oudenhoven, S.R.G., van Swaaij, W.P.M., and Kersten, S.R.A. 2011. Fractional Condensation of Biomass Pyrolysis Vapors. Energ Fuel. 25(4):1817-1829.
Yoder, J., Galinato, S., Granatstein, D., and Garcia-Perez, M. 2011. Economic tradeoff between biochar and bio-oil production via pyrolysis. Biomass Bioenerg. 35(5):1851-1862.
Zhang, T., Chao, Y., Liu, N., Thompson, J., Garcia-Perez, M., He, B.B., Van Gerpen, J., and Chen, S. 2011. Case Study of Biodiesel-Diesel Blends as a Fuel in Marine Environment. Adv Chem Eng Sci. 1(2):65-71.
Li, X., Gunawan, R., Lievens, C., Wang, Y., Mourant, D., Wang, S., Wu, H., Garcia-Perez, M, and Li, C.-Z. 2011. Simultaneous catalytic esterification of carboxylic acids and acetalisation of aldehydes in a fast pyrolysis bio-oil from mallee biomass. Fuel. 90(7):2530-2537.
Liaw, S.-S., Wang, Z., Ndegwa, P., Frear, C., Ha, S., Li, C.-Z., and Garcia-Perez, M. 2012. Effect of pyrolysis temperature on the yield and properties of bio-oils obtained from the auger pyrolysis of Douglas Fir wood. J Anal Appl Pyrol. 93:52-62.
Mourant, D., Wang, Z., He, M., Wang, X.S., Garcia-Perez, M., Ling, K., and Li, C.Z. 2011. Mallee wood fast pyrolysis: Effects of alkali and alkaline earth metallic species on the yield and composition of bio-oil. Fuel. 90(9):2915-2922.

Progress 01/01/10 to 12/31/10

Outputs
OUTPUTS: During 2010 we progressed on our goal of building a nationally reputed program in biomass thermochemical conversion. A new pyrolysis spoon reactor was built and another reactor is under construction (a mesh reactor) to study the mechanisms and kinetics of biomass thermochemical reactions. A system to continuously remove and cool down the charcoal produced in the Auger reactor has been built and is now operational. Detailed studies by Py-GC/MS were conducted to understand the effect of a mild torrefaction on the production of anhydrosugars during biomass pyrolysis. The results obtained suggest that although in some conditions it is possible to increase the yield of sugars produced by a mild thermal pretreatment, the increases observed were modest and were feedstock dependent. This was confirmed in the tests conducted by Py-GC/MS. So, we decided to study the effect of additives (H2SO4 and NH4H2PO4) on the production of sugars. Although these additives effectively allowed for a doubling of the production of sugars, this occurred at the expense of reducing the yield of lignin oligomers which are also precursors for the production of transportation fuels. New additives are being tested to increase both the production of sugars and lignin derived products. In collaboration with our partners in the Netherlands and Australia, we have advanced our understanding on the effect of alkalines on biomass thermal degradation mechanisms and on how to control the operation of two stepped condensers to separate small oxygenated molecules from the precursors of transportation fuels. Papers on the separation and fermentation of pyrolytic sugars, on the antioxidant properties of bio-oils and on the fuel properties of bio-oil/bio-diesel blends have been published. An evaluation of the economic trade-off between bio-char and bio-oil production via pyrolysis was conducted in collaboration with the WSU School of Economic Sciences. PARTICIPANTS: Washington State University, Pullman: Manuel Garcia-Perez, Assistant Professor/Scientist; and Shulin Chen, Professor/Scientist. TARGET AUDIENCES: Students, engineers, scientists and policy makers in academia, industry and government. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
The results obtained last year could lead to the development of more selective pyrolysis units used to convert lignocellulosic materials into desirable intermediates and the development of rural bio-oil refineries to convert bio-oils into high value products (ethanol, anti-oxidant, fuel additives). We have advanced our understanding of the conditions needed to oxidize bio-char (formation of acidic functional groups on the surface) to enhance its effect on soil fertility. Three other papers have also been submitted for evaluation. The results obtained in 2010 were presented in eight conferences. Six graduate students were advised. Two graduate courses were offered and a biomass thermochemical conversion summer internship was organized with three high school students and two undergraduate students.

Publications

Garcia-Perez, M., Adams, T.T., Goodrum, J.W., Das, K.C., and Geller, D.P. 2010. DSC studies to evaluate the impact of bio-oil on cold flow properties and oxidation stability of bio-diesel. Bioresour Technol. 101(15):6219-6224.
Garcia-Perez, M., Shen, J., Wang, X.S., and Li, C-Z. 2010. Production and fuel properties of fast pyrolysis oil/bio-diesel blends. Fuel Process Technol. 91(3):296-305.
Lian, J., Chen, S., Zhou, S., Wang, Z., O'Fallon, J., Li, C-Z., and Garcia-Perez, M. 2010. Separation, hydrolysis and fermentation of pyrolytic sugars to produce ethanol and lipids. Bioresour Technol. 101(24):9688-9699.

Progress 01/01/09 to 12/31/09

Outputs
OUTPUTS: We have further improved our analytical laboratories to study the selectivity of thermochemical reactions and characterize pyrolysis oils. A new 2 kg/h Auger pyrolysis reactor is now operational and we are upgrading the initial design with a system to continuously remove and cool down the charcoal produced. We have expanded our research to understand the impact of pre-treatment conditions on biomass structure and its effect on the yields of sugars obtained by pyrolysis using Py-GC/MS (pyrolysis gas chromatography/mass spectrometry). We have proven that it is possible to increase the yields of anhydrosugars if the lignocellulosic materials are pre-treated between 200 and 300 degrees C. However the optimal pre-treatment conditions are feedstock dependent. We have also proven that under certain circumstances it is possible to obtain high yields of bio-oils in Auger pyrolysis reactors. Our group has also advanced in the development of advanced analytical techniques to characterize bio-oils. We are currently analyzing oils produced in Australia and the Netherlands as part of our collaborations with leading foreign universities. Our lab was able for the first time to detoxify and ferment pyrolysis sugars. Although the method used should be optimized our results proved for the first time that it is possible to utilize the pyrolytic sugars present in bio-oils to produce ethanol. PARTICIPANTS: Washington State University, Pullman: Manuel Garcia-Perez, Assistant Professor/Scientist and Shulin Chen, Professor/Scientist. TARGET AUDIENCES: Students, engineers and scientists in academia, industry and government. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
These results may lead to the development of highly selective fast pyrolysis units to convert most of the cellulose into anhydrosugars and in bio-oil refineries to separate, detoxify and ferment the pyrolytic sugars to produce ethanol.

Publications

Johnson, R.L., Liaw, S.-S., Garcia-Perez, M., Ha, S., Lin, S.S.-Y., McDonald, A.G., and Chen, S. 2009. Pyrolysis Gas Chromatography Mass Spectrometry Studies to Evaluate High-Temperature Aqueous Pretreatment as a Way to Modify the Composition of Bio-Oil from Fast Pyrolysis of Wheat Straw. Energ. Fuel. 23(12):6242-6252.
Shen, J., Wang, X.-S., Garcia-Perez, M., Mourant, D., Rhodes, M.J., and Li, C.-Z. 2009. Effects of particle size on the fast pyrolysis of oil mallee woody biomass. Fuel. 88(10):1810-1817.
Smith, J., Garcia-Perez, M., and Das, K.C. 2009. Producing fuel and specialty chemicals from the slow pyrolysis of poultry DAF skimmings. J Anal. Appl. Pyrol. 86(1):115-121.

Progress 01/01/08 to 12/31/08

Outputs
OUTPUTS: We have made progress in creating a new analytical laboratory to characterize pyrolysis oils. A new 2 kg/h auger pyrolysis reactor was built. The impact of pre-treatment conditions on biomass structure and its effect on the yields of sugars obtained by fast pyrolysis was studied using Py-GC/MS (pyrolysis gas chromatography/mass spectrometry). It was proven that the yields of pyrolytic sugars from wheat straw and cellulose can be increased if the biomass is pretreated at temperatures between 200 and 240 degrees C. Our studies also confirmed that the yields of pyrolytic sugars can be enhanced when pyrolysis is carried out at temperatures around 400 degrees C. PARTICIPANTS: Manuel Garcia-Perez, Assistant Professor, Washington State University; Shulin Chen, Professor/Scientist, Washington State University. TARGET AUDIENCES: Students, engineers and scientists in academia, industry and government. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
These results may lead to the development of a highly selective thermo chemical process, which will maximize the yield of pyrolytic sugars from biomass. These sugars can be further hydrolyzed, detoxified and fermented to produce Ethanol.

Publications

No publications reported this period