Source: WASHINGTON STATE UNIVERSITY submitted to NRP
NANO CELLULOSE-BASED NANOPARTICLE CATALYSTS FOR BIO-JET FUEL RANGED CYCLOALKANES PRODUCTION
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
1015123
Grant No.
2018-67009-27904
Cumulative Award Amt.
$499,955.00
Proposal No.
2017-05966
Multistate No.
(N/A)
Project Start Date
Mar 1, 2018
Project End Date
Feb 28, 2023
Grant Year
2018
Program Code
[A6162]- Co-products from Biomass Feedstocks
Recipient Organization
WASHINGTON STATE UNIVERSITY
240 FRENCH ADMINISTRATION BLDG
PULLMAN,WA 99164-0001
Performing Department
(N/A)
Non Technical Summary
The existing conversion pathway for bio-jet fuel ranged cycloalkanes involves a series of heterogeneous catalysis, which usually occur at high operating temperatures (150-300 C) and high H2 pressures (up to 5 MPa) in presence of supported metal catalysts. However, the as-prepared heterogeneous catalysts often suffer the problems of aggregation and leaching-out of active species due to their high surface energy and weak interaction with the matrices, which inevitably lead to reduced catalytic activity and reusability. To reduce the energy and hydrogen demand and improve the catalytic performance of bio-jet fuel ranged cycloalkanes production, we propose a new catalyst design by leveraging an environmental-friendly nature molecules, nanocrystalline cellulose (NCC), a rod-like nanocrystals which can be sourced from any agroforestry wastes. It is expected that the presence of abundant reducing functional groups (e.g. hydroxyl and ehter) can stabilize metal nanoparticles in a highly monodispersed form, thus reduce the chance of agglomeration and lead to the improvement of catalytic activity and recyclability. The obtained metal-NCC nanoparticles is expected to catalyze hydrogenation of aromatics into cycloalkanes at room temperature and reduced H2 pressure. Our proposed project is transformative in two ways: 1) we present an emerging new innovative idea to create a "green catalyst" that can potentially be used for bio-jet fuels production with less energy input and H2 consumption compared to the state-of-the-art hydrotreating process; and 2) by using cutting-edge separation and enzymatic hydrolysis approaches, we are applying new knowledge and approaches to solve the challenges in the state-of-the-art of nanocrystalline cellulose extraction.
Animal Health Component
100%
Research Effort Categories
Basic
(N/A)
Applied
100%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
5110650202050%
5111510202050%
Goals / Objectives
The long-term goal of this proposed project is to advance the development and application of agricultural products in biofuels synthesis area, and to improve the domestic energy security and boost agricultural economy. The supporting objectives include: 1) develop a novel synthesis of nanocrystalline cellulose with high surface area, controllable surface chemistry and good thermal stability; and 2) evaluate these nanocellulosic materials' potential application as catalysts for jet fuels production.
Project Methods
Method 1. Extraction of nanocrystalline cellulose (NCC) from agroforestrial waste via enzymatic hydrolysis:The initial step, isolation of cellulosic materials, will be performed following the "clean biomass fractionation" developed in our lab. Ethyl acetate is used as lignin solvent and is mixed with ethanol and water to dissolve the lignin in corn stover and Douglas fir sawdust. Four factors will be evaluated for the optimization: temperature, sulfuric acid catalyst loading, ethyl acetate and ethanol content in the solvent mixture. The filtrated solid cellulose is then submitted to lignin bleaching using aqueous sodium chlorite under mechanical stirring. The pure solid cellulose is filtered out and washed with deionized water. We will apply Cellulolytic Enzyme Lignin (CEL) treatment and the FTIR spectra to analyze the obtained cellulose and ensure that all the lignin have been removed.We will use cellulase enzyme for hydrolysis. Prior to enzymatic hydrolysis, the resultant dispersion will be pretreated using microwave irradiation. The effects of microwave power and duration will be investigated. After microwave pretreatment, cellulase will be added into the dispersion. Enzymatic hydrolysis will be performed under continuous stirring using an incubated shaker. The colloidal suspension of NCC solution will be collected and lyophilized. For comparison, NCC will also be prepared by a conventional acid hydrolysis of the isolated cellulose. The yield of NCC will be calculated as the percentage ratios of the solid NCC to the initial raw biomass feedstock.Method 2. Characterization of NCC and its derived metal nanoparticles (MNPs):In the present project, an "economic" procedure by getting rid of hydrogen usage during NCC supported MNPs generation will be used. Ultrasonic treatment will be used, which can physically enhance the uniformity of metal ions adsorbed on NCC surface. Hydrothermal treatment will be conducted with the assistance of microwave heating. In this project, none-noble metal, such as Ni, Fe, Co, will be used for generating nano-particles on NCC surface. In a typical experiment, NCC suspension will be mixed with Ni(NO3)2 solution. The final mixture with various Ni(NO3)2 and NCC concentration will be stirred under magnetic stirring and then transferred to ultrasonic treatment to homogenize the suspension. Finally, the mixture will be placed in a hydrothermal synthesis reaction glass reactor with the microwave heating to obtain the Ni MNP@ NCC nanoparticle suspension.General characterizations will be conducted by X-ray diffraction (XRD) to verify the nanostructure of NCC and its derived MNPs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) will be used to observe the morphology and confirm the textural construction during the generation of NCC-based MNPs. BET surface area and pore structure are determined. Fourier transform infrared spectrums (FT-IR) of the NCC and MNPs samples are recorded by an IR Prestige 21 spectrometer in the attenuated total reflection mode. Thermogravimetric analysis (TGA) will be conducted to investigate the thermal degradation characteristics of NCC and MNPs samples.Method 3. Catalytic activity tests and molecular reaction mechanism:We will be the first time applying the NCC-based MNPs for the bio-oil upgrading focusing in cycloalkanes generation from aromatic hydrocarbon. Raw bio-oil obtained previously with high aromatic concentration will be used as feed stock. Specifically, mix the MNPs suspension with bio-oil in various catalyst/reactant weight ratio. The reaction will be carried out in the water suspension of the catalyst, with no addition of any other solvent. We will start the catalytic process from mild reaction condition, which are room temperature (25°C) and hydrogen pressure (4 bar). Also, higher temperature and pressure will be employed to investigate the catalyst performance in various conditions. After reaction, the products could be easily extracted out of the catalyst aqueous suspension. Aliquots of the reaction mixture will be analyzed by GC-MS.We will adopt the theoretical calculation of Density Function Theory (DFT) method to unveil the molecular pictures of catalytic reactions on the NCC-supported MNPs, obtaining a clear reaction steps on the catalyst surface that how the aromatic hydrocarbon convert to cycloalkanes. We will start theoretical calculation with two typical compounds with high concentration in boil-oil, 5-hydroxymethy furaldehyde (5-HMF) and guaiacol, which mainly come from cellulose and lignin pyrolysis, respectively, to determine the most favorable pathway thermodynamically and kinetically. Quantum calculation package, GAUSSIAN09, will be used throughout the calculations. TEMPERATURE and PRESSURE key words will also be added to simulate reaction conditions in actual experiments. All the calculations will be conducted on Kamiak supercomputing cluster in WSU research computing center.Method 4. Catalyst regeneration and improvement:The catalyst in this project is supported on the NCC and thus will be in the state of NCC suspension. We will use the organic solvent to extract the produced cycloalkanes leaving catalyst suspension in another phase. We anticipate that there is no coking in our nanoparticle catalysts, since the reaction undergoes at the room temperature, eliminating coking/re-polymerization of aromatics. Catalyst activity towards toluene hydrogenation indicates that complete conversion can be achieved at room temperature with water as the solvent. In the case coking is observed by XRD, SEM and TEM, we will regenerate nanoparticle catalyst by separating metal from NCC and regenerating the MNPs following the steps described in Method 2. Lifetime testing of the nano catalyst will be performed.Evaluation: we will assess initiatives and resource allocations which will ultimately influence the success of the project; we will make sure the project being implemented as intended with appropriate resources available for project implementation; Identify aspects of the project which are most effective and least effective; identify the challenges associated with project implementation and address them; we will collect quantitative and qualitative data related to project activities, analyze and report in a timely fashion to inform project modifications and improvements as necessary; we will examine the extent to which PI and his team have achieved each of the goals stated in this proposal; a comprehensive review of the objectives and evaluation findings - particularly the outputs/products/milestones - will be used to determine the extent to which the project has achieved its goals.Other evaluations include: we will develop a set of outputs/products/milestones for each task to facilitate accountability and overall evaluation; the team members will collaborate to create a set of baseline metrics and provide data needed to evaluate project outcomes and impacts; annual progress and final impact reports will be communicated to the project team and USDA NIFA on an annual basis; the team members will communicate their findings to both scientific and public audiences including biomass and biofuels industrial companies; the research team will create posters to showcase their findings in the annual campus-wide Academic Showcase at WSU, and annual CleanTech Showcase of the Pacific Northwest; PI and the post-doc and graduate students will present the research findings in annual scientific meetings, such as ASABE meetings; the news of research findings will be released and communicated to the general public; The students and post-doc co-authored with PI will publish their research results in peer-reviewed high-impact journals.

Progress 03/01/18 to 02/28/23

Outputs
Target Audience:Biomass industrial companies, biofuel-related industries, biomass and biofuel producers, processors, wholesalers, and retailers: including Creative Energy Systems Inc.,MS Sustainables, LLC., North America Green Pulp Inc., USS International Group,LLP.,Sustainable Fiber Technologies, Inc.,Ambient Energy LLC,Clearwater Supply, Inc., Energy Associates Intl., LLC, Conrad Industries, Inc., DTG Recycling Group, LLC., Molten Materials, LLC., Ruiz Energy Corporation,Sedron Technologies Inc. Efforts: Formal classroom instruction (new course lectures/sessions) about the project in BSysE 593 Renewable Energy Technologies, BSYSE 551 Advanced Biological Systems Engineering Topics: Bioprocess Engineering, BSysE 552 Advanced Biological Systems Engineering Topics: Biomass and Bioenergy; BSYSE 551 Advanced Biological Systems Engineering Topics:Mass Balances, Energy Balances, and Unit Operations; BSYSE 552 Advanced Biological Systems Engineering Topics:Economic and Environmental Sustainability of Energy. Development of curriculum (new lecture sessions on biomass conversion and catalysis, biomass-derived nanocellulose, nanocarbon catalysts, chemicals, bio-jet fuel); Trained graduate and undergraduate students and post-doctoral researchers who work on this project will eventually join the workforce and contribute to the effort of utilizing biomass and developing bioproducts (i.e. nanocellulose, nanocarbon catalysts) and renewable energy technology for the future energy needs: PhD students:Wendy Mateo, Rongge Zou, Erguang Huo, Yunfeng Zhao, Dengle Duan, ErguangHuo, Yunfeng Zhao, Qingfa Zhang; MS student: Zhiyang Huang; undergraduate students: Roy Leal, Erick Leal; and post-doc: Yayun Zhang, Chenxi Wang, Moriko Qian, Xiao Kong, Xiaona Lin, and Ying Wang; New experiential learning opportunities for involved students in the project; Presentations, seminars, and communications to local communities, such as 2018 WSU ShowCase Conference, NORM 2018, 73rd Northwest Regional Meeting of the American Chemical Society, 2019 WSU ShowCase Conference, 2019 Rotary Club of Pullman Meeting, International Conference on Biofuels and Bioenergy (BBC 2019), 2019 USDA/NIFA Nanotechnology Grantees Annual Meeting, 2020 PNNL Brownbag Series, Webinar of 2020 American Society of Agricultural and Biological Engineers (ASABE) Student Engineering Branch (SEB), 2020 Thermal & Catalytic Sciences Virtual Symposium, 2020 PNNL Brownbag Series, 2018, 2019, 2020, 2021, 2022, 2023 American Society of Agricultural and Biological Engineers (ASABE) Annual International Meeting, 2021 Virtual AFRI Nanotechnology Annual Grantees' Conference, 2021 Virtual International Conference on Environmental Pollution and Governance, 2021 Virtual International Chemical Congress of Pacific Basin Societies, 2021 1st Virtual International Conference through the e3-STArt, an annual International Academic Research and Development Festival (see the session of publication list in Product); 2022 meeting of Alaska Airlines SAF Technologies and Scale up in Washington State, 2022 Gordon Research Conference: Nanoscale Science and Engineering for Agriculture and Food Systems, 2023 28th North American Meeting (NAM) of the North American Catalysis Society, regional and national conferences (see the session of publication list in Product); Extension and outreach include outreach communications and presentations to biomass industrial companies, biofuels, and related industries. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training activities: The funding received from this project has been used to support 6 post-doc, 7 Ph.D. candidates, 1 MS student, and 2 undergraduate students in the WSU Biological Systems Engineering Program. 7 Ph.D. students, 6 post-doc research associates, 1 MS student, and 2 undergraduate students learned to develop new technologies, new processes, and new catalyst materials. Post-doc and graduate students have developed the experience in attaining greater proficiency in developing new technologies and conducting experiments. PIs incorporated the research results from this project in teaching BSysE 593 Renewable Energy Technologies; BSYSE 551 Advanced Biological Systems Engineering Topics: Bioprocess Engineering; BSysE 552 Advanced Biological Systems Engineering Topics: Biomass and Bioenergy; BSYSE 551 Advanced Biological Systems Engineering Topics: Mass Balances, Energy Balances, and Unit Operations; BSYSE 552 Advanced Biological Systems Engineering Topics: Economic and Environmental Sustainability of Energy. Professional development activities: PIs had monthly conference calls with industrial collaborators and active collaborations among each other, and the PI research group had weekly meetings to make sure the good progress of the project. PI and the research team had updates presented at group meetings. Students developed collaboration skills and exchanged technical information cross-group knowledge. Ph.D. Students and Post-docs have participated and presented papers at 2018 WSU ShowCase Conference, NORM 2018, 73rd Northwest Regional Meeting of the American Chemical Society, 2019 WSU ShowCase Conference, 2019 Rotary Club of Pullman Meeting, International Conference on Biofuels and Bioenergy (BBC 2019), 2019 USDA/NIFA Nanotechnology Grantees Annual Meeting, 2020 PNNL Brownbag Series, Webinar of 2020 American Society of Agricultural and Biological Engineers (ASABE) Student Engineering Branch (SEB), 2020 Thermal & Catalytic Sciences Virtual Symposium, 2020 PNNL Brownbag Series, 2018, 2019, 2020, 2021, 2022, 2023 American Society of Agricultural and Biological Engineers (ASABE) Annual International Meeting, 2021 Virtual AFRI Nanotechnology Annual Grantees' Conference, 2021 Virtual International Conference on Environmental Pollution and Governance, 2021 Virtual International Chemical Congress of Pacific Basin Societies, 2021 1st Virtual International Conference through the e3-STArt, an annual International Academic Research and Development Festival (see the session of publication list in Product); 2022 meeting of Alaska Airlines SAF Technologies and Scale up in Washington State, 2022 Gordon Research Conference: Nanoscale Science and Engineering for Agriculture and Food Systems, 2023 28th North American Meeting (NAM) of the North American Catalysis Society. How have the results been disseminated to communities of interest?The PI and the students and post-docs created posters and/or made oral presentations to showcase findings and present the study results. The research findings were communicated to the general public via national and international conferences, such as 2018 WSU ShowCase Conference, NORM 2018, 73rd Northwest Regional Meeting of the American Chemical Society, 2019 WSU ShowCase Conference, 2019 Rotary Club of Pullman Meeting, International Conference on Biofuels and Bioenergy (BBC 2019), 2019 USDA/NIFA Nanotechnology Grantees Annual Meeting, 2020 PNNL Brownbag Series, Webinar of 2020 American Society of Agricultural and Biological Engineers (ASABE) Student Engineering Branch (SEB), 2020 Thermal & Catalytic Sciences Virtual Symposium, 2020 PNNL Brownbag Series, 2018, 2019, 2020, 2021, 2022, 2023 American Society of Agricultural and Biological Engineers (ASABE) Annual International Meetings, 2021 Virtual AFRI Nanotechnology Annual Grantees' Conference, 2021 Virtual International Conference on Environmental Pollution and Governance, 2021 Virtual International Chemical Congress of Pacific Basin Societies, 2021 1st Virtual International Conference through the e3-STArt, an annual International Academic Research and Development Festival, 2022 meeting of Alaska Airlines SAF Technologies and Scale up in Washington State, 2022 Gordon Research Conference: Nanoscale Science and Engineering for Agriculture and Food Systems, 2023 28th North American Meeting (NAM) of the North American Catalysis Society. The published journal papers and proceedings can be found in previous sessions in this progress report. We also disseminated our research results to communities by presenting them to industrial delegations and academic communities. Our outreach dissemination efforts includevirtual and personal meetings with industrial experts, such as North America Green Pulp Inc., Sustainable Fiber Technologies, Inc.,Energy Associates Intl., LLC,Molten Materials, LLC., Ruiz Energy Corporation,Sedron Technologies Inc. etc. We made outreach communications and engagements with the biobased industrial companies, and signed Mutual Confidential Disclosure Agreement and Confidentiality and Noncircumvention Agreement withindustrial companies. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Impact: The recent development of functionalized nanocelluloses applied in various industrial sectors has resulted in a transformation in the nanocellulose market. The changes are driven by the increasing demand for biodegradable and non-toxic nanomaterials. The increasing market provides new opportunities for the agricultural economy and helps to activate the existing forestry industry, which suffered a significant recession due to the declining global demand for paper. The existing Nanocrystalline cellulose (NCC) technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (i.e. sulfuric acid, 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project is to develop a green process of NCC production based on enzymatic hydrolysis, which leads to less environmental concerns and unmodified surface chemistry of NCC. Our hypothesis is that by careful selection of cellulase enzymes and hydrolysis conditions, it is possible to efficiently produce NCC from biomass without using a high concentration of harsh acids, and subsequently synthesize metal-NCC nanoparticles for jet fuel production.The project team is focused directly on creating and integrating new technologiesand is lining and engaging related industries in our outreach and education efforts and involved them in the development of biomass-derived high-value catalysts, chemicals, and biofuels. Major activities completed / experiments conducted/ data collected/ results / key outcomes: Cellulose separation and delignification from Douglas fir sawdust: We developed a new process carrying out the carbonization and sulfonation in one single step which simplifies the process and substantially reduced the time and energy for the heterogeneous acid catalysts (sulfonated carbon catalysts (SCC)).The application of SCCin the delignification ofbiomass in an organosolv process using ethanol as solvent was first explored in this study. The SCC with the highest SO3H density (1.1887 mmol/g) was obtained in biomass treated at 92°C while the lowest SO3H density (0.6726 mmol/g) was recorded at 148°C. The SO3H density of the SCC (0.6726-1.1887 mmol/g) from this study was higher compared to the sulfonated mesoporous expanded starch called Starbon-400 (0.5 mmol/g) and the sulfonated biomass-based solid catalysts (0.39-0.66 mmol/g) reported in literature. Thus, the synthesis of SCC via simultaneous carbonization and sulfonation using H2SO4 as reagent can be an alternative approach for a more simple process that would greatly reduce the time and energy requirement. The highest ethanol organosolv lignin (EOL) yield of 63.56% with a substrate yield of 39.08% was achieved with SCC in the ethanol organosolv delignification ofbiomass. The FTIR spectra of the isolated lignin revealed typical features of G-lignin, indicating that no drastic changes took place in the lignin structure during the process. Reduced acid loading conditions on nanocrystalline cellulose (NCC) production: The conventional method of using highly concentrated sulfuric acid at optimum 63.5 wt.% produced an NCC yield of 30 wt.% from microcrystalline cellulose (MCC). The use of concentrated sulfuric acid raises numerous concerns associated with equipment maintenance, process viability, product safety, and environmental protection. A dilute-acid pretreatment assisted with microwave irradiation was developed to efficiently fabricate nanocrystalline cellulose (NCC) with the single use of the cellulase from Aspergillus niger. The use of microwave heating and diluted sulfuric acid solution (1, 2, 5, and 10 wt. %) increased the NCC yield of subsequent enzymatic hydrolysis with a maximum value of 84.4 wt.% from less than 10 wt.% without the pretreatment. The severity of pretreatment conditions affected the crystal dimension of rod-like nanocrystals. The crystallinity and thermal stability of extracted NCC varied by the acid concentration used in pretreatment conditions and also by the duration of enzymatic hydrolysis. The highest peak decomposition temperature of 378.1ºC as well as the highest NCC yield were recorded in the NCC extracted in 5 wt.% sulfuric acid with microwave heating. The pretreatment effectively facilitated enzymatic hydrolysis, and the synergetic effect of microwave irradiation in the presence of sulfuric acid was associated with the improved thermal stability and crystallinity in the final products. Nanoparticles-nanocellulose derived carbon catalysts: The remarkable enhancement of phenolic monomer generation and hydrogen was achieved through catalytic pyrolysis of Douglas fir over nanocellulose derived biochar catalyst for the first time. And at the temperature of 650ºC and 3 of nanocellulose biochar to biomass ratio, the quantification results showed that the concentration of phenol was increased to 53.77 mg/mL from 15.76 mg/mL of free of catalyst. The concentration of cresols were facilitated to 44.51 mg/mL from 20.95 mg/mL. Up to 85.32 vol.% of hydrogen was observed, increasing from 45.53 vol.% of the non-catalytic process. After 15 cycles of reuse, nanocellulose biochar catalysts still favored producing a much higher concentration of phenolic monomers and hydrogen than that of the absence of catalysts. A powerful simple carbon catalyst derived from nanocellulose was applied to the catalytic upcycling of waste plastics into H2 and liquid fuels for the first time. For the results from model low-density polyethylene (LDPE) pyrolysis, the C8-C16 aliphatics and monocyclic aromatics were dominant constitutes of the liquid product with the yields ranging from 22 to 68 wt.%. Up to 92 vol.% of H2 was detected in the gaseous product with a yield of 36 wt.%. Moreover, this nanocellulose derived carbon catalyst was tested effectively to convert the real waste plastics including grocery bags and packaging tray into valuable liquid and H2-enriched gas. Impregnation to nanocellulose-derived nanocarbon particles was performed to prepare a supported Ni catalyst for hydrotreating of aromatics. Selective benzene hydrogenation to cyclohexane over the Raney Ni/nanocellulose derived carbon catalysts with maximum conversion of 94.4 mol% obtained at 300ºC. As aromatics and cycloalkanes are major components of the jet fuels, a catalytically green route was achieved with the assistant of biomass-derived nanocellulose and nanocarbon catalysts, biomasses and waste plastics can be converted to jet fuels range hydrocarbons. Change in Knowledge: Increased understanding of the control and degree we tune for the nanocellulose microstructure during cellulose hydrolysis; Increased understanding of how the NCC yield was affected by acid concentrations, enzymatic hydrolysis, and pretreatment methods; Increased understanding of reaction mechanism and reactions responsible for the formation of aromatics and cycloalkanes from nanocellulose derived catalysts. Change in Action: A new way of producing nanocellulose and nanocarbon catalysts from lignocelluloses biomassand lay the foundation for achieving advanced bio-jet fuel production by using biomass-derived nanocelluose and nanocarbon catalysts. Change in Condition: The existing NCC technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (hydrochloric acid and sulfuric acid at typically 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project and the accelerated development of its technology will improve the current situation of nanocellulose production, biomass conversion, and enhance the economic and energy security of the United States and maintain a technological lead in developing and deploying advanced energy technologies. This conversion system will significantly reduce energy-related emissions, including greenhouse gases and have a positive carbon effect.

Publications

  • Type: Journal Articles Status: Published Year Published: 2023 Citation: X. Lin, H. Lei, C. Wang, M. Qian, W. Mateo, X. Chen, Y. Guo, E. Huo. 2023. The effects of pore structures and functional groups on the catalytic performance of activated carbon catalysts for the co-pyrolysis of biomass and plastic into aromatics and hydrogen-rich syngas. Renewable Energy, 202, 855-864.
  • Type: Journal Articles Status: Published Year Published: 2023 Citation: M Bai, Z Song, Z Yang, Z Guo, Y Liu, H Guo, H Lei, E Huo. 2023. Catalytic conversion mechanism of guaiacol as the intermediate of lignin catalytic pyrolysis on MgO surface: density functional theory calculation. Journal of Molecular Liquids, 369, 120920.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: L Dai, R Ruan, S You, H Lei. 2022. Paths to sustainable plastic waste recycling. Science, Vol 377, Issue 6609, p934.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: R Zou, C Wang, M Qian, E Huo, X Kong, Y Wang, L Dai, L Wang, X Zhang, W C Mateo, R Ruan, H Lei. 2022. Catalytic co-pyrolysis of solid wastes (low-density polyethylene and lignocellulosic biomass) over microwave assisted biochar for bio-oil upgrading and hydrogen production. Journal of Cleaner Production, 374, 133971.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: Bai, M; Song, Z; Yang, Z; Liu, Y ; Qian, M; Zou, R; Lei, H; Zhang, Y; Huo, E. 2022. Catalytic co-pyrolysis of low-density polyethylene (LDPE) and lignin for jet fuel range hydrocarbons over activated carbon catalyst. International Journal of Energy Research,46, 13, 18529-18539.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: M Qian, Y Zhao, E Huo, C Wang, X Zhang, X Lin, L Wang, X Kong, R Ruan, H Lei. 2022. Improving catalytic production of aromatic hydrocarbons with a mesoporous ZSM-5 modified with nanocellulose as a green template. Journal of Analytical and Applied Pyrolysis, 166, 105624.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: L Wang, T Li, L Tao, P Ma, H Lei, J Liu. 2022. A novel copper-doped porous carbon nanospheres film prepared by one-step ultrasonic spray pyrolytic deposition on monocrystalline silicon wafers for photocatalytic degradation of methyl orange. Process Safety and Environmental Protection, 158, 79-86.
  • Type: Journal Articles Status: Submitted Year Published: 2023 Citation: Y Zhao, Y Liu, H Lei, R Ruan, Y Wang, D Duan, L Fan, M Qian, R Zou, C Wang, E Huo, S Dong, Z Yue, Y jie. 2023. Microwave-assisted synthesis of nano-carbon-based composite catalyst catalysts for high-quality bio-oil production from pyrolysis of low-density polyethylene. Bioresource Technology. Submitted
  • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: (Invited) H Lei. 2023. Carbon from lignocellulosic biomass and its application as a catalyst. 2023 WSU/PNNL seminar
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2023 Citation: R Zou, M Qian, C Wang,, H Lei. 2023. Comparison between catalytic fast pyrolysis of plastics with carbon catalysts derived from lignin and cellulose. 2023 ASABE Annual International Meeting, Omaha, Nebraska, July 9-12, 2023
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2023 Citation: R Zou, M Qian, C Wang,, H Lei. 2023. Machine learning prediction of activated biochar yield and morphological characteristics based on biomass characteristics. 2023 ASABE Annual International Meeting, Omaha, Nebraska, July 9-12, 2023
  • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: R Zou, M Qian, C Wang,, H Lei. 2023. Nanocellulose-derived carbon catalysts for syngas upgrading in co-pyrolysis of plastics and biomass. The 28th North American Meeting (NAM) of the North American Catalysis Society will be held in Providence, Rhode Island, June 18-23, 2023
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: C Wang, R Zou, M Qian, W Mateo, H Lei. 2022. Toward advancing the resource recovery from carbon dioxide through microwave-irradiated gasification of biomass sourced biochar. 2022 ASABE Annual International Meeting, Houston, TX, July 17-20, 2022
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: C Wang, R Zou, M Qian, W Mateo, H Lei. 2022. Biomass sourced biochar catalyst to advance the catalytic upcycling of waste single-use mask. 2022 ASABE Annual International Meeting, Houston, TX, July 17-20, 2022
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: R Zou,C Wang, M Qian,H Lei�. 2022. Nano-cellulose derived biochar catalytic co-pyrolysis of LDPE and biomass for pyrolysis products upgrading. 2022 ASABE Annual International Meeting, Houston, TX, July 17-20, 2022
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: M Qian, H Lei�,C Wang, R Zou. 2022. Co-processing of plastic mixture in catalytic pyrolysis of biomass over mesoporous ZSN-5 prepared with nanocellulose-mediated synthesis.2022 ASABE Annual International Meeting, Houston, TX, July 17-20, 2022
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: M Qian,H Lei�,C Wang, R Zou. 2022. Synthesis of nickel-doped carbon-zeolite composite with nanocellulose for catalytic upcycling of waste disposable mask to gasoline and syngas.2022 ASABE Annual International Meeting, Houston, TX, July 17-20, 2022
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: H Lei, M Qian, C Wang, R Zou, E Villota, Y Zhao, E Huo, Q Zhang, W Mateo, X Lin. 2022.Nanocellulose as green template and precursor to metal nanoparticle catalyst support for catalytic upcycling of plastic and biomass wastes to jet fuel-range petrochemicals. 2022 Gordon Research Conference: Nanoscale Science and Engineering for Agriculture and Food Systems Convergence of Nanotechnology With Food and Agriculture, Manchester, NH, June 18-19, 2022
  • Type: Journal Articles Status: Submitted Year Published: 2023 Citation: R Zou, C Wang, M Qian, R Lei, Y Zhao, Q Zhang, E Huo, X Kong, X Lin, L Wang, X Zhang, A Gluth, B Harahap, Y Wang, L Dai, J Zhao,R Ruan, H Lei. 2023. Catalytic fast co-pyrolysis of Douglas Fir and low-density polyethylene with nanocellulose-derived carbon catalyst for enhancing syngas and bio-oil products. Chemical Engineering Journal. Submitted
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: C. Wang, R. Zou, M. Qian, X. Kong, E. Huo, X. Lin, L. Wang, X. Zhang, R. Ruan, H. Lei. 2022. Improvement of the carbon yield from biomass carbonization through sulfuric acid pre-dehydration at room temperature. Bioresource Technology 355, 127251.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: R. Zou, M. Qian, C. Wang, W. Mateo, Y. Wang, L. Dai, X. Lin, Y. Zhao, E. Huo, L. Wang, X. Zhang, X. Kong, R. Ruan, H Lei. 2022. Biochar: from by-products of agro-industrial lignocellulosic waste to tailored carbon-based catalysts for biomass thermochemical conversions. Chemical Engineering Journal, 441,135972.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: C. Wang, R. Zou, H. Lei, M. Qian, X. Lin, W. Mateo, L. Wang, X. Zhang, R. Ruan. 2022. Biochar-advanced thermocatalytic salvaging of the waste disposable mask with the production of hydrogen and mono-aromatic hydrocarbons. Journal of Hazardous Materials, 426, 128080.
  • Type: Journal Articles Status: Accepted Year Published: 2023 Citation: E. M. Villota, H. Lei, S. M. A. Villota, M. Qian, W. Mateo, Y. Zhao, E. Huo, Q. Zhang, X. Lin, Z. Huang. 2023. Adsorption Isotherm and Kinetics of Methylene Blue Dye on Chemically-Activated Porous Carbon from Douglas fir. Materials International. Accepted.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, X. Kong, R. Zou, M. Qian, Y. Zhao, W. Mateo. 2021. Catalytic upcycling of waste plastics over nanocellulose derived biochar catalyst for the coupling harvest of H2 and liquid fuels. Science of the Total Environment, 779, 146463.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: M. Qian, H. Lei, E. Villota, W. Mateo, Y. Zhao, E. Huo, C. Wang, R. Zou. 2021. Enhanced production of renewable aromatic hydrocarbons for jet-fuel from softwood biomass and plastic waste using hierarchical ZSM-5 modified with lignin-assisted re-assembly. Energy Conversion and Management, 236, 114020.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: M. Qian, H. Lei, Y. Zhao, C. Wang, E. Huo, Q. Zhang, W. Mateo, X. Lin, X. Kong, R. Zou. 2021. High yield production of nanocrystalline cellulose by microwave-assisted dilute-acid pretreatment combined with enzymatic hydrolysis.Chemical Engineering and Processing - Process Intensification, 160, 108292.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, Y. Zhao, M. Qian, X. Kong, W. Mateo, R. Zou, R. Ruan. 2021. Integrated harvest of phenolic monomers and hydrogen through catalytic pyrolysis of biomass over nanocellulose derived biochar catalyst. Bioresource Technology, 320A, 124352.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: W. Mateo, H. Lei, E. Villota, M. Qian, Y. Zhao, E. Huo, Q. Zhang, X. Lin, and C. Wang. 2021. One-step Synthesis of Biomass-based Sulfonated Carbon Catalyst by Direct Carbonization-Sulfonation for Organosolv Fractionation. Bioresource Technology, 319, 124194.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: X. Lin, H. Lei, W. Yi, H. Cai, X. Chen, Y. Guo. 2021. Catalytic co-pyrolysis of biomass and low-density polyethylene over activated carbon catalyst. Transactions of the CSAE, 37(15), 189-196.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: E. Huo, C. Liu, L. Xin, Y. Zhang, Y Zhao, M Qian, X Lin, H. Lei. 2021. High purity hydrocarbon fuel production by co-pyrolysis of low density polyethylene (LDPE) and wheat straw over activated carbon catalyst.Sustainable Energy & Fuels, 5, 23, 6145-6156.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: X. Lin, H. Lei, Q. Zhang, M. Qian, Y. Zhao, E. Huo, C. Wang, W. Mateo, E. Villota. 2020. Enhancing jet fuel range hydrocarbon production from catalytic co-pyrolysis of Douglas fir and low-density polyethylene over Fe-modified bifunctional activated carbon catalysts. Energy Conversion and Management, 211, 112757.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: Y. Zhao, H. Lei, Y. Liu, R. Ruan, M. Qian, E. Huo, Q. Zhang, Z. Huang, X. Lin, C. Wang, W. Mateo, E. M. Villota. 2020. Microwave-assisted Synthesis of Bifunctional Magnetic Solid Acid for Hydrolyzing Cellulose to Prepare Nanocellulose. Science of the Total Environment, 731, 138751.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: X. Kong, Y. Zhu, H. Lei, C. Wang, Y. Zhao, E. Huo, X. Lin, Q. Zhang, M. Qian, W. Mateo, R. Zou, Z. Fang, and R. Ruan. 2020. Synthesis of graphene-like carbon from biomass pyrolysis and its applications. Chemical Engineering Journal, 399, 125808.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: Q. Zhang, H. Lei, H. Cai, X. Han, X. Lin, M. Qian, Y. Zhao, E. Huo, E. M. Villota, W. Mateo. 2020. Improvement on the properties of microcrystalline cellulose/polylactic acid composites using activated biochar. Journal of Cleaner Production, 252, 119898.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: W. Mateo, H. Lei, E. Villota, M. Qian, D. Duan, Y. Zhao, E. Huo, Q. Zhang, X. Lin, and Z. Huang. 2020. Synthesis and characterization of sulfonated activated carbon as a catalyst for bio-jet fuel production from biomass and waste plastics. Bioresource Technology, 297,122411.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: D. Duan, Y. Zhang, H. Lei, M. Qian, E. Villota, Y. Wang, R. Ruan. 2020. A novel production of phase-divided jet-fuel-ranged hydrocarbons and phenols-enriched chemicals from catalytic co-pyrolysis of lignocellulosic biomass with waste plastics over carbon catalysts. Sustainable Energy & Fuels, 4, 3687 - 3700.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: D. Duan, Y. Zhang, Y. Wang, H. Lei, Q. Wang; R. Ruan. 2020. Production of renewable jet fuel and gasoline range hydrocarbons from catalytic pyrolysis of soapstock over corn cob-derived activated carbons. Energy, 209, 118454.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: C. Wang, H. Lei, M. Qian, E. Huo, Y. Zhao, Q. Zhang, W. Mateo, X. Lin, X. Kong, R. Zou, R. Ruan. 2020. Application of highly stable biochar catalysts for efficient pyrolysis of plastics: a readily accessible potential solution to a global waste crisis. Sustainable Energy & Fuels, 4, 4614 - 4624.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: E. Huo, D. Duan , H. Lei, C. Liu, Y. Zhang, J. Wu, Y. Zhao, Z. Huang, M. Qian, Q. Zhang, X. Lin, C. Wang, W. Mateo, E. M. Villota, R. Ruan. 2020. Phenols production from Douglas fir catalytic pyrolysis with MgO and biomass-derived activated carbon catalysts. Energy, 199, 117459.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: M. Qian, H. Lei, Y. Zhao, E. Villota, E. Huo, C. Wang, X. Zhang. 2021. Lignin-mediated preparation of hierarchical ZSM-5 catalysts and their effects in catalytic co-pyrolysis of softwood biomass and low-density polyethylene mixtures. ACS Sustainable Chemistry & Engineering. 9(37), 12602-12613.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, R. Zou, M. Qian, W. Mateo, X. Lin, R. Ruan. 2021. Biochar-driven simplification of the compositions of cellulose-pyrolysis-derived biocrude oil coupled with the promotion of hydrogen generation. Bioresource Technology. 334, 125251.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: X. Lin, L. Kong, X. Ren, D. Zhang, H Cai, H. Lei. 2021. Catalytic co-pyrolysis of torrefied poplar wood and high-density polyethylene over hierarchical HZSM-5 for mono-aromatics production. Renewable Energy, 164, 87-95.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: D. Duan, X. Dong, Q. Wang, Y. Zhang, R. Ruan, Y. Wang, H. Lei. 2021. Production of renewable phenols from corn cob using catalytic pyrolysis over self-derived activated carbons prepared with torrefaction pretreatment and chemical activation. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 126507.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: D. Duan, D. Chen, L. Huang, Y. Zhang, Q. Wang,G. Xiao,W. Zhang, H. Lei, R. Ruan. 2021. Activated carbon from lignocellulosic biomass as catalyst: A review of the applications in fast pyrolysis process. Journal of Analytical and Applied Pyrolysis, 158, 105246.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: E. Huo, H. Lei, C. Liu, Y. Zhang, L. Xin, Y. Zhao, M. Qian, Q. Zhang, X. Lin, C. Wang, W. Mateo, E. M. Villota, R. Ruan. 2020. Jet fuel and hydrogen produced from waste plastics catalytic pyrolysis with activated carbon and MgO. Science of the Total Environment, 727, 138411.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: Y. Zhang, D. Duan, H. Lei, C. Wang, M. Qian, E. Villota, W. Mateo. 2020. From Douglas fir to renewable H2-enriched syngas via ex-situ catalytic pyrolysis over metal nanoparticles-nanocellulose derived carbon catalysts. Sustainable Energy and Fuels, 4 1084-1087.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: M. Qian, H. Lei, E. Villota, W. Mateo, Y. Zhao, E. Huo, Q. Zhang, X. Lin, and Z. Huang. 2019. Optimization of delignification from Douglas fir sawdust by alkaline pretreatment with sodium hydroxide and its effect on structural and chemical properties of lignin and pyrolysis products. Bioresource Technology Reports, 8, 100339.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: D. Duan, Y. Zhang, H. Lei, E. Villota, R. Ruan. 2019. Renewable jet-fuel range hydrocarbons production from co-pyrolysis of lignin and soapstock with the activated carbon catalyst. Waste Management, 88, 1-9.
  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, D.Duan, E. Villota, R.Ruan. 2018. From Glucose-Based Carbohydrates to Phenol-rich Bio-oil Integrated with Syngas Production via Catalytic Pyrolysis over Activated Carbon Catalyst. Green Chemistry, 20, 3346 - 3358.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: D. Duan, H. Lei, Y. Wang, Y. Liu, R. Ruan, Y Liu, L. Ding, Y. Zhang, L. Liu. 2019. Renewable phenol production from lignin with acid pretreatment and ex-situ catalytic pyrolysis. Journal of Cleaner Production, 231, 331-340.
  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, K. Qian, E. Villota. 2018. Renewable High-Purity Mono-Phenol Production from Catalytic Microwave-Induced Pyrolysis of Cellulose over Biomass-Derived Activated Carbon Catalyst. ACS Sustainable Chemistry & Engineering, 6 (4), pp 53495357.
  • Type: Book Chapters Status: Published Year Published: 2022 Citation: Y. Zhou, X. Li, N. Zhao, H. Elshareef, Y. Yu, M. Qian, H. Lei. 2022. Thermal processing of biomass for energy and fuel production in Advances in Bioenergy Vol. 7 ISBN: 9780323989848. Elsevier.
  • Type: Book Chapters Status: Published Year Published: 2020 Citation: R. Ruan, K. Ding, S. Liu, P. Peng, N. Zhou, A. He, P. Chen, Y. Cheng, Y. Wang, Y. Liu, H. Lei, M. Addy, K. Cobb. 2020. Gasification and pyrolysis of waste, in Current Developments in Biotechnology and Bioengineering, chapter 12, pp 263-297. Elsevier.doi: 10.1016/B978-0-444-64309-4.00012-X.
  • Type: Book Chapters Status: Published Year Published: 2019 Citation: R. Ruan, Y. Zhang, P. Chen, S. Liu, L. Fan, N. Zhou, K. Ding, P. Peng, M. Addy, Y. Cheng, E. Anderson, Y. Wang, Y. Liu, H. Lei, B. Li. 2019. Biofuels: Introduction, in Biofuels: Alternative Feedstocks and Conversion Processes for the Production of Liquid and Gaseous Biofuels in Biomass, Biofuels, Biochemicals (2nd Edition). pp. 343. Academic Press.
  • Type: Theses/Dissertations Status: Published Year Published: 2021 Citation: Wendy Mateo. 2021. PhD thesis: Development and optimization of catalytic pyrolysis process of lignocellulosic biomass over sulfonated carbon-based catalyst.
  • Type: Theses/Dissertations Status: Published Year Published: 2020 Citation: Moriko Qian. 2020. PhD thesis: Biomass-assisted synthesis of hierarchical zeolites for catalytic fast pyrolysis of lignocellulose biomass and waste plastic
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: M. Qian, H. Lei�, C. Wang, R. Zou, W. Mateo. 2021. Integrated production of syngas and aromatic hydrocarbons from low-density polyethylene using metal-doped nanocarbon-zeolite composites.2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: M. Qian, H. Lei�, C. Wang, R. Zou, W. Mateo. 2021. Impacts of acid and base activations on nanocellulose-derived carbons for catalytic co-pyrolysis of lignocellulosic biomass and polyethylene mixture. 2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, R. Zou, M. Qian, W. Mateo. 2021. Biochar-driven simplification of the compositions of cellulose-pyrolysis-derived oil coupled with the promotion of hydrogen generation. 2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, R. Zou, M. Qian, W. Mateo. 2021. Catalytic upcycling of waste plastics over nanocellulose derived biochar catalyst for the coupling harvest of hydrogen and liquid fuels. 2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: R. Zou, H. Lei, C. Wang, M. Qian, W. Mateo. 2021. Catalytic upgrading of LDPE pyrolysis gas over nanocellulose derived biochar supported Ni/Pd catalysts. 2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: M. Qian, H. Lei�, C. Wang, R. Zou, W. Mateo. Nanocellulose extraction and catalytic pyrolysis for bio jet fuel. 2021. 1st Virtual International Conference through the e3-STArt, an annual International Academic Research and Development Festival, October 26 to 28, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Invited. C. Wang, H. Lei, R. Zou, M. Qian, W. Mateo. 2021.Catalytic upcycling of waste plastics over nanocellulose derived biochar catalyst for the coupling harvest of hydrogen and liquid fuels. 2021 Virtual International Conference on Environmental Pollution and Governance (ICEPG 2021). May 21-23, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: H. Lei, M. Qian, C. Wang, R. Zou, E. Villota, Y. Zhao, E. Huo, Q. Zhang, W. Mateo, X. Lin. 2021. Nano cellulose-based nanoparticle catalysts for bio-jet fuel ranged cycloalkanes production.2021 Virtual AFRI Nanotechnology Annual Grantees' Conference. October 6-7, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: M. Qian, H. Lei�, C. Wang, R. Zou, W. Mateo. 2021. Introduction of nanocellulose in hydrothermal treatment of ZSM-5 and its effect on catalytic pyrolysis of lignocellulosic biomass. Virtual International Chemical Congress of Pacific Basin Societies, December 16-21, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: C. Wang, H. Lei, Y. Zhao, M. Qian, W. Mateo, E. Mateo, E. Huo. 2020. Enhancement of H2 generation via catalytic pyrolysis of biomass over nanocellulose derived biochar catalyst. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Y. Zhao, R. Zou, H. Lei, Y. Liu, R. Ruan,Y. Wang, M. Qian. 2020. Preparation of nanocellulose by enzymatic hydrolysis of cellulose pretreated with carbon-based solid acid. 2020 Thermal & Catalytic Sciences Virtual Symposium, October 5 - 7, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Y. Zhao, R. Zou,H. Lei�, M. Qian, E. Villota, E. Huo, W. Mateo, Q. Zhang, X. Lin, C. Wang. 2020.Preparation of nanocellulose by enzymatic hydrolysis of cellulose pretreated with carbon-based solid acid. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: C. Wang, H. Lei, M. Qian, Y. Zhao, R. Zou, W. Mateo, X. Kong. 2020. Enhancing the Generation of Phenolic Monomers and H2 through Catalytic Pyrolysis of Biomass over Nanocellulose Derived Biochar Catalyst. 2020 Thermal & Catalytic Sciences Virtual Symposium, October 5 - 7, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Y. Zhao, R. Zou,H. Lei�, M. Qian, E. Villota, E. Huo, W. Mateo, Q. Zhang, X. Lin, C. Wang. 2020.Microwave-assisted synthesis of nano-biocarbon-based catalysts to improve the quality of low-density polyethylene pyrolysis bio-oil. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: M. Qian, H. Lei�, Y. Zhao, C. Wang, X. Kong, W. Mateo., R. Zou. 2020. Hydrothermal treatment with nanocellulose for enhancing the catalytic performance of H-ZSM-5 zeolite in aromatic hydrocarbon production. 2020 Thermal & Catalytic Sciences Virtual Symposium, October 5 - 7, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: M. Qian, H. Lei�, E. Villota, Y. Zhao, E. Huo, W. Mateo, C, Wang. 2020. Development of meso-micro structure in MFI zeolites via nanocrystalline cellulose templating for conversion of lignocellulosic biomass to aromatic hydrocarbons. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: M. Qian, H. Lei�, Y. Zhao, E. Villota, E. Huo, W. Mateo, Q. Zhang, X. Lin, C. Wang. 2020. Synthesis of zeolite-nanocarbon composite using nanocellulose for catalytic conversion of plastic waste to liquid oil integrated with syngas production. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: M. Qian, H Lei�,E, M. Villota, W, C. Mateo, D. Duan, Y. Zhao. 2019. Modification of ZSM-5 zeolites for improving aromatic hydrocarbon production in co-fed biomass pyrolysis with waste plastics. 2019 WSU ShowCase Conference, Pullman, WA, March 25, 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: (Invited) H. Lei, Y. Zhang, D. Duan, E. Villota, Y. Zhao, Y. Liu, R., Ruan. 2019. Activated carbon as catalyst for biomass and waste plastics conversions to chemicals and biofuels. International Conference on Biofuels and Bioenergy (BBC 2019), San Francisco, CA, USA, April 29-May 01, 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: (Invited) H. Lei. 2020.Fuel and chemical production from waste plastics via catalytic pyrolysis over carbon catalysts. 2020 PNNL Brownbag Series, June 24, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: M. Qian, H. Lei, E. Villota, W. Mateo, D. Duan, Y. Zhao, E., Huo, Q. Zhang, X. Lin, Z. Huang. 2019. A green approach to nanocrystalline cellulose production with cellulase from Aspergillus niger. 2019 ASABE Annual International Meeting, Boston, Massachusetts USA, July 7-10, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Y. Zhao, H. Lei, Y. Liu, D. Duan, R. Ruan, M. Qian, E. Huo, E. Villota, W. Mateo, Q. Zhang, X. Lin, Z. Huang. 2019. Preparation of magnetic biochar-based solid acid and its nano-effect on cellulose. 2019 ASABE Annual International Meeting, Boston, Massachusetts USA, July 7-10, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: M. Qian, Y. Zhang, D. Duan, Y. Zhao, W. Mateo, E. Huo, H. Lei. 2019.Nano Cellulose-Based Nanoparticle Catalysts For Bio-Jet Fuel Ranged Cycloalkanes Production. 2019 USDA/NIFA Nanotechnology Grantees Annual Meeting, Vanderbilt University, May 20-21, 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: M. Qian, H. Lei, E. Villota, W. Mateo, D. Duan, Y. Zhao. 2019. Enhancement of aromatic hydrocarbons from co-feeding of lignocellulosic biomass with plastics over hierarchical zeolites. 2019 ASABE Annual International Meeting, Boston, Massachusetts USA, July 7-10, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: H. Lei. 2019. H2 saving process for production of aromatics for jet fuels. 2019 Five-Year Reflection. Sun Grant Western Regional Center, Newport, OR, August 21-22, 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: (Invited) H. Lei, M. Qian, Y. Zhang, D. Duan, E. Villota, W. Mateo, Y. Zhao. 2019. Carbon catalysts for producing jet fuel from plasticwaste via catalytic pyrolysis. 2019 Rottary Club meeting, Pullman, WA, July 24, 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, E. Villota, M. Qian. 2018.Nanocellulose production and its derived carbon catalysts for syngas upgrading. 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29 - August 01, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, E. Villota, M. Qian. 2018. Bio-oil Upgrading over Nanocellulose-Derived Nano-Carbon Catalysts Doped with Metal Atoms. 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29 - August 01, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: W. Mateo, H. Lei, E. Villota, Z. Yang, Y. Zhang, M. Qian, K. Qian, D. Duan. 2018. Synthesis and Performance of Carbon-based Solid Acid Catalyst for Organosolv Fractionation. 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29 - August 01, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, E. Villota, M. Qian, D. Duan. 2018. Nanocellulose-Derived Nano-Carbon Catalysts for Biomass Conversion and Bio-oil Upgrading. Nanoscale Science and Engineering for Agriculture and Food Systems Gordon Research Conference, South Hadley, MA, June 03 - 08, 2018
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, D. Duan, E. Villota, M. Qian. 2018. From Carbohydrates to Phenol-rich Bio-oil Integrated with Syngas Production via Catalytic Pyrolysis over Activated Carbon Catalyst. 2018 WSU ShowCase Conference, Pullman, WA, March 25, 2018


Progress 03/01/21 to 02/28/22

Outputs
Target Audience:Biomass industrial companies, biofuel-related industries, biomass and biofuel producers, processors, wholesalers, and retailers: including Creative Energy Systems Inc., MS Sustainables, LLC., North America Green Pulp Inc., USS International Group, LLP., Sustainable Fiber Technologies, Inc., Ambient Energy LLC, Clearwater Supply, Inc., Energy Associates Intl., LLC,Conrad Industries, Inc., DTG Recycling Group, LLC., Molten Materials, LLC., Ruiz Energy Corporation, Sedron Technologies Inc. Efforts: Formal classroom instruction (new course lectures/sessions) about the project in BSYSE 551 Advanced Biological Systems Engineering Topics: Bioprocess Engineering, BSysE 552 Advanced Biological Systems Engineering Topics: Biomass and Bioenergy; Mass Balances, Energy Balances, and Unit Operations; Economic and Environmental Sustainability of Energy. Development of curriculum (new lecture sessions on biomass conversion and catalysis, biomass-derived nanocellulose, nanocarbon catalysts, chemicals, bio-jet fuel); Trained graduate and undergraduate students and post-doctoral researchers who work on this project will eventually join the workforce and contribute to the effort of utilizing biomass and developing bioproducts (i.e. nanocellulose, nanocarbon catalysts) and renewable energy technology for the future energy needs: PhD students: Wendy Mateo, Rongge Zou, Erguang Huo, Yunfeng Zhao; and post-doc: Chenxi Wang, Moriko Qian, and Ying Wang; New experiential learning opportunities for involved students in the project; Presentations, seminars, and communications to local communities, regional and national conferences, such as 2021 Virtual American Society of Agricultural and Biological Engineers (ASABE) Annual International Meeting, 2021 Virtual AFRI Nanotechnology Annual Grantees' Conference, 2021 Virtual International Conference on Environmental Pollution and Governance, 2021 Virtual International Chemical Congress of Pacific Basin Societies, 2021 1st Virtual International Conference through the e3-STArt, an annual International Academic Research and Development Festival (see the session of publication list in Product); Extension and outreach include outreach communications and presentations to biomass industrial companies, biofuels, and related industries. Changes/Problems:None. What opportunities for training and professional development has the project provided?Training activities: The funding received from this project has been used to support 3 post-doc, 4 Ph.D. candidates in the WSU Biological Systems Engineering Program. 4 Ph.D. students and 3 post-doc research associates learned to develop new technologies, new processes, and new catalyst materials. Post-doc and Ph.D. students have developed the experience in attaining greater proficiency in developing new technologies and conducting experiments. PIs incorporated the research results from this project in teaching BSYSE 551 Advanced Biological Systems Engineering Topics: Bioprocess Engineering, BSysE 552 Advanced Biological Systems Engineering Topics: Biomass and Bioenergy; Mass Balances, Energy Balances, and Unit Operations; Economic and Environmental Sustainability of Energy. Professional development activities: PIs had monthly conference calls with industrial collaborators and active collaborations among each other, and the PI research group had weekly meetings to make sure the good progress of the project. PI and the research team had updates presented at group meetings. Students developed collaboration skills and exchanged technical information cross-group knowledge. Ph.D. Students and Post-docs have participated and presented papers at the 2021 Virtual American Society of Agricultural and Biological Engineers (ASABE) Annual International Meeting, 2021 Virtual AFRI Nanotechnology Annual Grantees' Conference, 2021 Virtual International Conference on Environmental Pollution and Governance, 2021 Virtual International Chemical Congress of Pacific Basin Societies, 2021 1st Virtual International Conference through the e3-STArt, an annual International Academic Research and Development Festival. How have the results been disseminated to communities of interest?The PI and the students and post-docs created posters and/or made oral presentations to showcase findings and present the study results. The research findings were communicated to the general public via national and international conferences, such as 2021 Virtual American Society of Agricultural and Biological Engineers (ASABE) Annual International Meeting, 2021 Virtual AFRI Nanotechnology Annual Grantees' Conference, 2021 Virtual International Conference on Environmental Pollution and Governance, 2021 Virtual International Chemical Congress of Pacific Basin Societies, 2021 1st Virtual International Conference through the e3-STArt, an annual International Academic Research and Development Festival. The published journal papers and proceedings can be found in previous sessions in this progress report. We also disseminated our research results to communities by presenting them to industrial delegations and academic communities. Our outreach dissemination efforts include virtual and personal meetings with industrial experts, such as North America Green Pulp Inc., Sustainable Fiber Technologies, Inc., Energy Associates Intl., LLC, Molten Materials, LLC., Ruiz Energy Corporation, Sedron Technologies Inc. etc. We made outreach communications and engagements with the biobased industrial companies, and signed Mutual Confidential Disclosure Agreement and Confidentiality and Noncircumvention Agreement with industrial companies. What do you plan to do during the next reporting period to accomplish the goals?During the next year of 2022, we will investigate the physical structure and chemical complexity of carbon catalysts from biomass-derived nanocellulose, and understand the microscopic structure and identify and control the functional groups which are related to process conditions and nanocarbon catalyst performance. We will continue developing and fabricating the nanocatalysts, and study the carbonization behavior of nanocellulose in order to develop a best performance nanocarbon catalyst. We anticipate that we will meet the objectives of the proposed work in a timely manner.

Impacts
What was accomplished under these goals? Impact: The recent development of functionalized nanocelluloses applied in various industrial sectors has resulted in a transformation in the nanocellulose market. The changes are driven by the increasing demand for biodegradable and non-toxic nanomaterials. The increasing market provides new opportunities for the agricultural economy and helps to activate the existing forestry industry, which suffered a significant recession due to the declining global demand for paper. The existing Nanocrystalline cellulose (NCC) technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (i.e. sulfuric acid, 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project is to develop a green process of NCC production based on enzymatic hydrolysis, which leads to less environmental concerns and unmodified surface chemistry of NCC. Our hypothesis is that by careful selection of cellulase enzymes and hydrolysis conditions, it is possible to efficiently produce NCC from biomass without using a high concentration of harsh acids, and subsequently synthesize metal-NCC nanoparticles for jet fuel production. The project team is focused directly on creating and integrating new technologies and is lining and engaging related industries in our outreach and education efforts and involved them in the development of biomass-derived high-value catalysts, chemicals, and biofuels. Major activities completed / experiments conducted / data collected / results / key outcomes: Cellulose separation and delignification from Douglas fir sawdust: We developed a new process carrying out the carbonization and sulfonation in one single step which simplifies the process and could substantially reduce the time and energy for the preparation of heterogeneous acid catalysts (sulfonated carbon catalysts (SCC)). The application of SCC as a catalyst in the delignification of lignocellulosic biomass in an organosolv process using ethanol as solvent was first explored in this study. The highest SCC yield of 62.16% was recorded at a temperature of 92°C. Lower SCC yields of 59.74% and 53.51% were obtained when sulfonation temperature increased to 120°C and 148°C, respectively. The SCC with the highest SO3H density (1.1887 mmol/g) was obtained in biomass treated at 92°C while the lowest SO3H density (0.6726 mmol/g) was recorded at 148°C. The reduction in SO3H density with the increase in temperature was due to the adsorption-desorption equilibrium of SO3H groups on the SCC surface thus lowering the rate of sulfonation reaction. It is worth mentioning that the SO3H density of the SCC (0.6726-1.1887 mmol/g) from this study was higher compared to the sulfonated mesoporous expanded starch called Starbon-400 (0.5 mmol/g) and the sulfonated biomass-based solid catalysts (0.39-0.66 mmol/g) reported in literature. Thus, the synthesis of SCC via simultaneous carbonization and sulfonation using H2SO4 as reagent can be an alternative approach for a more simple process that would greatly reduce the time and energy requirement in the preparation of SCC. The highest ethanol organosolv lignin (EOL) yield of 63.56% with a substrate yield of 39.08% was achieved with SCC in the ethanol organosolv delignification of lignocellulosic biomass. The FTIR spectra of the isolated lignin revealed typical features of G-lignin, indicating that no drastic changes took place in the lignin structure during the process. Reduced acid loading conditions on nanocrystalline cellulose (NCC) production: The conventional method of using highly concentrated sulfuric acid at optimum 63.5 wt.% produced an NCC yield of 30 wt.% from microcrystalline cellulose (MCC). The crystalline nature of purified cellulosic fibers increases acid concentration and treatment duration, which could inversely affect the control of crystal size and crystallinity of the NCC product. Furthermore, the use of concentrated sulfuric acid raises numerous concerns associated with equipment maintenance, process viability, product safety, and environmental protection. A dilute-acid pretreatment assisted with microwave irradiation was developed to efficiently fabricate nanocrystalline cellulose (NCC) with the single use of the cellulase from Aspergillus niger. The use of microwave heating and diluted sulfuric acid solution (1, 2, 5, and 10 wt. %) in pretreatment considerably increased the NCC yield of subsequent enzymatic hydrolysis (feedstock to enzyme ratio of 2:1) with a maximum value of 84.4 wt.% from less than 10 wt.% without the pretreatment. The severity of pretreatment conditions affected the crystal dimension of rod-like nanocrystals. The crystallinity and thermal stability of extracted NCC varied by the acid concentration used in pretreatment conditions and also by the duration of enzymatic hydrolysis. The highest peak decomposition temperature of 378.1 ?C as well as the highest NCC yield were recorded in the NCC extracted in 5 wt.% sulfuric acid with microwave heating. The pretreatment effectively facilitated enzymatic hydrolysis, and the synergetic effect of microwave irradiation in the presence of sulfuric acid was associated with the improved thermal stability and crystallinity in the final products. Nanoparticles-nanocellulose derived carbon catalysts: A powerful simple carbon catalyst derived from nanocellulose was applied to the catalytic upcycling of waste plastics into H2 and liquid fuels for the first time. For the results from model low-density polyethylene (LDPE) pyrolysis, the C8-C16 aliphatics and monocyclic aromatics were dominant constitutes of the liquid product with the yields ranging from 22 to 68 wt.%. At the temperature of 500 ºC and nanocellulose derived carbon catalyst to LDPE ratio surpassing 3, the LDPE could be completely degraded into liquid and gas without wax production. A wax yield of 16 wt.% was observed at the temperature of 450 ºC and catalyst to LDPE ratio of 4, which was dramatically lower than that (77 wt.%) from the absence of catalyst at the temperature of 500 ºC. Up to 92 vol.% of H2 was detected in the gaseous product with a yield of 36 wt.%. The lower temperatures and higher catalyst to LDPE ratios favored increasing the generation of H2 at the expense of light gas CnHm especially CH4. Moreover, this nanocellulose derived carbon catalyst was tested effectively to convert the real waste plastics including grocery bags and packaging tray into valuable liquid and H2-enriched gas. Change in Knowledge: Increased understanding of the control and degree we tune for the nanocellulose microstructure during cellulose hydrolysis; Increased understanding of how the NCC yield was affected by acid concentrations, enzymatic hydrolysis, and pretreatment methods; Increased understanding of reaction mechanism and reactions responsible for the formation of nanocellulose. Change in Action: A new way of producing nanocellulose and nanocarbon catalysts from lignocelluloses biomass and lay the foundation for achieving advanced bio-jet fuel production by using biomass-derived nanocelluose and nanocarbon catalysts. Change in Condition: The existing NCC technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (hydrochloric acid and sulfuric acid at typically 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project and the accelerated development of its technology will improve the current situation of nanocellulose production, biomass conversion, and enhance the economic and energy security of the United States and maintain a technological lead in developing and deploying advanced energy technologies. This conversion system will significantly reduce energy-related emissions, including greenhouse gases and have a positive carbon effect.

Publications

  • Type: Journal Articles Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, X. Kong, R. Zou, M. Qian, Y. Zhao, W. Mateo. 2021. Catalytic upcycling of waste plastics over nanocellulose derived biochar catalyst for the coupling harvest of H2 and liquid fuels. Science of the Total Environment, 779, 146463. doi: 10.1016/j.scitotenv.2021.146463.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: M. Qian, H. Lei, E. Villota, W. Mateo, Y. Zhao, E. Huo, C. Wang, R. Zou. 2021. Enhanced production of renewable aromatic hydrocarbons for jet-fuel from softwood biomass and plastic waste using hierarchical ZSM-5 modified with lignin-assisted re-assembly. Energy Conversion and Management, 236, 114020. doi: 10.1016/j.enconman.2021.114020.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: M. Qian, H. Lei, Y. Zhao, C. Wang, E. Huo, Q. Zhang, W. Mateo, X. Lin, X. Kong, R. Zou. 2021. High yield production of nanocrystalline cellulose by microwave-assisted dilute-acid pretreatment combined with enzymatic hydrolysis. Chemical Engineering and Processing - Process Intensification, 160, 108292. doi: 10.1016/j.cep.2020.108292.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: C. Wang, R. Zou, H. Lei, M. Qian, X. Lin, W. Mateo, L. Wang, X. Zhang, R. Ruan. 2022. Biochar-advanced thermocatalytic salvaging of the waste disposable mask with the production of hydrogen and mono-aromatic hydrocarbons. Journal of Hazardous Materials, 426, 128080. Doi: 10.1016/j.jhazmat.2021.128080.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: C. Wang, R. Zou, M. Qian, X. Kong, E. Huo, X. Lin, L. Wang, X. Zhang, R. Ruan, H. Lei. 2022. Improvement of the carbon yield from biomass carbonization through sulfuric acid pre-dehydration at room temperature. Bioresource Technology 355, 127251. doi: 10.1016/j.biortech.2022.127251.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, Y. Zhao, M. Qian, X. Kong, W. Mateo, R. Zou, R. Ruan. 2021. Integrated harvest of phenolic monomers and hydrogen through catalytic pyrolysis of biomass over nanocellulose derived biochar catalyst. Bioresource Technology, 320A, 124352. doi: 10.1016/j.biortech.2020.124352.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: W. Mateo, H. Lei, E. Villota, M. Qian, Y. Zhao, E. Huo, Q. Zhang, X. Lin, and C. Wang. 2021. One-step Synthesis of Biomass-based Sulfonated Carbon Catalyst by Direct Carbonization-Sulfonation for Organosolv Fractionation. Bioresource Technology, 319, 124194. doi: 10.1016/j.biortech.2020.124194.
  • Type: Journal Articles Status: Accepted Year Published: 2022 Citation: E. M. Villota, H. Lei, S. M. A. Villota, M. Qian, W. Mateo, Y. Zhao, E. Huo, Q. Zhang, X. Lin, Z. Huang. 2020. Adsorption Isotherm and Kinetics of Methylene Blue Dye on Chemically-Activated Porous Carbon from Douglas fir. Materials International. Accepted.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: R. Zou, M. Qian, C. Wang, W. Mateo, Y. Wang, L. Dai, X. Lin, Y. Zhao, E. Huo, L. Wang, X. Zhang, X. Kong, R. Ruan, H Lei. 2022. Biochar: from by-products of agro-industrial lignocellulosic waste to tailored carbon-based catalysts for biomass thermochemical conversions. Chemical Engineering Journal, 441,135972. Doi: 10.1016/j.cej.2022.135972.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: X. Lin, H. Lei, W. Yi, H. Cai, X. Chen, Y. Guo. 2021. Catalytic co-pyrolysis of biomass and low-density polyethylene over activated carbon catalyst. Transactions of the CSAE, 37(15), 189-196. doi: 10.11975/j.issn.1002-6819.2021.15.023.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: M. Qian, H. Lei, Y. Zhao, E. Villota, E. Huo, C. Wang, X. Zhang. 2021. Lignin-mediated preparation of hierarchical ZSM-5 catalysts and their effects in catalytic co-pyrolysis of softwood biomass and low-density polyethylene mixtures. ACS Sustainable Chemistry & Engineering. 9(37), 12602-12613. doi: 10.1021/acssuschemeng.1c03863.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, R. Zou, M. Qian, W. Mateo, X. Lin, R. Ruan. 2021. Biochar-driven simplification of the compositions of cellulose-pyrolysis-derived biocrude oil coupled with the promotion of hydrogen generation. Bioresource Technology. 334, 125251. doi: 10.1016/j.biortech.2021.125251.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: X. Lin, L. Kong, X. Ren, D. Zhang, H Cai, H. Lei. 2021. Catalytic co-pyrolysis of torrefied poplar wood and high-density polyethylene over hierarchical HZSM-5 for mono-aromatics production. Renewable Energy, 164, 87-95. doi: 10.1016/j.renene.2020.09.071
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: M. Qian, H. Lei�, C. Wang, R. Zou, W. Mateo. 2021. Impacts of acid and base activations on nanocellulose-derived carbons for catalytic co-pyrolysis of lignocellulosic biomass and polyethylene mixture. 2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, R. Zou, M. Qian, W. Mateo. 2021. Biochar-driven simplification of the compositions of cellulose-pyrolysis-derived oil coupled with the promotion of hydrogen generation. 2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, R. Zou, M. Qian, W. Mateo. 2021. Catalytic upcycling of waste plastics over nanocellulose derived biochar catalyst for the coupling harvest of hydrogen and liquid fuels. 2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: R. Zou, H. Lei, C. Wang, M. Qian, W. Mateo. 2021. Catalytic upgrading of LDPE pyrolysis gas over nanocellulose derived biochar supported Ni/Pd catalysts. 2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: D. Duan, X. Dong, Q. Wang, Y. Zhang, R. Ruan, Y. Wang, H. Lei. 2021. Production of renewable phenols from corn cob using catalytic pyrolysis over self-derived activated carbons prepared with torrefaction pretreatment and chemical activation. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 126507. doi: 10.1016/j.colsurfa.2021.126507.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: D. Duan, D. Chen, L. Huang, Y. Zhang, Q. Wang, G. Xiao, W. Zhang, H. Lei, R. Ruan. 2021. Activated carbon from lignocellulosic biomass as catalyst: A review of the applications in fast pyrolysis process. Journal of Analytical and Applied Pyrolysis, 158, 105246. doi: 10.1016/j.jaap.2021.105246.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: E. Huo, C. Liu, L. Xin, Y. Zhang, Y Zhao, M Qian, X Lin, H. Lei. 2021. High purity hydrocarbon fuel production by co-pyrolysis of low density polyethylene (LDPE) and wheat straw over activated carbon catalyst. Sustainable Energy & Fuels, 5, 23, 6145-6156. doi: 10.1039/D1SE01108A.
  • Type: Book Chapters Status: Accepted Year Published: 2022 Citation: Y. Zhou, X. Li, N. Zhao, H. Elshareef, Y. Yu, M. Qian, H. Lei. 2022. Thermal processing of biomass for energy and fuel production in Advances in Bioenergy Vol. 7 ISBN: 9780323989848. Elsevier. Accepted.
  • Type: Theses/Dissertations Status: Published Year Published: 2021 Citation: Wendy Mateo. 2021. PhD thesis: Development and optimization of catalytic pyrolysis process of lignocellulosic biomass over sulfonated carbon-based catalyst.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: M. Qian, H. Lei�, C. Wang, R. Zou, W. Mateo. 2021. Integrated production of syngas and aromatic hydrocarbons from low-density polyethylene using metal-doped nanocarbon-zeolite composites. 2021 ASABE Annual International Meeting, virtual, July 12-16, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: M. Qian, H. Lei�, C. Wang, R. Zou, W. Mateo. Nanocellulose extraction and catalytic pyrolysis for bio jet fuel. 2021. 1st Virtual International Conference through the e3-STArt, an annual International Academic Research and Development Festival, October 26 to 28, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Invited. C. Wang, H. Lei, R. Zou, M. Qian, W. Mateo. 2021. Catalytic upcycling of waste plastics over nanocellulose derived biochar catalyst for the coupling harvest of hydrogen and liquid fuels. 2021 Virtual International Conference on Environmental Pollution and Governance (ICEPG 2021). May 21-23, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: H. Lei, M. Qian, C. Wang, R. Zou, E. Villota, Y. Zhao, E. Huo, Q. Zhang, W. Mateo, X. Lin. 2021. Nano cellulose-based nanoparticle catalysts for bio-jet fuel ranged cycloalkanes production. 2021 Virtual AFRI Nanotechnology Annual Grantees' Conference. October 6-7, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: M. Qian, H. Lei�, C. Wang, R. Zou, W. Mateo. 2021. Introduction of nanocellulose in hydrothermal treatment of ZSM-5 and its effect on catalytic pyrolysis of lignocellulosic biomass. Virtual International Chemical Congress of Pacific Basin Societies, December 16-21, 2021.


Progress 03/01/20 to 02/28/21

Outputs
Target Audience:Biomass industrial companies, biofuel-related industries, biomass and biofuel producers, processors, wholesalers, and retailers: including Creative Energy Systems Inc., MS Sustainables, LLC., North America Green Pulp Inc., USS International Group, LLP., Sustainable Fiber Technologies, Inc., Ambient Energy LLC, Clearwater Supply, Inc., Energy Associates Intl., LLC,Conrad Industries, Inc., DTG Recycling Group, LLC. Efforts: Formal classroom instruction (new course lectures/sessions) about the project in BSYSE 551 Advanced Biological Systems Engineering Topics: Bioprocess Engineering, BSysE 552 Advanced Biological Systems Engineering Topics: Biomass and Bioenergy; Development of curriculum (new lecture sessions on biomass conversion and catalysis, biomass-derived nanocellulose, nanocarbon catalysts, chemicals, bio-jet fuel); Trained graduate and undergraduate students and post-doctoral researchers who work on this project will eventually join the workforce and contribute to the effort of utilizing biomass and developing bioproducts (i.e. nanocellulose, nanocarbon catalysts) and renewable energy technology for the future energy needs: PhD students: Wendy Mateo, Rongge Zou, Erguang Huo, Yunfeng Zhao, Qingfa Zhang; and post-doc: Chenxi Wang, Moriko Qian, and Xiaona Lin; New experiential learning opportunities for involved students in the project; Presentations, seminars, and communications to local communities, such as 2020 PNNL Brownbag Series, Webinar of 2020 American Society of Agricultural and Biological Engineers (ASABE) Student Engineering Branch (SEB), and regional and national conferences, such as 2020 Thermal & Catalytic Sciences Virtual Symposium, (see the session of publication list in Product); Extension and outreach include outreach communications and presentations to biomass industrial companies, biofuels, and related industries. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training activities: The funding received from this project has been used to support 3 post-doc, 5 Ph.D. candidates in the WSU Biological Systems Engineering Program. 5 Ph.D. students and 3 post-doc research associates learned to develop new technologies, new processes, and new catalyst materials. Post-doc and Ph.D. students have developed the experience in attaining greater proficiency in developing new technologies and conducting experiments. PIs incorporated the research results from this project in teaching BSYSE 551 Advanced Biological Systems Engineering Topics: Bioprocess Engineering, BSysE 552 Advanced Biological Systems Engineering Topics: Economic and Environmental Sustainability of Energy. Professional development activities: PIs had monthly conference calls with industrial collaborators and active collaborations among each other, and the PI research group had weekly meetings to make sure the good progress of the project. PI and the research team had updates presented at group meetings. Students developed collaboration skills and exchanged technical information cross-group knowledge. Ph.D. Students and Post-doc have participated and presented papers at the American Society of Agricultural and Biological Engineers (ASABE) 2020 Annual International Meeting,virtual, July 12-15, 2020; 2020 Thermal & Catalytic Sciences Virtual Symposium, October 5 - 7, 2020; 2020 PNNL Brownbag Series, June 24, 2020; 2020 PNNL Brownbag Series, June 02, 2020; 2020 American Society of Agricultural and Biological Engineers (ASABE) Student Engineering Branch (SEB), November 18, 2020. How have the results been disseminated to communities of interest?The PI and the students and post-doc created posters and/or made oral presentations to showcase findings and present the study results. The research findings were communicated to the general public via national and international conferences, such as the American Society of Agricultural and Biological Engineers (ASABE) 2020 Annual International Meeting,virtual, July 12-15, 2020; 2020 Thermal & Catalytic Sciences Virtual Symposium, October 5 - 7, 2020; 2020 PNNL Brownbag Series, June 24, 2020; 2020 PNNL Brownbag Series, June 02, 2020; 2020 American Society of Agricultural and Biological Engineers (ASABE) Student Engineering Branch (SEB), November 18, 2020. The published journal papers and proceedings can be found in previous sessions in this progress report. We also disseminated our research results to communities by presenting them to industrial delegations and academic communities. Our outreach dissemination efforts include virtual meetings with industrial experts, such as North America Green Pulp Inc., Sustainable Fiber Technologies, Inc., Energy Associates Intl., LLC, etc. We made outreach communications and engagements with the biobased industrial companies, and signed Mutual Confidential Disclosure Agreement and Confidentiality and Noncircumvention Agreement with industrial companies. What do you plan to do during the next reporting period to accomplish the goals?During the next year of 2021, we will continue working on studying the cellulose isolation from biomass and determine the effects of microwave-irradiation pretreatment on enzymatic hydrolysis for nanocrystalline cellulose (NCC) production. We will investigate the physical structure and chemical complexity of biomass-derived nanocellulose, and understand the microscopic structure and identify and control the functional groups which are related to nanocellulose process conditions and nanocarbon catalyst performance. We will continue developing and fabricating the nanocatalysts, and study the carbonization behavior of nanocellulose in order to develop a best performance nanocarbon catalyst. We anticipate that we will meet the objectives of the proposed work in a timely manner.

Impacts
What was accomplished under these goals? Impact: The recent development of functionalized nanocelluloses applied in various industrial sectors has resulted in a transformation in the nanocellulose market. The changes are driven by the increasing demand for biodegradable and non-toxic nanomaterials. The increasing market provides new opportunities for the agricultural economy and helps to activate the existing forestry industry, which suffered a significant recession due to the declining global demand for paper. The existing Nanocrystalline cellulose (NCC) technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (i.e. sulfuric acid, 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project is to develop a green process of NCC production based on enzymatic hydrolysis, which leads to less environmental concerns and unmodified surface chemistry of NCC. Our hypothesis is that by careful selection of cellulase enzymes and hydrolysis conditions, it is possible to efficiently produce NCC from biomass without using a high concentration of harsh acids, and subsequently synthesize metal-NCC nanoparticles for jet fuel production. The project team is focused directly on creating and integrating new technologies and is lining and engaging related industries in our outreach and education efforts and involved them in the development of biomass-derived high-value catalysts, chemicals, and biofuels. Major activities completed / experiments conducted / data collected / results / key outcomes: Cellulose separation and delignification from Douglas fir sawdust: Various conversion processes for bio-based fuels and chemicals production from lignocellulosic biomass typically require fractionation and specific valorization of the raw biomass into its simpler component for a more facile and economically feasible process. The homogeneous acids (e.g. H2SO4 and HCl) are most frequently used in biomass fractionation, however, they have several disadvantages including the high cost of separating the catalyst from the homogeneous reaction mixture, a large volume of waste products, and environmental pollution. Promising heterogeneous acid catalysts can be produced via the integration of surface functional group, sulfonic acid (SO3H), into the surface of solid materials such as carbon or silica. Sulfonated carbon materials have the advantages of low cost, high stability, and high activity catalysts. Preparation of sulfonated carbon catalysts (SCC) is usually done by carbonization of organic raw materials followed by sulfonation treatment to integrate SO3H groups into the carbon products. The processes require relatively high temperatures for a long period of reaction times. We developed a new process carrying out the carbonization and sulfonation in one single step which simplifies the process and could substantially reduce the time and energy for the preparation of SCC. SCC was synthesized from agricultural wastes via a one-step facile method of direct carbonization-sulfonation in a reflux system using H2SO4 as a reagent. The goal of this work was to evaluate the influence of reaction temperature and time in SCC yield and SO3H density of the SCC. Reduced acid loading conditions on nanocrystalline cellulose (NCC) production: The conventional studies on the preparation of nanocellulose used a high concentration of sulfuric acid that is difficult to remove and recover. A biochar-based solid acid with magnetic properties was developed to hydrolyze cellulose to prepare nanocellulose in this work. Two different methods were selected to investigate the properties of the synthesized magnetic carbon-based solid acids. The synthesized catalysts were characterized by SEM, TEM, XRD, NH3-TPD, and FT-IR. The experimental results showed that two solid acids by the microwave-assisted synthesis had good magnetic properties by magnet adsorption. Analysis by SEM and TEM showed that the two solid acids had rich pore structures. According to mineral element analysis, both solid acids contained high sulfur content. The solid acid was an amorphous carbon structural material with a surface rich in active groups. The catalytic activity of the biochar-based solid acids in cellulose hydrolysis to prepare nano-scale cellulosic material was evaluated. It was found that magnetic biochar-based solid acid (MBC-SA1) could achieve a high yield, which produced up to 57.68% for hydrolyzing cellulose into nanometers. MBC-SA1 had a higher specific surface area and a higher acidity. In addition, MBC-SA1 had the best hydrolysis effect on cellulose, and the best loading amount was found to be 20%. On the other hand, MBC-SA2 had the best magnetic properties, which is particularly beneficial to the separation and reuse of MBC-SA. The addition of the magnetic material allowed the solid acid to be separated efficiently from the product. Nanoparticles-nanocellulose derived carbon catalysts: The remarkable enhancement of phenolic monomer generation and hydrogen was achieved through catalytic pyrolysis of Douglas fir over nanocellulose derived biochar catalyst for the first time. Hydrogen, as the most abundant element in the universe and an eco-friendly energy carrier, appears to be an evolving alternative fuel for the future. Phenol and its derivatives are important aromatics in the chemical industry. Aromaticsplay a key role inaviation fuelsas they enhance the density and elastomer swelling properties of thesefuels. Phenols are added as antioxidants in aviation jet fuels. Integrated harvest of phenolic monomers and hydrogen through catalytic pyrolysis of biomass over nanocellulose derived biochar catalyst was achieved in this study. The main compositions of produced bio-oil were phenolic monomers, furans, and naphthalenes, etc., in which the phenolic monomers were dominant compositions. And at the temperature of 650 ºC and 3 of nanocellulose biochar to biomass ratio, the quantification results showed that the concentration of phenol was increased to 53.77 mg/mL from 15.76 mg/mL of free of catalyst. The concentration of cresols were facilitated to 44.51 mg/mL from 20.95 mg/mL, while the concentration of dimethylphenols reduced to 7.76 mg/mL from 9.11 mg/mL. Up to 85.32 vol.% of hydrogen was observed, increasing from 45.53 vol.% of the non-catalytic process. After 15 cycles of reuse, nanocellulose biochar catalysts still favored producing a much higher concentration of phenolic monomers and hydrogen than that of the absence of catalysts. Change in Knowledge: Increased understanding of the control and degree we tune for the nanocellulose microstructure during cellulose hydrolysis; Increased understanding of how the NCC yield was affected by acid concentrations, enzymatic hydrolysis, and pretreatment methods; Increased understanding of reaction mechanism and reactions responsible for the formation of nanocellulose. Change in Action: A new way of producing nanocellulose and nanocarbon catalysts from lignocelluloses biomass and lay the foundation for achieving advanced bio-jet fuel production by using biomass-derived nanocelluose and nanocarbon catalysts. Change in Condition: The existing NCC technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (hydrochloric acid and sulfuric acid at typically 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project and the accelerated development of its technology will improve the current situation of nanocellulose production, biomass conversion, and enhance the economic and energy security of the United States and maintain a technological lead in developing and deploying advanced energy technologies. This conversion system will significantly reduce energy-related emissions, including greenhouse gases and have a positive carbon effect.

Publications

  • Type: Journal Articles Status: Published Year Published: 2021 Citation: C. Wang, H. Lei, Y. Zhao, M. Qian, X. Kong, W. Mateo, R. Zou, R. Ruan. 2021. Integrated harvest of phenolic monomers and hydrogen through catalytic pyrolysis of biomass over nanocellulose derived biochar catalyst. Bioresource Technology, 320A, 124352. doi: 10.1016/j.biortech.2020.124352.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: W. Mateo, H. Lei, E. Villota, M. Qian, Y. Zhao, E. Huo, Q. Zhang, X. Lin, and C. Wang. 2021. One-step Synthesis of Biomass-based Sulfonated Carbon Catalyst by Direct Carbonization-Sulfonation for Organosolv Fractionation. Bioresource Technology, 319, 124194. doi: 10.1016/j.biortech.2020.124194.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: Y. Zhao, H. Lei, Y. Liu, R. Ruan, M. Qian, E. Huo, Q. Zhang, Z. Huang, X. Lin, C. Wang, W. Mateo, E. M. Villota. 2020. Microwave-assisted Synthesis of Bifunctional Magnetic Solid Acid for Hydrolyzing Cellulose to Prepare Nanocellulose. Science of the Total Environment, 731, 138751. doi: 10.1016/j.scitotenv.2020.138751.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: X. Kong, Y. Zhu, H. Lei, C. Wang, Y. Zhao, E. Huo, X. Lin, Q. Zhang, M. Qian, W. Mateo, R. Zou, Z. Fang, and R. Ruan. 2020. Synthesis of graphene-like carbon from biomass pyrolysis and its applications. Chemical Engineering Journal, 399, 125808. doi: 10.1016/j.cej.2020.125808.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: W. Mateo, H. Lei, E. Villota, M. Qian, D. Duan, Y. Zhao, E. Huo, Q. Zhang, X. Lin, and Z. Huang. 2020. Synthesis and characterization of sulfonated activated carbon as a catalyst for bio-jet fuel production from biomass and waste plastics. Bioresource Technology, 297,122411. doi: 10.1016/j.biortech.2019.122411.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: D. Duan, Y. Zhang, H. Lei, M. Qian, E. Villota, Y. Wang, R. Ruan. 2020. A novel production of phase-divided jet-fuel-ranged hydrocarbons and phenols-enriched chemicals from catalytic co-pyrolysis of lignocellulosic biomass with waste plastics over carbon catalysts. Sustainable Energy & Fuels, 4, 3687 - 3700. doi: 10.1039/D0SE00419G.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: Q. Zhang, H. Lei, H. Cai, X. Han, X. Lin, M. Qian, Y. Zhao, E. Huo, E. M. Villota, W. Mateo. 2020. Improvement on the properties of microcrystalline cellulose/polylactic acid composites using activated biochar. Journal of Cleaner Production, 252, 119898. doi: 10.1016/j.jclepro.2019.119898.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: X. Lin, H. Lei, Q. Zhang, M. Qian, Y. Zhao, E. Huo, C. Wang, W. Mateo, E. Villota. 2020. Enhancing jet fuel range hydrocarbon production from catalytic co-pyrolysis of Douglas fir and low-density polyethylene over Fe-modified bifunctional activated carbon catalysts. Energy Conversion and Management, 211, 112757. doi: 10.1016/j.enconman.2020.112757.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: D. Duan, Y. Zhang, Y. Wang, H. Lei, Q. Wang; R. Ruan. 2020. Production of renewable jet fuel and gasoline range hydrocarbons from catalytic pyrolysis of soapstock over corn cob-derived activated carbons. Energy, 209, 118454. doi: 10.1016/j.energy.2020.118454.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: C. Wang, H. Lei, M. Qian, E. Huo, Y. Zhao, Q. Zhang, W. Mateo, X. Lin, X. Kong, R. Zou, R. Ruan. 2020. Application of highly stable biochar catalysts for efficient pyrolysis of plastics: a readily accessible potential solution to a global waste crisis. Sustainable Energy & Fuels, 4, 4614 - 4624. doi: 10.1039/D0SE00652A.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: E. Huo, D. Duan , H. Lei, C. Liu, Y. Zhang, J. Wu, Y. Zhao, Z. Huang, M. Qian, Q. Zhang, X. Lin, C. Wang, W. Mateo, E. M. Villota, R. Ruan. 2020. Phenols production from Douglas fir catalytic pyrolysis with MgO and biomass-derived activated carbon catalysts. Energy, 199, 117459. doi: 10.1016/j.energy.2020.117459.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: E. Huo, H. Lei, C. Liu, Y. Zhang, L. Xin, Y. Zhao, M. Qian, Q. Zhang, X. Lin, C. Wang, W. Mateo, E. M. Villota, R. Ruan. 2020. Jet fuel and hydrogen produced from waste plastics catalytic pyrolysis with activated carbon and MgO. Science of the Total Environment, 727, 138411. doi: 10.1016/j.scitotenv.2020.138411.
  • Type: Book Chapters Status: Published Year Published: 2020 Citation: R. Ruan, K. Ding, S. Liu, P. Peng, N. Zhou, A. He, P. Chen, Y. Cheng, Y. Wang, Y. Liu, H. Lei, M. Addy, K. Cobb. 2020. Gasification and pyrolysis of waste, in Current Developments in Biotechnology and Bioengineering, chapter 12, pp 263-297. Elsevier. doi: 10.1016/B978-0-444-64309-4.00012-X.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: C. Wang, H. Lei, Y. Zhao, M. Qian, W. Mateo, E. Mateo, E. Huo. 2020. Enhancement of H2 generation via catalytic pyrolysis of biomass over nanocellulose derived biochar catalyst. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Y. Zhao, R. Zou, H. Lei�, M. Qian, E. Villota, E. Huo, W. Mateo, Q. Zhang, X. Lin, C. Wang. 2020. Preparation of nanocellulose by enzymatic hydrolysis of cellulose pretreated with carbon-based solid acid. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: C. Wang, H. Lei, M. Qian, Y. Zhao, R. Zou, W. Mateo, X. Kong. 2020. Enhancing the Generation of Phenolic Monomers and H2 through Catalytic Pyrolysis of Biomass over Nanocellulose Derived Biochar Catalyst. 2020 Thermal & Catalytic Sciences Virtual Symposium, October 5 - 7, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Y. Zhao, R. Zou, H. Lei�, M. Qian, E. Villota, E. Huo, W. Mateo, Q. Zhang, X. Lin, C. Wang. 2020. Microwave-assisted synthesis of nano-biocarbon-based catalysts to improve the quality of low-density polyethylene pyrolysis bio-oil. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Y. Zhao, R. Zou, H. Lei, Y. Liu, R. Ruan,Y. Wang, M. Qian. 2020. Preparation of nanocellulose by enzymatic hydrolysis of cellulose pretreated with carbon-based solid acid. 2020 Thermal & Catalytic Sciences Virtual Symposium, October 5 - 7, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: M. Qian, H. Lei�, Y. Zhao, C. Wang, X. Kong, W. Mateo., R. Zou. 2020. Hydrothermal treatment with nanocellulose for enhancing the catalytic performance of H-ZSM-5 zeolite in aromatic hydrocarbon production. 2020 Thermal & Catalytic Sciences Virtual Symposium, October 5 - 7, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: M. Qian, H. Lei�, E. Villota, Y. Zhao, E. Huo, W. Mateo, C, Wang. 2020. Development of meso-micro structure in MFI zeolites via nanocrystalline cellulose templating for conversion of lignocellulosic biomass to aromatic hydrocarbons. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: M. Qian, H. Lei�, Y. Zhao, E. Villota, E. Huo, W. Mateo, Q. Zhang, X. Lin, C. Wang. 2020. Synthesis of zeolite-nanocarbon composite using nanocellulose for catalytic conversion of plastic waste to liquid oil integrated with syngas production. 2020 ASABE Annual International Meeting, virtual, July 12-15, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: (Invited) H. Lei. 2020. Fuel and chemical production from waste plastics via catalytic pyrolysis over carbon catalysts. 2020 PNNL Brownbag Series, June 24, 2020.


Progress 03/01/19 to 02/29/20

Outputs
Target Audience:Biomass industrial companies, biofuel-related industries, biomass and biofuel producers, processors, wholesalers, and retailers: including Creative Energy Systems Inc., MS Sustainables, LLC., North America Green Pulp Inc., USS International Group, LLP., Sustainable Fiber Technologies, Inc. Washington Bio-oils Inc., Clearwater Supply, Inc., Energy Associates Intl., LLC.,Conrad Industries, Inc. Efforts: Formal classroom instruction (new course lectures/sessions) about the project in BSYSE 551 Advanced Biological Systems Engineering Topics: Bioprocess Engineering, BSysE 552 Advanced Biological Systems Engineering Topics: Economic and Environmental Sustainability of Energy; Development of curriculum (new lecture sessions on biomass conversion and catalysis, biomass-derived nanocellulose, nanocarbon catalysts, chemicals, bio jet fuel); Trained graduate and undergraduate students and post-doctoral researchers who work on this project will eventually join the workforce and contribute to the effort of utilizing biomass and developing bioproducts (i.e. nanocellulose, nanocarbon catalysts) and renewable energy technology for the future energy needs: PhD students: Marie Qian, Wendy Mateo, Dengle Duan, Erguang Huo, Yunfeng Zhao, Qingfa Zhang, Rongge Zou; MS student: Zhiyang Huang; undergraduate students: Roy Leal, Erick Leal; and post-doc: Chenxi Wang, Xiao Kong. New experiential learning opportunities for involved students in the project; Presentations, seminars, and communications to local communities, such as 2019 WSU ShowCase Conference, 2019 Rotary Club of Pullman Meeting, regional and national conferences (see the session of publication list in Product; Extension and outreach include outreach communications and presentations to biomass industrial companies, biofuels, and related industries. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training activities: The funding received from this project has been used to support 2 post-doc, 7 Ph.D. candidates, 1 MS student, and 2 undergraduate students in the WSU Biological Systems Engineering Program. 7 Ph.D. students, 1 MS student, 2 undergraduate students, and 2 post-doc research associates learned to develop new technologies, new processes, and new catalyst materials. Post-doc and Ph.D. students have developed the experience assisting MS students and undergraduate students in attaining greater proficiency in developing new technologies and conducting experiments. PIs incorporated the research results from this project in teaching BSYSE 551 Advanced Biological Systems Engineering Topics: Bioprocess Engineering, BSysE 552 Advanced Biological Systems Engineering Topics: Economic and Environmental Sustainability of Energy. Professional development activities: PIs had monthly conference calls with industrial collaborators and active collaborations among each other, and PI research group had weekly meetings to make sure the good progress of the project. PI and the research team had updates presented at group meetings. Students developed collaboration skills and exchanged technical information cross group knowledge. Ph.D. Students and Post-doc have participated and presented papers at American Society of Agricultural and Biological Engineers (ASABE) 2019 Annual International Meeting at Boston, Massachusetts USA, July 7-10, 2019, International Conference on Biofuels and Bioenergy (BBC 2019), San Francisco, CA, USA, April 29-May 01, 2019, 2019 USDA/NIFA Nanotechnology Grantees Annual Meeting, Vanderbilt University, May 20-21, 2019, and WSU ShowCase Conference, Pullman, WA, March 25, 2019. How have the results been disseminated to communities of interest?The PI and the students and post-doc created posters and/or made oral presentations to showcase findings and present the study results. The research findings were communicated to the general public via national and international conferences, such as the American Society of Agricultural and Biological Engineers (ASABE) 2019 Annual International Meeting at Boston, Massachusetts USA, July 7-10, 2019, International Conference on Biofuels and Bioenergy (BBC 2019), San Francisco, CA, USA, April 29-May 01, 2019, 2019 USDA/NIFA Nanotechnology Grantees Annual Meeting, Vanderbilt University, May 20-21, 2019, 2019 Five-Year Reflection Sun Grant Western Regional Center, Newport, OR, August 21-22, 2019, and WSU ShowCase Conference, Pullman, WA, March 25, 2019. The published journal papers and proceedings can be found in previous sessions in this progress report. We also disseminated our research results to communities by presenting to industrial delegations and academic communities. Our outreach dissemination efforts include: 2019 Rottary Club meeting, Pullman, WA, July 24, 2019, 2019 Meetings of biomass conversions for biofuels and bioproducts with Creative Energy Systems Inc., MS Sustainables, LLC., North America Green Pulp Inc., USS International Group, LLP., Sustainable Fiber Technologies, Inc. Washington Bio-oils Inc., Clearwater Supply, Inc., Energy Associates Intl., LLC, Conrad Industries, Inc. What do you plan to do during the next reporting period to accomplish the goals?During the next year of 2020, we will continue working on studying the cellulose isolation from biomass and determine the effects of microwave-irradiation pretreatment on enzymatic hydrolysis for nanocrystalline cellulose (NCC) production. We will investigate the physical structure and chemical complexity of biomass-derived nanocellulose, and understand the microscopic structure and identify and control the functional groups which are related to nanocellulose process conditions and nanocarbon catalyst performance. We will continue developing and fabricating the nanocatalysts, and study the carbonization behavior of nanocellulose in order to develop a best performance nanocarbon catalyst. We anticipate that we will meet the objectives of the proposed work in a timely manner.

Impacts
What was accomplished under these goals? Impact: The recent development of functionalized nanocelluloses applied in various industrial sectors has resulted in a transformation on nanocellulose market. The changes are driven by the increasing demand for biodegradable and non-toxic nanomaterials. The increasing market provides new opportunities for the agricultural economy and helps to activate the existing forestry industry, which suffered a significant recession due to the declining global demand for paper. The existing Nanocrystalline cellulose (NCC) technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (i.e. sulfuric acid, 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project is to develop a green process of NCCproduction based on enzymatic hydrolysis, which leads to less environmental concerns and unmodified surface chemistry of NCC. Our hypothesis is that by careful selection of cellulase enzymes and hydrolysis conditions, it is possible to efficiently produce NCC from biomass without using a high concentration of harsh acids, and subsequently synthesize metal-NCnanoparticles for jet fuel production. The project team is focused directly on creating and integrating new technologies and is lining and engaging related industries in our outreach and education efforts and involved them in the development of biomass-derived high-value catalysts, chemicals, and biofuels. Major activities completed / experiments conducted / data collected / results / key outcomes: Cellulose separation and delignification from Douglas fir sawdust: Alkaline pretreatment using sodium hydroxide can result in high selectivity of delignification and retention of carbohydrates. Sodium hydroxide removes lignin from plant cell wall by attacking the ether and ester bonds between carbohydrates and lignin, and also effectively breaks C - C bonds in lignin by hydrolysis. The extraction of softwood lignin from Douglas fir through alkaline pretreatment was optimized at moderate treatment conditions. A central composition experimental design (CCD) was used to investigate the effect of three extraction factors: extraction temperature (63.2 - 96.8 ºC), sodium hydroxide loading (0.10 - 0.60 g/g feedstock) and heating time (2.6 - 9.4 hour). Response surface methodology indicates the interactive effects of sodium hydroxide loading and extraction temperature on enhancing the extraction of solid alkaline lignin at mild conditions. Optimization analysis of alkaline lignin extraction was performed with the emphasis on product yield and process economy. Extracted alkaline lignins were characterized by FT-IR spectroscopy, UV-vis spectrometry, elemental analysis, and pyrolysis product analysis. The diversity of functional groups was retained and the removal of methoxyl groups was significantly impacted by alkali loading, the individual extraction factors, as well as their combinations. Reduced acid loading conditions on nanocrystalline cellulose (NCC) production: Various types of nanomaterials can be extracted from cellulose owing to its hierarchical structure and semicrystalline nature, in addition to different cellulose sources and various extraction methods. Typically, sulfuric acid is employed, for example, the conventional method using sulfuric acid (63.5 wt. %) for the hydrolysis of microcrystalline cellulose (MCC) produced a yield of 30 wt.%, and the NCC had 200 - 400 nm in length and 10 nm in width. Since increasing acid concentration and heating time negatively affects the crystal size and crystallinity of the NCC product, a breakthrough in the process is essential to improve the NCC yield with high quality from raw material. A green and facile pretreatment process was developed in this project to fabricate nanocrystalline cellulose (NCC) via enzymatic hydrolysis using the cellulase from Aspergillus niger. Microwave irradiation induces direct and fast heating by causing vibration to water at a molecular level with the electromagnetic radiation. Specifically, cellulose was pretreated with 1, 2, 5 and 10 wt. % sulfuric acid (fiber to liquor ratio of 1:30) at 95 ºC with microwave heating at 300 W for 6 hours. For comparison, cellulose was pretreated with sulfuric acid in conventional oven 95 ºC for the same duration of time as microwave-assisted pretreatment. The structural features and physicochemical properties of the extracted NCC products were further evaluated by SEM, TEM, FTIR, XRD, and TG/DTG analysis. We found that the microwave-assisted dilute-acid pretreatment significantly reduced the consumption of acid in the process to promote product security, environmental-friendliness, and energy conservation. Metal nanoparticles-nanocellulose derived carbon catalysts: The nanocrystalline cellulose (NCC) is equipped with various advanced properties such as high surface area, nanoscale dimension, superior tensile strength, rigidity, and elastic modulus, and low thermal expansion. The nature of NCC has made NCC an eco-friendly, precious and green alternative material to replace the traditional high-strength source produced from petroleum fossil fuels. Metal nanoparticles are favorable to afford a bridge between the homogeneous and heterogeneous catalytic systems due to the unique characters of NCC. Our current work pointed out a novel and green route to NCC production and the down-stream usage of NCC to create carbon catalysts in biomass conversion. The nano-sized metal-carbon catalysts were synthesis by using wet impregnation with subsequent pyrolysis. Various nano-sized metals including Co, Ni, Cu, or Zn were added into NCC suspension. Then the suspensions were heated in a shaker at 60 ºC with constant stirring at 150 rpm for 6 h. After reaction, the suspensions were cooled to room temperature and frozen dried under vacuum condition. Lastly, the solids were pyrolyzed at a target temperature by a facile fixed bed reactor. Then the solid residue was collected as metal doped-NCC carbon catalysts. The micromorphology and size of NCC suspension and obtained catalysts were characterized by a transmission electron microscope (TEM). The TEM results showed that the prepared NCC rendered a spider-web-network-like structure. In addition, the length and width of NC was 200-500 nm and around 20 nm, respectively. Fine particles and good metal dispersion were achieved for the Co, Ni, Cu, and Zn doped-NCC carbon catalysts, respectively. The doped metal crystals were uniformly dispersed with the diameter ranging from 5~20 nm. Change in Knowledge: Increased understanding of the lignin and cellulose separation under alkaline pretreatment; Increased understanding of how the NCC yield was affected by acid concentrations, enzymatic hydrolysis, and pretreatment methods; Increased understanding of reaction mechanisms and reactions responsible for the formation of nanocellulose. Change in Action: A new way of producing nanocellulose and nanocarbon catalysts from lignocelluloses biomass and lay the foundation for achieving advanced bio-jet fuel production by using biomass-derived nanocelluose and nanocarbon catalysts. Change in Condition: The existing NCC technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (hydrochloric acid and sulfuric acid at typically 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project and the accelerated development of its technology will improve the current situation of nanocellulose production, biomass conversion, and enhance the economic and energy security of the United States and maintain a technological lead in developing and deploying advanced energy technologies. This conversion system will significantly reduce energy-related emissions, including greenhouse gases and have a positive carbon effect.

Publications

  • Type: Journal Articles Status: Published Year Published: 2019 Citation: M. Qian, H. Lei, E. Villota, W. Mateo, Y. Zhao, E. Huo, Q. Zhang, X. Lin, and Z. Huang. 2019. Optimization of delignification from Douglas fir sawdust by alkaline pretreatment with sodium hydroxide and its effect on structural and chemical properties of lignin and pyrolysis products. Bioresource Technology Reports, 8, 100339. doi: 10.1016/j.biteb.2019.100339.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: D. Duan, Y. Zhang, H. Lei, E. Villota, R. Ruan. 2019. Renewable jet-fuel range hydrocarbons production from co-pyrolysis of lignin and soapstock with the activated carbon catalyst. Waste Management, 88, 1-9. doi: 10.1016/j.wasman.2019.03.030.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: D. Duan, H. Lei, Y. Wang, Y. Liu, R. Ruan, Y Liu, L. Ding, Y. Zhang, L. Liu. 2019. Renewable phenol production from lignin with acid pretreatment and ex-situ catalytic pyrolysis. Journal of Cleaner Production, 231, 331-340. doi: 10.1016/j.jclepro.2019.05.206.
  • Type: Book Chapters Status: Published Year Published: 2019 Citation: R. Ruan, Y. Zhang, P. Chen, S. Liu, L. Fan, N. Zhou, K. Ding, P. Peng, M. Addy, Y. Cheng, E. Anderson, Y. Wang, Y. Liu, H. Lei, B. Li. 2019. Biofuels: Introduction, in Biofuels: Alternative Feedstocks and Conversion Processes for the Production of Liquid and Gaseous Biofuels in Biomass, Biofuels, Biochemicals (2nd Edition). pp. 343. Academic Press.
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: Y. Zhang, D. Duan, H. Lei, C. Wang, M. Qian, E. Villota, W. Mateo. 2020. From Douglas fir to renewable H2-enriched syngas via ex-situ catalytic pyrolysis over metal nanoparticles-nanocellulose derived carbon catalysts. Sustainable Energy and Fuels, 4 1084-1087. doi: 10.1039/C9SE00860H.
  • Type: Theses/Dissertations Status: Published Year Published: 2020 Citation: Moriko Qian. 2020. PhD thesis: Biomass-assisted synthesis of hierarchical zeolites for catalytic fast pyrolysis of lignocellulose biomass and waste plastic
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: M. Qian, H. Lei, E. Villota, W. Mateo, D. Duan, Y. Zhao, E., Huo, Q. Zhang, X. Lin, Z. Huang. 2019. A green approach to nanocrystalline cellulose production with cellulase from Aspergillus niger. 2019 ASABE Annual International Meeting, Boston, Massachusetts USA, July 7-10, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Y. Zhao, H. Lei, Y. Liu, D. Duan, R. Ruan, M. Qian, E. Huo, E. Villota, W. Mateo, Q. Zhang, X. Lin, Z. Huang. 2019. Preparation of magnetic biochar-based solid acid and its nano-effect on cellulose. 2019 ASABE Annual International Meeting, Boston, Massachusetts USA, July 7-10, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: M. Qian, Y. Zhang, D. Duan, Y. Zhao, W. Mateo, E. Huo, H. Lei. 2019. Nano Cellulose-Based Nanoparticle Catalysts For Bio-Jet Fuel Ranged Cycloalkanes Production. 2019 USDA/NIFA Nanotechnology Grantees Annual Meeting, Vanderbilt University, May 20-21, 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: M. Qian, H. Lei, E. Villota, W. Mateo, D. Duan, Y. Zhao. 2019. Enhancement of aromatic hydrocarbons from co-feeding of lignocellulosic biomass with plastics over hierarchical zeolites. 2019 ASABE Annual International Meeting, Boston, Massachusetts USA, July 7-10, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: H. Lei. 2019. H2 saving process for production of aromatics for jet fuels. 2019 Five-Year Reflection Sun Grant Western Regional Center, Newport, OR, August 21-22, 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: (Invited) H. Lei, Y. Zhang, D. Duan, E. Villota, Y. Zhao, Y. Liu, R., Ruan. 2019. Activated carbon as catalyst for biomass and waste plastics conversions to chemicals and biofuels. International Conference on Biofuels and Bioenergy (BBC 2019), San Francisco, CA, USA, April 29-May 01, 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: (Invited) H. Lei, M. Qian, Y. Zhang, D. Duan, E. Villota, W. Mateo, Y. Zhao. 2019. Carbon catalysts for producing jet fuel from plastic waste via catalytic pyrolysis. 2019 Rottary Club meeting, Pullman, WA, July 24, 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: M. Qian, H Lei, E, M. Villota, W, C. Mateo, D. Duan, Y. Zhao. 2019. Modification of ZSM-5 zeolites for improving aromatic hydrocarbon production in co-fed biomass pyrolysis with waste plastics. 2019 WSU ShowCase Conference, Pullman, WA, March 25, 2019


Progress 03/01/18 to 02/28/19

Outputs
Target Audience:Biomass industrial companies, biofuel-related industries, biomass and biofuel producers, processors, wholesalers, and retailers: including Creative Energy Systems Inc., MS Sustainables, LLC., North America Green Pulp Inc., USS International Group, LLP., Sustainable Fiber Technologies, Inc. Efforts: Formal classroom instruction (new course lectures/sessions) about the project in BSysE 593 Renewable Energy Technologies, BSYSE 551 Advanced Biological Systems Engineering Topics: Mass Balances, Energy Balances, and Unit Operations; BSysE 552 Advanced Biological Systems Engineering Topics: Economic and Environmental Sustainability of Energy; Development of curriculum (new lecture sessions on biomass conversion and catalysis, biomass-derived nanocellulose, nanocarbon catalysts, chemicals, bio jet fuel); Trained graduate and undergraduate students and post-doctoral researchers who work on this project will eventually join the workforce and contribute to the effort of utilizing biomass and developing bioproducts (i.e. nanocellulose, nanocarbon catalysts) and renewable energy technology for the future energy needs: PhD students: Marie Qian, Wendy Mateo, Dengle Duan, Erguang Huo, Yunfeng Zhao; undergraduate students: Roy Leal, Erick Leal; and post-doc: Yayun Zhang. New experiential learning opportunities for involved students in the project; Presentations, seminars, and communications to local communities, such as 2018 WSU ShowCase Conference, NORM 2018, 73rd Northwest Regional Meeting of the American Chemical Society, regional and national conferences (see the session of publication list in Product); Extension and outreach include outreach communications and presentations to biomass industrial companies, biofuels, and related industries. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training activities: The funding received from this project has been used to support 1 post-doc, 5 Ph.D. candidates, and 2 undergraduate students in the WSU Biological Systems Engineering Program. 5 Ph.D. students, 2 undergraduate students, and 1 post-doc research associates learned to develop new technologies, new processes, and new catalyst materials. Post-doc and Ph.D. students have developed the experience assisting MS students and undergraduate students attaining greater proficiency in developing new technologies and conducting experiments. PIs incorporated the research results from this project in teaching BSysE 593 Renewable Energy Technologies, BSYSE 551 and 552 Advanced Biological Systems Engineering Topics. Professional development activities: PIs had monthly conference calls with industrial collaborators and active collaborations among each other, and PI research group had weekly meetings to make sure the good progress of the project. PI and the research team had updates presented at group meetings. Students developed collaboration skills and exchanged technical information cross group knowledge. Ph.D. Students and Post-doc have participated and presented papers at American Society of Agricultural and Biological Engineers (ASABE) 2018 Annual International Meeting at Detroit, Michigan, July 29 - August 01, 2018, 2018, Nanoscale Science and Engineering for Agriculture and Food Systems Gordon Research Conference, South Hadley, MA, June 03 - 08, 2018, NORM 2018, 73rd Northwest Regional Meeting of the American Chemical Society, and WSU ShowCase Conference, Pullman, WA, March 25, 2018. How have the results been disseminated to communities of interest?The PI and the students and post-doc created posters and/or made oral presentations to showcase findings and present the study results. The research findings were communicated to the general public via national and international conferences, such as the American Society of Agricultural and Biological Engineers (ASABE) 2018 Annual International Meeting at Detroit, Michigan, July 29 - August 01, 2018, Nanoscale Science and Engineering for Agriculture and Food Systems Gordon Research Conference, South Hadley, MA, June 03 - 08, 2018, 2018 WSU ShowCase Conference, Pullman, WA, March 25, 2018. The published journal papers and proceedings can be found in previous sessions in this progress report. We also disseminated our research results to communities by presenting to industrial delegations and academic communities. Our outreach dissemination efforts include: NORM 2018, 73rd Northwest Regional Meeting of the American Chemical Society, Richland WA; 2018 Meetings of biomass conversions for biofuels and bioproducts with Creative Energy Systems Inc., MSS Sustainable LLC, USS International LLP, North America Green Pulp Inc., Washington Biooils Inc., Sustainable Fiber Technologies, Inc. What do you plan to do during the next reporting period to accomplish the goals?During the next year of 2019, we will continue working on studying the cellulose isolation from biomass and determine the effects of microwave-irradiation pretreatment on enzymatic hydrolysis for nanocrystalline cellulose (NCC) production. We will investigate the physical structure and chemical complexity of biomass-derived nanocellulose, and understand the microscopic structure and identify and control the functional groups which are related to nanocellulose process conditions and nanocarbon catalyst performance. We will continue developing and fabricating the nanocatalysts, and study the carbonization behavior of nanocellulose in order to develop a best performance nanocarbon catalyst. We anticipate that we will meet the objectives of the proposed work in a timely manner.

Impacts
What was accomplished under these goals? Impact: The recent development of functionalized nanocelluloses applied in various industrial sectors has resulted in transformation on nanocellulose market. The changes are driven by the increasing demand for biodegradable and non-toxic nanomaterials. The increasing market provides new opportunities for the agricultural economy and helps to activate the existing forestry industry, which suffered a significant recession due to the declining global demand for paper. The existing Nanocrystalline cellulose (NCC) technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (i.e. sulfuric acid, 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project is to develop a green process of NCC production based on enzymatic hydrolysis, which leads to less environmental concerns and unmodified surface chemistry of NCC. Our hypothesis is that by careful selection of cellulase enzymes and hydrolysis conditions, it is possible to efficiently produce NCC from biomass without using a high concentration of harsh acids, and subsequently synthesize metal-NCC nanoparticles for jet fuel production. The project team is focused directly on creating and integrating new technologies and is lining and engaging related industries in our outreach and education efforts and involved them in the development of biomass-derived high-value catalysts, chemicals, and biofuels. Major activities completed / experiments conducted / data collected / results / key outcomes: Isolation of cellulosic materials: We are conducting the "clean biomass fractionation" by developing a biomass-based sulfonated solid acid catalyst from corncob by direct sulfuric acid carbonization-sulfonation in a reflux system. We investigated the one-step preparation process based on central composite experimental design. The reaction parameters studied were temperature (100-140oC) and time (5-9 hours). The -SO3H functional groups were successfully introduced into the biomass-based solid acid catalyst as evidenced by FTIR, acid-base titration and sulfur analysis. Numerical optimization results showed that reaction temperature of 100oC and time of 5 hours are the optimum conditions for maximizing yield (61.13%), SO3H acid density (1.6130 mmol/g) and sulfur content (1.1508 mmol/g). Reduced acid loading conditions on NCC production: The nanocrystalline cellulose (NCC) was prepared with an acid treatment and enzymatic hydrolysis. The cellulose was acid hydrolyzed by a reduced sulfuric acid loading from 10 to 20 wt.% for 3 days at 50 ?C under agitation. A cellulase from Aspergillus niger was added for enzymatic hydrolysis at 50 ?C under agitation. We investigated the enzymatic hydrolysis under factors of fiber to liquor ratio, feedstock to enzyme ratio, and 24, 48, 72 or 96 hours of enzymatic hydrolysis. All NCC products and residue from enzymatic hydrolysis were freeze-dried at -54 ?C for further characterization after recording the product yields. Diluted acid conditions on NCC production: Aiming to reduce the amount of acid consumption as well as to improve the efficiency of diluted-acid pretreatment, microwave irradiation was applied to the process. Specifically, cellulose was pretreated with 1, 2, 5 and 10 wt.% sulfuric acid at 95 ?C with microwave heating at 300 W. For comparison, cellulose was also pretreated with sulfuric acid in a conventional oven at 50 or 95 ?C. The pretreated cellulose was added with cellulase from Aspergillus niger and kept at 50 ?C for 3 or 6 days. The produced NCC is indicated by heating type and temperature followed by the enzymatic hydrolysis time, for example, microwave heating at 95 ?C with sulfuric acid and 3 days of enzymatic hydrolysis is M95-3. The yields of extracted NCC from reduced acid loadings were investigated. The highest yield was recorded at 81.3 wt.% with C50-12, however, the incubation time of 12 days was excessively long in comparison to other reports on biological processing of cellulose for NCC. Under the reduced acid loadings, the NCC yields ranged from 36.9 to 52.6 wt.%. The reason for the low yield is due to the high recalcitrance of cellulose since there are very few amorphous contents remaining in cellulose for the acid or enzyme to fractionate. The NCC yield from diluted-acid pretreatment with microwave irradiation and with conventional heating was reported. It is noteworthy that diluted low-acid pretreatment was effective in improving the low yield of NCC (from 9.5 to 16.9 wt.%) in blank/control runs (no acid). In general, the higher acid concentration favored higher NCC yield during pretreatment, however, longer enzymatic hydrolysis time could increase the yield with lower acid concentrations. The effect of microwave heating on the NCC yield was significant with M95-3-10wt% which was observed at 96.2 wt.% based on the raw material. Interestingly, the cellulose pretreated by 5 wt.% sulfuric acid from both microwave and conventional heatings had the highest NCC yield among other concentrations of acid with longer enzymatic hydrolysis time. The pH reduction and enzyme deactivation may have resulted in changes of the enzymatic hydrolysis, and the statistical analysis is necessary to further testify this trend. The pH of the effluent is affected by many factors, such as chemical ions in the solution and its concentration, and the chemical functionalization of cellulose during sulfuric acid pretreatment. The results suggest that the balance of acid concentration during pretreatment and the time of consequent enzymatic hydrolysis should be focused on process optimization. The carbonization of glucose (1 nm), nanocellulose (50-100 nm), and cellulose was compared to elucidate the carbon yield using both a fixed-bed and a microwave assisted carbonization reactors. We found that microwave carbonization resulted in a significant higher carbon yield compared to that using a fixed bed. The two-carbonization methods will be further studied for the preparation of nanocarbon catalysts. The prepared NCCs were characterized by TEM imaging to observe the structure and size distribution of the crystals. The rod-like crystals with a length of approximately 50 to 100 nm were observed. The NCC prepared with a lower concentration of acid in pretreatment has less association among each crystal, however, the NCC from pretreatment in 2, 5, and 10 wt.% of the sulfuric acid solution seemed to form large aggregations during drying. As a result, the observation of each crystal of NCC becomes very difficult with TEM imaging. Change in Knowledge: Increased understanding of the control and degree we tune for the nanocellulose microstructure during cellulose hydrolysis; Increased understanding of how the NCC yield was affected by acid concentrations, enzymatic hydrolysis, and pretreatment methods; Increased understanding of reaction mechanism and reactions responsible for the formation of nanocellulose. Change in Action: A new way of producing nanocellulose and nanocarbon catalysts from lignocelluloses biomass and lay the foundation for achieving advanced bio-jet fuel production by using biomass-derived nanocelluose and nanocarbon catalysts. Change in Condition: The existing NCC technology is mainly based on hydrolysis in the presence of highly concentrated mineral acids (hydrochloric acid and sulfuric acid at typically 55-65 wt.%), which raises challenges associated with process control, safety, maintenance, and environmental protection. This project and the accelerated development of its technology will improve the current situation of nanocellulose production, biomass conversion, and enhance the economic and energy security of the United States and maintain a technological lead in developing and deploying advanced energy technologies. This conversion system will significantly reduce energy-related emissions, including greenhouse gases and have a positive carbon effect.

Publications

  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, D. Duan, E. Villota, R. Ruan. 2018. From Glucose-Based Carbohydrates to Phenol-rich Bio-oil Integrated with Syngas Production via Catalytic Pyrolysis over Activated Carbon Catalyst. Green Chemistry, 20, 3346 - 3358.
  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, K. Qian, E. Villota. 2018. Renewable High-Purity Mono-Phenol Production from Catalytic Microwave-Induced Pyrolysis of Cellulose over Biomass-Derived Activated Carbon Catalyst. ACS Sustainable Chemistry & Engineering, 6 (4), pp 53495357.
  • Type: Journal Articles Status: Other Year Published: 2018 Citation: Y. Zhang, H. Lei, D. Duan, M. Qian, W. Mateo, E. Huo, Y. Zhao. 2019. From Douglas fir to renewable H2-enriched syngas via ex-situ catalytic pyrolysis over metal nanoparticles-nanocellulose derived carbon catalysts, manuscript prepared and to be submitted in May 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, E. Villota, M. Qian. 2018. Nanocellulose production and its derived carbon catalysts for syngas upgrading. 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29 - August 01, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, E. Villota, M. Qian. 2018. Bio-oil Upgrading over Nanocellulose-Derived Nano-Carbon Catalysts Doped with Metal Atoms. 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29 - August 01, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: W. Mateo, H. Lei, E. Villota, Z. Yang, Y. Zhang, M. Qian, K. Qian, D. Duan. 2018. Synthesis and Performance of Carbon-based Solid Acid Catalyst for Organosolv Fractionation. 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29 - August 01, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, E. Villota, M. Qian, D. Duan. 2018. Nanocellulose-Derived Nano-Carbon Catalysts for Biomass Conversion and Bio-oil Upgrading. Nanoscale Science and Engineering for Agriculture and Food Systems Gordon Research Conference, South Hadley, MA, June 03 - 08, 2018
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Y. Zhang, H. Lei, Z. Yang, D. Duan, E. Villota, M. Qian. 2018. From Carbohydrates to Phenol-rich Bio-oil Integrated with Syngas Production via Catalytic Pyrolysis over Activated Carbon Catalyst. 2018 WSU ShowCase Conference, Pullman, WA, March 25, 2018