$2 billion in U.S.).Phenols concentration or OH number in pyrolysis oil is the most important parameter for producing resins using pyrolysis oil. The pyrolysis study in this project will evaluate different techniques to increase the OH number in bio-oil. The long-term goal of our research is to develop a better understanding of different bio-oil production techniques to increase the OH number and understand the relationship between the chemical structure in bio-oil and solid-state properties of the proposed IPNs in the context of developing resins and conductive polymer systems from renewable resources. During the proposed three years, the team will conduct the necessary study needed to design, synthesize, and test final properties of IPNs suitable for high mechanical performance, good adhesion properties and electrical and thermal conductivities. To reach this goal, five specific objectives are proposed as follows: (a) investigate different alternatives for enhancing the quality of bio-oil in terms of phenol concentration or OH number to promote polymerization reactions; (b) identify the role of different bio-oil compounds for polymerization reactions and produce novolac and novolac based IPNs from bio-oil; (c) evaluate mechanical and other properties of resins; (d) investigate the possibility of replacing petroleum based resins with bio-based resins; and (e) perform techno-economic analysis of the proposed process.This project specifically addresses the goals of the Agricultural Systems and Technology Priority focused on Engineering, Products and Processes. The production of adhesives/resins from pyrolysis oil using lignocellulosic biomass would lead to sustainable and innovative solutions for U.S. and global agriculture and biobased industries.' />
Source: AUBURN UNIVERSITY submitted to NRP
FORMATION OF PHENOLIC RESIN BASED INTERPENETRATING POLYMER NETWORK FROM PYROLYSIS OIL
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
AFRI COMPETITIVE GRANT
Reporting Frequency
Annual
Accession No.
1005077
Grant No.
2015-67021-22842
Cumulative Award Amt.
$494,336.00
Proposal No.
2014-03812
Multistate No.
(N/A)
Project Start Date
Dec 1, 2014
Project End Date
Nov 30, 2017
Grant Year
2015
Program Code
[A1521]- Agricultural Engineering
Recipient Organization
AUBURN UNIVERSITY
108 M. WHITE SMITH HALL
AUBURN,AL 36849
Performing Department
Biosystems Engineering
Non Technical Summary
Our overarching goal is to produce resins (novolac) and epoxy- novolac and novolac-polyaniline based interpenetrating polymer networks (IPNs) from fast pyrolysis bio-oil to replace petroleum based adhesives and conductive paints. The market share of these products is several billions of dollars. For example, phenol formaldehyde (PF) is the dominant resin for engineered wood composites, and accounts for $2.3 billion in revenue in North America and $10 billion worldwide. In addition, the conductive polymers' market is worth more than $14 billion worldwide (>$2 billion in U.S.).Phenols concentration or OH number in pyrolysis oil is the most important parameter for producing resins using pyrolysis oil. The pyrolysis study in this project will evaluate different techniques to increase the OH number in bio-oil. The long-term goal of our research is to develop a better understanding of different bio-oil production techniques to increase the OH number and understand the relationship between the chemical structure in bio-oil and solid-state properties of the proposed IPNs in the context of developing resins and conductive polymer systems from renewable resources. During the proposed three years, the team will conduct the necessary study needed to design, synthesize, and test final properties of IPNs suitable for high mechanical performance, good adhesion properties and electrical and thermal conductivities. To reach this goal, five specific objectives are proposed as follows: (a) investigate different alternatives for enhancing the quality of bio-oil in terms of phenol concentration or OH number to promote polymerization reactions; (b) identify the role of different bio-oil compounds for polymerization reactions and produce novolac and novolac based IPNs from bio-oil; (c) evaluate mechanical and other properties of resins; (d) investigate the possibility of replacing petroleum based resins with bio-based resins; and (e) perform techno-economic analysis of the proposed process.This project specifically addresses the goals of the Agricultural Systems and Technology Priority focused on Engineering, Products and Processes. The production of adhesives/resins from pyrolysis oil using lignocellulosic biomass would lead to sustainable and innovative solutions for U.S. and global agriculture and biobased industries.
Animal Health Component
30%
Research Effort Categories
Basic
30%
Applied
30%
Developmental
40%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
40206502020100%
Knowledge Area
402 - Engineering Systems and Equipment;

Subject Of Investigation
0650 - Wood and wood products;

Field Of Science
2020 - Engineering;
Goals / Objectives
The long-term goal of our research is to develop a better understanding of different bio-oil production techniques to increase the OH number and understand the relationship between the chemical structure in bio-oil and solid-state properties of the proposed interpenetrating networks (IPNs) in the context of developing resins and conductive polymer systems from renewable resources. During the proposed three years, the team will conduct the necessary study needed to design, synthesize, and test final properties of IPNs suitable for high mechanical performance, good adhesion properties and electrical and thermal conductivities.To reach this goal, five specific objectives are proposed as follows: (a) investigate different alternatives for enhancing the quality of bio-oil in terms of phenol concentration or OH number to promote polymerization reactions; (b) identify the role of different bio-oil compounds for polymerization reactions and produce novolac and novolac based IPNs from bio-oil; (c) evaluate mechanical and other properties of resins; (d) investigate the possibility of replacing petroleum based resins with bio-based resins; and (e) perform techno-economic analysis of the proposed process.
Project Methods
The proposed research is divided into four tasks. Task 1: Investigate different alternatives for enhancing the quality of bio-oil to promote polymerization reactionsIn this task, three different approaches will be used to increase phenols concentration or OH number in the pyrolysis oil. First, three torrefied biomass feedstocks types (pine wood, switchgrass, and corn stover) will be used to determine whether or not biomass type has significant influence on OH number. Prior to experiments, biomass feedstocks will be characterized using routine analyses. Torrefaction of these feedstocks will be performed at a temperature of 250oC and 30 min. Pyrolysis oil will be produced at 500oC using a bubbling bed fluidized reactor. Second, we will test five zeolite catalysts with different pore sizes [e.g., ZK-5 (pore size = 3.9 Ao), SAPO-34 (4.3 Ao), ZSM-5(5.1 Ao), b zeolite (6.6 Ao), Y zeolite (7.4 Ao)] to evaluate the effect of pore size on phenols concentration. Third, the effect of acidity will also be investigated, and the acidity of the selected catalysts will be changed by varying the silica to alumina ratio. Pyrolysis oils collected from condensers and ESP will be characterized for OH number (ASTM D2849-69) and other properties (ASTM D7544-09) such as water content, elemental composition, TAN number, pH and heating. Catalyst deactivation and regeneration studies will also be performed to collect necessary data needed for techno-economic analysis of the proposed pathway for making resins.Task 2: Demonstrate innovative technologies to create novolac-based IPNIn this task, we will synthesize IPNs using different polymer systems to form phenolic-based (novolac-epoxy phase) and conductive (novolac-polyaniline phase) IPNs. "As-produced" IPNs will have complicated component formulations, which may contain or trap small organic molecules and water molecules in the polymer network. A post-synthesis purification step might be necessary in order to separate the product and the impurities or small molecules from the bio-oil or the reagents. The post-synthesis purification step will include washing, extracting, dialyzing, centrifuge, and drying the "as-produced" polymer resins with regular solvents, such as water, acetone or toluene. The aforementioned solvents are used to remove the small organic compounds, moisture and other impurities.Task 3: Application of Epoxy-Novalac and Novolac-PANI IPNsTask 3-1 Wood based structural composite manufacture and testingBio-oil based IPNs will be tested for composite manufactures. Southern pine flakes obtained from a local manufacturer will be placed into a rotary blender and run at approximately 20 rpm for the phenol-formaldehyde (PF) resin control application. Given the anticipated higher viscosity of the new resin, we will use solvent to control the viscosity so that homogenous wood-polymer mixtures can be obtained prior to press. The target density of the panel will be 577 kg/m3 (i.e., 36 lb/ft3) and the dimensions will be 11 mm thick by 609 mm wide and 609 mm long. Just before pressing, a thermocouple will be placed into the center of the panel to monitor internal temperature. The temperature curve will be monitored, and the reduction in press time with novolac-PANI IPNs will then be measured and reported. A constant pressure of 1400 psi will be applied through the entire press schedule and metal strips will be used to stop the press at the 11 mm thickness to produce the panel. Modulus of elasticity (MOE) and modulus of rupture (MOR) will be measured, and the Parallel D-4 Maximum Moment will be computed from the MOR test data to ensure that the product meets industry standards. Internal bond (IB) samples (6 replicates per board) will be milled (2 x 2 inch) and the IB will be measured to determine the strength of the resin bond.Task 3-2 Application of Novolac-PANI IPNs as Conductive PaintsA number of tests following ASTM standards will be performed to determine the suitability of bio-oil based paints. Some of the tests that will be performed are based on ASTM D2197-13, ASTM D4541-09e1, ASTM D3359-09e2 and ASTM D4145-10. In addition, TGA will be used to determine the longevity of the paints using different heating rates. The effectiveness of this paint for anti-corrosion will be measured by immersing a plate into artificial seawater, prepared with sea salt mix (ASTM D1141-52) after painting. The open-circuit potential will be recorded under the treatment of this artificial seawater. An Arbin electrochemical station will be used in Dr. Zhang's (Co-PI) lab to monitor the anti-corrosion tests.Task 4: Techo-Economic Analysis (TEA)Sustainability (economic, environmental, and social acceptance) of bio-based products is critical to develop green economy. The investigators understand that the most important question is whether or not the proposed technology will actually work to develop bio-oil based IPNs. However, in order to identify critical steps in the process, techno-economic analysis (TEA) will be performed by developing a process model, and detailed material and energy balance data will be generated using SuperPro Designer software (Intelligen, Inc., Scotch Plains, NJ). Input data to the process model will mainly be supplied from the experimental data generated in Tasks 1-3 and partially from a review of the published literature and database. Process modeling results will then be utilized to determine the resource requirements, including feedstock, process equipment, land, infrastructure, energy, labor, and chemicals (catalysts, formaldehyde, epoxy resin, etc.). This will be followed by an economic analysis to estimate the production cost of phenolic resin based IPN in the proposed system. Finally, sensitivity analysis will be performed to identify and rank the key parameters contributing to the overall phenolic resin based IPN production cost in the proposed system.

Progress 12/01/16 to 11/30/17

Outputs
Target Audience:The target audiences for this project were graduate students, researchers working in the area of bioproducts and companies that are interested in developing resins and adhesives from pyrolysis oil. The team approached to these groups via direct interaction and research presentations at the regional, national and international meetings. Changes/Problems:Because carbon nanotubes were expensive and hard to acquire industrially, we transitioned to graphite. We were able to make a bio-oil-phenol formaldehyde-graphite adhesive composite to improve strength and conductivity but at a lower cost than carbon nanotubes. What opportunities for training and professional development has the project provided?Personnel involved in this project learned various analytical tools to characterize bio-oil and resins. Also, students developed methods to synthesize resins from bio-oil. How have the results been disseminated to communities of interest?Results from this study have been disseminated mainly through presentation at local, regional, and national meetings and publication at peer-reviewed journals. What do you plan to do during the next reporting period to accomplish the goals?The project has been completed so there is no immediate activities planned but we will actively explore funding opportunities to advance the this study further.

Impacts
What was accomplished under these goals? Biomass pyrolysis oil (bio-oil) was substituted in place of phenol to varying extent (10wt%, 50wt%) and reacted with formaldehyde to produce bio-oil based phenol-formaldehyde novolac type polymer (bio-novolac). Bio-novolac was glycidylated to yield epoxidized bio-novolac resin. Glycidylation was also performed directly with bio-oil to yield epoxidized bio-oil. The resulting epoxy resins (epoxidized bio-novolac and epoxidized bio-oil) were crosslinked with commercially available amine hardener to form crosslinked materials. Organic phase of bio-oil was reacted with cyanogen bromide to produce bio-oil based cyanate ester resin, which was heat-cured to produce thermoset materials possessing high glass transition temperature. On the other hand, aqueous phase of bio-oil was treated with several reagents in separate attempts to introduce olefin functionality. Organic compounds in aqueous phase of bio-oil, such as alcohols, phenols, carboxylic acids, aldehydes and ketones were converted into olefinated derivatives by different routes. Wittig reaction was performed to convert aldehydes and ketones to terminal alkenes. Methacryloyl chloride and maleic anhydride were reacted separately with bio-oil to yield methacrylated and maleinated bio-oil. The olefin groups were polymerized by free radical polymerization. Fourier transform infrared spectroscopy (FTIR) revealed disappearance of peaks corresponding to C=C and =C-H, indicating the initiation of C=C by free radical initiator followed by polymerization. Bio-oil based epoxy resins indicated comparable thermo-mechanical performance (glass transition temperature and storage modulus) to their petroleum-based epoxy counterparts. No bisphenol-A was used in bio-oil derived epoxy resins, indicating a less toxic system than conventional epoxy resins based on diglycidyl ether of bisphenol-A (DGEBPA). Cyanate ester resins required no crosslinking agent unlike epoxy resins and hence, proved to increase the renewable content by a remarkable extent. Moreover, formation of aromatic triazine rings enhanced the glass transition temperature. Additionaly, we were able to develope a self curing epoxy resin from bio-oil. This technology is novel because it not only replaces petroleum based epoxy, but if it can cure within the wood composite without a cross linking agent. It could result in a practical adhesive for wood composite use. The corrosion performance of steel was successfully enhanced significantly by studying the dopant effect on electrodeposition of conducting polymer coating. The dopants used in the study are: p-toluene sulfonic acid (p-TSA), sulfuric acid (SA), sodium dodecyl sulfate (SDS), and sodium dodecylbenzene sulfonate (SDBS). The protection mechanism depends on size and alignment of dopant in the polymer backbone. The protection efficiency was better for bigger and bulkier dopants when compared to smaller ones. This is due to the steric hindrance in the polymer created by bulkier groups acts a barrier to ions that diffuses through the coating. The protection was further extended by using conducting polymer with bio-oil derived epoxy that makes the barrier stronger than single conducting polymer layer. This coating can replace the expensive and hazardous heavy metal primers used commercially available epoxy or acrylics based paints. In conclusion, conducting polymer coating was successfully used to protect the steel surface from corrosion by providing anodic protection. The protection performance can be influenced by the size of the dopant used for conducting polymer film, the bigger dopants provided better protection than those of smaller size. Further protection was improved by introducing aromatic group (such as benzene) to the dopants. This increases the electron density in the coating system that repels the negatively charged chloride ion. In addition to the corrosion performance, the adhesion of the coating was significantly enhanced by the adding decanoic acid. The decanoic acid provides an anchor between the coating and metal surface making it adhere to the surface better. Moreover, polyaniline and epoxy coating system was fabricated to study the durability of the coating system in corrosive medium. The polyaniline with bio-oil derived epoxy happened to be more durable for longer time when compared to polyaniline and commercial epoxy coating. It showed great potential to replace currently available heavy metal primers that are toxic and hazardous to living being. It can be used in commercial paint along with commercially available epoxy, acrylic resin based paints. A techno-economic model for Novolac resin production in a commercial scale plant has been developed. The model also incorporates the production of bio-oil by fast pyrolysis of southern pine wood with and without torrefaction. The techno-economic feasibility of substituting a portion of phenol used for Novolac resin synthesis by phenolic components present in biooil was analyzed. For analysis, two different production scales were considered: 1) 22,000 MT/year of novolac resin production based on the existing resin production facility in Ohio. This was based on the information on the two resin production facilities in Ohio with cumulative production capacity of 44,000 MT/year. Thus, for a single plant, we assumed 22,000 MT/year production capacity. However, there are production facilities with higher production capacities in other parts of the U.S. 2) A large-scale production facility of 550,000 MT/year of novolac resin was also considered for the analysis, which requires 2,000 dry MT/day of biomass feedstock. Thus, the size and cost of the equipment used for the study were also taken from the same report. For these two production capacities, three scenarios were analyzed: Scenario 1: Base case scenario in which all the phenol used for novolac resin synthesis is obtained from petroleum sources. Scenario 2: Biooil is obtained via direct pyrolysis of pine wood chips and the phenolic fraction is separated to be used in resin synthesis as a partial substitute for phenol obtained from the petroleum sources. Scenario 3: Phenolic fraction present in biooil to be used for resin synthesis is obtained by fast pyrolysis of the torrefied pine wood chips, followed by the fractionation of phenolic compounds. The key results from TEA analysis is summarized below. For the resin production capacity of 22,000 MT/year, the resin production cost based on the partial substitution of phenol by phenolic fraction from biooil for resin synthesis was comparatively higher than that with the use of petroleum based phenol. The resin production cost using phenolic fraction of biooil without torrefaction was $1.42/kg and that with torrefaction was $1.62/kg, which is higher than $1.25/kg when the phenol used in resin synthesis is obtained from the petroleum sources. However, partially substituting phenol using biooil produced from a larger scale biooil production facility with 550,000 MT/year capacity could reduce the cost of resin production compared to using phenol. For the base case scenario where all the phenol for resin synthesis is obtained from petroleum, the resin production cost comprises largely of raw materials (~88%), fixed capital costs (~4%), and labor (~7%). For the second scenario considered in the study, in which the phenol used for resin synthesis was partially substituted with biooil, raw materials (~60%), labor (~20%), capital cost (~11%) and utilities (~7%) had significant shares in the total production cost. For the third scenario, in which phenol used in resin synthesis was partially substituted with biooil produced from pyrolysis of torrefied, biomass, raw materials (~57%), labor (~18%), capital cost (~15%) and utilities (~6%) contributed significantly to the total production cost

Publications

  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Baral, N. & Shah, A. (2017). Techno-economic analysis of utilization of stillage from a cellulosic biorefinery. Fuel Processing Technology. 166: 59-68.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Celikbag Y., Meadows S., Barde M., Adhikari S., Buschle-Diller, G., Auad M. L., Via B., (2017) Synthesis and Characterization of Bio-oil-based Self-curing Epoxy Resin. Industrial & Engineering Chemistry Research. 56: 9389-9400
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Hern�ndez B. S., Barde M., Via B., Auad M. L. (2017) Sustainable products from bio-oils. MRS Bulletin. 42: 365-370
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Katrina Avery, Mehul Barde,Maria L. Auad. Aqueous Phase of Biomass Pyrolysis Oil as a Raw Material for Polymer Synthesis. 2017 AIChE Annual Meeting, Minneapolis, MN.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Mehul Barde, Bernal Sibaja, Yusuf Celikbag,Brian Via, Sushil Adhikari, William Edmunds, Nicole Labbe,Maria L. Auad. Novel thermoset polymeric networks from fast pyrolysis bio-oil. 253rd American Chemical Society National Meeting, San Francisco, CA. April 2017.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: A. Nautiyal, M. Qiao, J.E. Cook, X. Zhang, T.-S. Huang, High performance polypyrrole coating for corrosion protection and biocidal applications, Appl. Surf. Sci. 2018, 427, 922930.
  • Type: Journal Articles Status: Accepted Year Published: 2017 Citation: Sibaja, B., Adhikari, S., Celikbag, Y., Via, B. K., Auad, M. L. 2017. Fast Pyrolysis Bio-oil as Precursor of Thermosetting Epoxy Resins. Polymer Engineering & Science. DOI: 10.1002/pen.24694
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Celikbag, Y., Meadows, S., Barde, M., Adhikari, S., Buschle-Diller, G., Auad, M. L., Via, B. 2017. Synthesis and Characterization of Bio-oil-based Self-curing Epoxy Resin.71st Forest Product Society (FPS) International Convention. Starkville, MS. June 26th, 2017
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Celikbag, Y., Meadows, S., Barde, M., Adhikari, S., Buschle-Diller, G., Auad, M. L., Via, B. 2017. Self-curing Epoxy Resin as a Bio-based Adhesive for Wood Products. 11th International Conference on Wood Adhesives  Forest Product Society (FPS). Atlanta, GA. October 25-27, 2017.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Celikbag, Y., Meadows, S., Barde, M., Adhikari, S., Buschle-Diller, G., Auad, M. L., Via, B. 2017. Synthesis and Characterization of Bio-oil-based Self-curing Epoxy Resin. 253rd American Chemical Society (ACS) National Meeting and Exposition. San Francisco, CA. USA. April 5th, 2017


Progress 12/01/14 to 11/30/17

Outputs
Target Audience:The target audiences for this project were graduate students, researchers working in the area of bioproducts and companies that are interested in developing resins and adhesives from pyrolysis oil. The team approached to these groups via direct interaction and research presentations at the regional, national and international meetings. Changes/Problems:Because carbon nanotubes were expensive and hard to acquire industrially, we transitioned to graphite. We were able to make a bio-oil-phenol formaldehyde-graphite adhesive composite to improve strength and conductivity but at a lower cost than carbon nanotubes. What opportunities for training and professional development has the project provided?Personnel involved in this project learned various analytical tools to characterize bio-oil and resins. Also, students developed methods to synthesize resins from bio-oil. How have the results been disseminated to communities of interest?Results from this study have been disseminated mainly through presentation at local, regional, and national meetings and publication at peer-reviewed journals. What do you plan to do during the next reporting period to accomplish the goals?The project has been completed so there is no immediate activities planned but we will actively explore funding opportunities to advance the this study further.

Impacts
What was accomplished under these goals? Biomass pyrolysis oil (bio-oil) was substituted in place of phenol to varying extent (10wt%, 50wt%) and reacted with formaldehyde to produce bio-oil based phenol-formaldehyde novolac type polymer (bio-novolac). Bio-novolac was glycidylated to yield epoxidized bio-novolac resin. Glycidylation was also performed directly with bio-oil to yield epoxidized biooil. The resulting epoxy resins (epoxidized bio-novolac and epoxidized bio-oil) were crosslinked with commercially available amine hardener to form crosslinked materials. Organic phase of bio-oil was reacted with cyanogen bromide to produce bio-oil based cyanate ester resin, which was heat-cured to produce thermoset materials possessing high glass transition temperature. On the other hand, aqueous phase of bio-oil was treated with several reagents in separate attempts to introduce olefin functionality. Organic compounds in aqueous phase of bio-oil, such as alcohols, phenols, carboxylic acids, aldehydes and ketones were converted into olefinated derivatives by different routes. Wittig reaction was performed to convert aldehydes and ketones to terminal alkenes. Methacryloyl chloride and maleic anhydride were reacted separately with bio-oil to yield methacrylated and maleinated bio-oil. The olefin groups were polymerized by free radical polymerization. Fourier transform infrared spectroscopy (FTIR) revealed disappearance of peaks corresponding to C=C and =C-H, indicating the initiation of C=C by free radical initiator followed by polymerization. Bio-oil based epoxy resins indicated comparable thermo-mechanical performance (glass transition temperature and storage modulus) to their petroleum-based epoxy counterparts. No bisphenol-A was used in bio-oil derived epoxy resins, indicating a less toxic system than conventional epoxy resins based on diglycidyl ether of bisphenol-A (DGEBPA). Cyanate ester resins required no crosslinking agent unlike epoxy resins and hence, proved to increase the renewable content by a remarkable extent. Moreover, formation of aromatic triazine rings enhanced the glass transition temperature. Additionaly, we were able to develope a self curing epoxy resin from bio-oil. This technology is novel because it not only replaces petroleum based epoxy, but if it can cure within the wood composite without a cross linking agent. It could result in a practical adhesive for wood composite use. The corrosion performance of steel was successfully enhanced significantly by studying the dopant effect on electrodeposition of conducting polymer coating. The dopants used in the study are: p-toluene sulfonic acid (p-TSA), sulfuric acid (SA), sodium dodecyl sulfate (SDS), and sodium dodecylbenzene sulfonate (SDBS). The protection mechanism depends on size and alignment of dopant in the polymer backbone. The protection efficiency was better for bigger and bulkier dopants when compared to smaller ones. This is due to the steric hindrance in the polymer created by bulkier groups acts a barrier to ions that diffuses through the coating. The protection was further extended by using conducting polymer with bio-oil derived epoxy that makes the barrier stronger than single conducting polymer layer. This coating can replace the expensive and hazardous heavy metal primers used commercially available epoxy or acrylics based paints. In conclusion, conducting polymer coating was successfully used to protect the steel surface from corrosion by providing anodic protection. The protection performance can be influenced by the size of the dopant used for conducting polymer film, the bigger dopants provided better protection than those of smaller size. Further protection was improved by introducing aromatic group (such as benzene) to the dopants. This increases the electron density in the coating system that repels the negatively charged chloride ion. In addition to the corrosion performance, the adhesion of the coating was significantly enhanced by the adding decanoic acid. The decanoic acid provides an anchor between the coating and metal surface making it adhere to the surface better. Moreover, polyaniline and epoxy coating system was fabricated to study the durability of the coating system in corrosive medium. The polyaniline with bio-oil derived epoxy happened to be more durable for longer time when compared to polyaniline and commercial epoxy coating. It showed great potential to replace currently available heavy metal primers that are toxic and hazardous to living being. It can be used in commercial paint along with commercially available epoxy, acrylic resin based paints. A techno-economic model for Novolac resin production in a commercial scale plant has been developed. The model also incorporates the production of bio-oil by fast pyrolysis of southern pine wood with and without torrefaction. The technoeconomic feasibility of substituting a portion of phenol used for Novolac resin synthesis by phenolic components present in biooil was analyzed. For analysis, two different production scales were considered: 1) 22,000 MT/year of novolac resin production based on the existing resin production facility in Ohio. This was based on the information on the two resin production facilities in Ohio with cumulative production capacity of 44,000 MT/year. Thus, for a single plant, we assumed 22,000 MT/year production capacity. However, there are production facilities with higher production capacities in other parts of the U.S. 2) A large-scale production facility of 550,000 MT/year of novolac resin was also considered for the analysis, which requires 2,000 dry MT/day of biomass feedstock. Thus, the size and cost of the equipment used for the study were also taken from the same report. For these two production capacities, three scenarios were analyzed: Scenario 1: Base case scenario in which all the phenol used for novolac resin synthesis is obtained from petroleum sources. Scenario 2: Biooil is obtained via direct pyrolysis of pine wood chips and the phenolic fraction is separated to be used in resin synthesis as a partial substitute for phenol obtained from the petroleum sources. Scenario 3: Phenolic fraction present in biooil to be used for resin synthesis is obtained by fast pyrolysis of the torrefied pine wood chips, followed by the fractionation of phenolic compounds. The key results from TEA analysis is summarized below. • For the resin production capacity of 22,000 MT/year, the resin production cost based on the partial substitution of phenol by phenolic fraction from biooil for resin synthesis was comparatively higher than that with the use of petroleum based phenol. The resin production cost using phenolic fraction of biooil without torrefaction was $1.42/kg and that with torrefaction was $1.62/kg, which is higher than $1.25/kg when the phenol used in resin synthesis is obtained from the petroleum sources. However, partially substituting phenol using biooil produced from a larger scale biooil production facility with 550,000 MT/year capacity could reduce the cost of resin production compared to using phenol. • For the base case scenario where all the phenol for resin synthesis is obtained from petroleum, the resin production cost comprises largely of raw materials (~88%), fixed capital costs (~4%), and labor (~7%). For the second scenario considered in the study, in which the phenol used for resin synthesis was partially substituted with biooil, raw materials (~60%), labor (~20%), capital cost (~11%) and utilities (~7%) had significant shares in the total production cost. For the third scenario, in which phenol used in resin synthesis was partially substituted with biooil produced from pyrolysis of torrefied, biomass, raw materials (~57%), labor (~18%), capital cost (~15%) and utilities (~6%) contributed significantly

Publications


    Progress 12/01/15 to 11/30/16

    Outputs
    Target Audience:This year our work was mainly focused on producing pyrolysis oils and converting them into resins. Our target was mainly on training graduate studentsto make sure they understand the process of making pyrolysis oil and resins from it. We were also published some papers from our work, and the target audiences were mainly scientific community. Changes/Problems:Graphite was used instead of carbon nanotubes for potential decrease in press time due to competitive performance to cost ratio. Carbon nanotubes can still be investigated for comparison.Over the next year, these adhesive-oil-graphite systems will be combined to see if press time can be reduced during wood composite manufacture. Conducting polymer based paints will be formulated along with commercially available resins (epoxy or bio-oil based resin) and further anti-corrosion test will be tested on bigger samples including salt fog test for 24hr. Further, conducting polymer hollow nanostructures can be made to incorporate with either self-healing agents or any nobler metals, which can be released by applying potential to protect the steel surface. These nanostructures can be added to the formulated paints as an anticorrosive/self-healing agents and can also be used as a primer, which helps in obviating the use of toxic heavy metal primers. Also, adhesion issues will be enhanced by pretreatment of steel surface with adhesion promoter like n-alkanoid acids. What opportunities for training and professional development has the project provided?Graduate students were trained in producing pyrolysis oil and characterizing it. In addition, some students were trained to produced epoxy and novolac from bio-oil. One graduate student developed a framework for technoeconomic analysis. How have the results been disseminated to communities of interest?Yes. Most of the results were disseminated to scientific community through peer-reviewed manuscripts and conference presentations. What do you plan to do during the next reporting period to accomplish the goals?We will continue work to better understand the role of bio-oil on phyical and chemical properties of adhesives.

    Impacts
    What was accomplished under these goals? The biomass pyrolysis oil was mainly used for synthesizing phenol-formaldehyde novolac type polymers. During the synthesis, it was possible to make use of the functioanlities of phenol derivatives and polyphenolic nature of bio-oil to react with formaldehyde, in addition to phenol-formaldehyde reaction. The phenol was partially replaced on weight basis to form bio-oil-phenol-formaldehyde polymer. In an attempt to design interpenetrating polymer networks, BioNovolac polymer was added as a network to the epoxy resin from α-resorcylic acid which was crosslinked. Bio-oil/phenol, in molar excess, was reacted with formaldehyde using oxalic acid as catalyst to yield novolac-type biopolymer (BioNovolac). With the help of Fourier Transform Infrared (FTIR) spectroscopy, it was possible to monitor the reaction, by following the consumption of phenol. BioNovolac was purified by removing free phenol and catalyst and was physically blended with epoxy resin earlier derived from α-resorcylic acid. The resins are compatible and non-reactive. With such a physical blend, it was possible to polymerize epoxy resin in immediate presence of BioNovolac network to form bio-based interpenetrating polymer networks. The polymerization of α-resorcylic acid epoxy resin was carried out by amine hardeners in one type of systems (condensation polymerization) and by 4-(dimethylamino)pyridine in other (anionic polymerization). Both systems have were analyzed using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) to assess the thermal behavior. The results reveal that the interpenetrating polymer networks have high glass transition temperatures and modulus as compared to the crosslinked epoxy polymer. Further, the polypyrrole (PPy) coating was electrochemically synthesized on carbon steel using sulfonic acids as a dopant: short chain dopants [p-toluene sulfonic acid (p-TSA), sulfuric acid (SA)] and anionic surfactants; long chain dopants [sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS)]. The effect of acidic dopants (p-TSA, SA) on passivation of carbon steel was investigated by linear potentiodynamic and compared with morphology and corrosion protection performance of the coating produced. The types of the dopant used were significantly affecting the protection efficiency of the coating against chloride ion attack on the metal surface. The corrosion performance depends on size and alignment of dopant in the polymer backbone. During this period, we are more focused on influence of types of dopant on passivation of carbon steel, electrodeposition of polypyrrole coating and their effect on corrosion performance which helps us to optimize the dopant system for polypyrrole coating to obviate the use of toxic heavy metal primer used in commercially available paints. In addition to experimental work,a techno-economic model of biomass fast pyrolysis system has been developed, which will be integrated with biomass torrefaction and bio-oil to Novolac resin synthesis systems and required process equipment for biomass torrefaction system has been identified, and operating and equipment associated data are being gathered.

    Publications

    • Type: Journal Articles Status: Published Year Published: 2016 Citation: Celikbag, Y., Via, B. K., Adhikari, S., Buschle-Diller, G., & Auad, M. L. (2016). The effect of ethanol on hydroxyl and carbonyl groups in biopolyol produced by hydrothermal liquefaction of loblolly pine: 31 P-NMR and 19 F-NMR analysis. Bioresource Technology, 214, 37-44.
    • Type: Journal Articles Status: Published Year Published: 2016 Citation: Celikbag, Y., & Via, B. K. (2016). Characterization of residue and bio-oil produced by liquefaction of loblolly pine at different reaction times. Forest Products Journal, 66(1), 29-36.
    • Type: Journal Articles Status: Published Year Published: 2016 Citation: Baral, N.R., Wituszynski, D.M., Martin, J.F. & Shah, A. (2016). Sustainability Assessment of Cellulosic Biorefinery Stillage Utilization Methods Using Emergy Analysis. Energy 109, 13-28.
    • Type: Conference Papers and Presentations Status: Accepted Year Published: 2016 Citation: Baral, N.R., & Shah, A. (2015). Techno-Economic Analysis of Fast Pyrolysis of Stillage from Cellulosic Biorefineries. ASABE Annual International Meeting 2015, July 26-29, New Orleans, LA.
    • Type: Journal Articles Status: Accepted Year Published: 2016 Citation: Ravishankar Mahadevan, Sushil Adhikari, Rajdeep Shakya, Kaige Wang, David Dayton, Michael Lehrich and Steven Taylor. (2016) Effect of alkali and alkaline earth metals on in-situ catalytic fast pyrolysis of lignocellulosic biomass. Energy Fuels. Vol. 30 (4), pp. 30453056
    • Type: Conference Papers and Presentations Status: Accepted Year Published: 2016 Citation: Zhouhong Wang, Sushil Adhikari, Maria Auad, Mehul Barde and Melanie McDonald. Substitute phenol with bio-oil in the production of novolac resin. American Society of Agricultural and Biological Engineers (ASABE) annual international meeting, Orlando, FL. July 17-20, 2016
    • Type: Conference Papers and Presentations Status: Accepted Year Published: 2016 Citation: Maria L. Auad. Bio-Based Polymers based on Fast Pyrolysis Bio-oil. Invited keynote speaker, 7th Green Chemistry Conference, San Jose, Costa Rica, September 20-24th 2016.


    Progress 12/01/14 to 11/30/15

    Outputs
    Target Audience:This year the project was maninly focused on developing the methods formaking resins from bio-oilso we did not reach to any audience. However, one paper was published on biomass pyrolysis and reached to researchers working in the pyrolysis area. Changes/Problems:The graduate student hired for novolac resin production decided not to continue PhD and instead taking MS degree, and this has delayed the project slightly. What opportunities for training and professional development has the project provided?Graduate students involved in this project have presented their work at national meetings to share the results to discipline specific audiences. How have the results been disseminated to communities of interest?Through peer-reviewed publications and conferences. What do you plan to do during the next reporting period to accomplish the goals?1. Characterize novolac resins produced from bio-oil and understand the role of different bio-oil model compounds 2. Produce bio-oil number different biomass feedstocks and characterize them. 3. Develop techno-economic model for biomass pyrolysis and resin production

    Impacts
    What was accomplished under these goals? The major accomplishments for this period are: Two different bamboo species (Pseudosasa amabilis and Pleioblastus chino) were chosen as potential resources for producing biofuels and chemicals. Specifically, in this study, three stages (one year, two years and three years old) were considered to find the influence of aging on biomass properties, pyrolysis products distribution, and the properties of bamboo bio-oil. Changing trends of chemical components were similar for the two bamboo species, and their contents were comparable. Ash content of bamboo biomass increased with age; whereas, the soluble part of ash actually decreased. The insoluble part of ash contributed on char production. Bamboo lignin has more syringyl units than guaiacyl units. Higher heating value (HHV) of the two bamboo species were in the range of 19.4-19.9MJ/kg. Products distributions of bamboo pyrolysis were similar between two species; the yield of bio-oil (water free) was increasing with bamboo aging. Physical and chemical properties (e.g., density, pH, HHV, viscosity, water content and CHNO) as well as the chemical composition of the bio-oil were analyzed. Significant reduction in water content (from 26.30% to 9.65%) was observed in P. chino bio-oil, whereas it was fairly stable (from 16.26% to 15.82%) in P. amabilis bio-oil. The aging influence on the bio-oil properties was much lower for P. amabilis as compared to P. chino. α-resorcylic acid (α-RA) was successfully reacted with epichlorohydrin and an aqueous solution of sodium hydroxide in the presence ofa phase transfer catalyst to generate the triglycidylated ether of α-RA. In order to generate a polymeric material, epoxy monomers can undergo a chain homopolymerization in the presence of both Lewis acids and bases such as tertiary amines (known as anionic homopolymerization). The effect in the thermo-mechanical properties was assessed by dynamic mechanical analysis (DMA), following the change in the storage modulus as well as the evolution of the tan δ as a function of the temperature. Results revealed that the materials behaved as thermosets. As seen in figure 1 , the storage modulus initially remained approximately constant. As the temperature increased, the storage modulus exhibited a drop over a wide temperature range, followed by a modulus plateau at high temperatures, where the material behaved like a rubber. The modulus drop is associated with the beginning of segmental mobility in the cross-linked polymer network; whereas the constant modulus at temperatures above 150 °C is the result of the cross-linked structure of the polymer. Conducting polymers of various forms had been electrodeposited onto steel and electrochemical and environmental means have been used to access their capability for corrosion protection. Electrochemical deposition is to apply small driving force in form of potential that oxidizes the monomer to polymer, this process of polymerization is known as electropolymerization. This technique is best for conducting polymer deposition as they are electrically conducting and it's easy to make controlled coating thickness by changing the experimental factors like potential, scan rate, number of cycles etc.The steel sample (low carbon steel, LCS) was used as the surface, on which conducting polymer (CP) coating has been made. Polyaniline (PANI) has been studied so far and has been found to be good barrier for corrosion protection. PANI is electrodeposited from the monomer solution containing 3:1 dopant to monomer ratio. Oxalic acid was chosen for dopant as it helps in doping of polymer to make it conducting, which helps in deposition of polymer on the substrate. The coating was developed using cyclic voltammetry (CV) technique by sweeping the potential from -950mV (OCP) to 1200mV vs. Mercury Sulfate Electrode (MSE) for different number of cycles. The open circuit potential (OCP) has been measured for uncoated and PANI coated steel in 0.6M NaCl. It is also know as rest potential. The measured potential for bare steel (uncoated) is ~-1.08V and for PANI coated steel it's ~-1.04V, which is better for protecting steel from corrosion. The more negative the potential of metal is, the more readily it corrodes. So we can say there is ~40mV positive shift in the potential for PANI coated steel. A graduate student has developed the hydrothermal liquefaction of wood to bio-oil for improved yield and OH group production. He found that ethanol addition to water was very helpful in improving the yield of bio-oil. Another student has begun to work on adding graphene to phenol formaldehyde (PF) to see if we can improve the conduction of heat through the adhesive. We are currently using graphene until we can get carbon nanotubes through our collaborators.

    Publications

    • Type: Journal Articles Status: Published Year Published: 2015 Citation: Liang Cheng, Sushil Adhikari, Zhouhong Wang, Yulong Ding. Characterization of bamboo species at different ages and bio-oil production. Journal of Analytical and Applied Pyrolysis. doi:10.1016/j.jaap.2015.09.008
    • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: "Source and variation of Hydroxyl Groups in Liquefaction Oil of Loblolly Pine Produced at Different Temperatures." Celikbag, Y., Via, B.K., Adhikari, S., Auad, M.L. 2015. Forest Products Society Convention, Atlanta, GA.
    • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: "Optimization study of novolac resins using fast pyrolysis bio-oil characteristics" Melanie McDonald, Sushil Adhikari and Maria L. Auad. ASABE Annual meeting. New Orleans, July 26-29, 2015
    • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: "Techno-Economic Analysis of Fast Pyrolysis of Stillage from Cellulosic Biorefineries", Baral, N.R., & Shah, A. 2015 ASABE Annual International Meeting, New Orleans, Louisiana. July 26-29, 2015
    • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: "Renewable Resources as Precursors of Bio-based Thermosetting Resins, Bernal Sibaja, Yusuf Celikbag, Brian Via, Sushil Adhikari, Maria L. Auad, ACS, Cellulose and Renewable Materials Division, March 22-26, 2015, Denver Colorado, (Oral)
    • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Bio-Based Thermosetting Epoxy Resins, Bernal Sibaja, Yusuf Celikbag, Brian Via, Sushil Adhikari, Maria L. Auad, Forestry Product Society FSP Atlanta June 10-12, 2015 (Oral)