Progress 05/01/15 to 04/30/16
Outputs
Target Audience:In Year 5 target audiences included elected officials, personnel, and their delegates at local, state, and federal levels; students, scientists, and professionals in related technologies; and companies interested in lignin and derivative products. Many were reached via journal articles and conference presentations and proceedings (reported in the Products section). Also, extensive global outreach was carried out to industry through sales and marketing activities for BioChoiceTM lignin and its potential derivative products. Instances of reaching target audiences included: Domtar was credited as a leading company for global lignin sales in the report, Global Lignin Market Growth of 3.2% CAGR by 2020 - Analysis, Technologies & Forecast Report 2015-2020, released February 25, 2016, by Research and Markets, the world's largest market research firm. Research and Markets released an additional report on February 26, Global Kraft Lignin Market Assessment Report, by Application & by Geography 2015-2021. Domtar's lignin sales are the primary, immediate outcome of the BRDI project. Dr. Marcoccia, BRDI Project Director, addressed an open session of the Canadian parliament's Natural Resources Committee on May 14, 2015. The speech cited both the USDA-DOE BRDI demonstration project and another demonstration project supported by the Canadian government, highlighting the central importance of government support towards revitalizing the declining pulp and paper industry. An article by GreenBiz Group Inc., Domtar Rewrites Rules for Paper and Pulp Production, was published on July 21, 2015, at http://www.forestindustry.com/domtar-rewrites-rules-for-paper-and-pulp-production/. The article highlights Domtar's R&D focus on turning waste into a marketable commodity through the first commercial-scale lignin separation plant in Plymouth, NC, supported by the USDA-DOE BRDI program. Changes/Problems:No further modifications are required to this project. What opportunities for training and professional development has the project provided?Domtar. Domtar project managers and process engineers continued to receive on-the-job training in the LignoBoost process. During the past year: Post Doctorate Industrial Research Fellow, Dr. Shabnam Sanai, is nearing completion of a two-year assignment at Domtar on "Evaluation and Development of Lignin Valorization Opportunities." Domtar is offering her the new-created, permanent position of R&D Scientist, Biorefinery Specialist. Greg Fullenwider was named the plant operations lead for the biorefinery operation. Joshua Armstrong commenced a 1 year Entry-Level Engineer (ELE) assignment on lignin plant operations, optimization, and characterization. Jonathan Dunn completed a 6 month ELE assignment. Melvin Platt commenced a 6 month project lead assignment on final optimization and evaluation of the plant. FPL. Through the CRADA with MSU, one post-doctoral researcher and one Ph.D. candidate were trained on processes to convert lignin to graphene, as well as characterization methods in XRD, SEM and TEM. How have the results been disseminated to communities of interest?See section on Target Audiences. What do you plan to do during the next reporting period to accomplish the goals?The BRDI project is now concluded. Over the duration of the project, Domtar contributed over $17 million in additional cost share to augment $7 million in BRDI funding, for a total project cost of $24 million. Production of lignin is continuing with 100% of the produced lignin being sold. In addition, value-added products in a range of markets, arising from BRDI-sponsored R&D, are in active development with over a hundred partners in the lignin and derivative markets. Overall, a high priority in the near-term is to build out the BioChoiceTM brand and business. A Biomaterials Business Unit has been newly created at Domtar in anticipation of the biorefinery as a significant growth platform, with additional financial and staffing resources dedicated to its development. Plans include increasing the capacity and reliability and reducing costs, including evaluation and development of new system installations; and continuing to increase market breadth and depth, including development of lignin valorization opportunities. Additionally, the BioChoice™ brand and business is being used as a platform for further development and evolution of the integrated Biorefinery, with plans and some activities already underway to: Extend several high promise BRDI projects (lignin valorization, subject to reaching agreement on Joint Development Agreements (JDAs); Re-visit sugar platform and sugar valorization opportunities, develop mid- to long-term proposal for R&D investment and framework; and Supplement lignin, polysacharides, and sugars with advanced fibers/particles.
Impacts
What was accomplished under these goals?
Task 1. Economic Analysis (Conlon/Domtar) Completed in year four. Task 2. Lignin Removal Demonstration Project (Domtar/Valmet) As a direct result of the capital project (which was a first of its kind for the Lignoboost process), both Domtar and Valmet have significantly advanced their process, mechanical, and operational knowledge of this system. This enhanced knowledge and experience will be of great value in achieving future widespread commercialization of the technology. In particular, the operating experience is the first of its kind in the world for a complete, commercial scale system and specifically, for a southeastern U.S. softwood-derived feedstock. At the end of 2014 a proposal to upgrade and/or replicate the semi-works plant to a larger commercial scale was prepared and evaluated. It was concluded that additional optimization is required to reduce cash costs of manufacturing, and more importantly, additional market and applications development was required in order to justify capacity expansion. Both of these initiatives are presently being worked and the results and projections to date look very promising. Present estimates and projections call for a capacity expansion in late 2017 to early 2018, although the possibility exists for large demand increases much sooner than that. Optimization and troubleshooting continue. To date, the plant is very close to design production rates, target availability and reliability metrics, and target operating costs. The progress towards these goals was slower than anticipated, due to the need for numerous process and mechanical changes during start up and troubleshooting. This process evolution continues to date and is expected to continue to the end of 2015. Results to date from operating the commercial scale demonstration plant have quantitatively confirmed that lignin removal has de-bottlenecked the recovery boiler (resulting in increased capacity, productivity and efficiency for the mill). Further, the anticipated impact (or lack of impact) on other mill unit operations has also been confirmed. Operating and unit costs continue to decline but must improve further, thus process optimization continues. Market and applications development has progressed better than expected. As with last year, we continue to believe that expansion and market demand will take hold in 2017-2018. However, our challenge now is to improve process and manufacturing economics in order to capitalize on this opportunity. We continue to be hopeful that we will be able to expand capacity by 2018, but that will depend on successfully reducing capital and maintenance costs. Marketing results of BioChoiceTM lignin have been excellent. Present capacity is sold out, and several lignin upgrading projects continue to show great promise for large volumes with good margins. Sales results to date suggest that external sales margins and volumes can justify additional lignin removal projects if projected demand growth is realized. Task 3. Hydrolysis Demonstration Work (CSI/Domtar) Completed in year four. Task 4. Lignin as a Fuel Additive/Extender Study (NCSU/Domtar) Completed in year four. Task 5. Lignin as a Biomaterial Study (NCSU/FPL/Domtar) Outcomes of the FPL/MSU graphene work to date include the ability to generate graphene at the rate of about 1 gram per day, in layers up to 20-30 atoms thick. Currently the graphene contains significant quantities of impurities from catalysts used in the conversion process. Since the BRDI project ends in April 2016 and the results of the graphene work to date are promising, Domtar intends to continue funding the work through a separate contract in the coming months. Licensing arrangements are in process. Future objectives are to: (1) further purify the graphene to remove processing residuals, (2) reduce the layer thickness, (3) scale-up the production rate using a continuous processing mode, and (4) explore potential applications of the produced material. Task 6. Sugar for Algae Nutrient Study (KAS/Domtar/CSI) Completed in year four. Task 7. Process Engineering and Life Cycle Analysis (NCSU) Completed in year four.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2016
Citation:
Charles Culbertson, Trevor Treasure, Richard Venditti, Hasan Jameel, and Richard Phillips, Life Cycle Assessment of Lignin Extraction in a Kraft Pulp Mill, Nordic Pulp and Paper Journal, Vol. 31, 2016, Issue No. 1, pp. 30-40.
- Type:
Journal Articles
Status:
Other
Year Published:
2016
Citation:
Xuefeng Zhang, Qiangu Yan, Zhiyong Cai, and Jilei Zhang, Synthesis of graphene-encapsulated iron nanoparticles from kraft lignin, in preparation for submittal to Materials Letters.
- Type:
Journal Articles
Status:
Other
Year Published:
2016
Citation:
Weiqi Leng, H. Michael Barnes, Qiangu Yan, Zhiyong Cai, and Jilei Zhang, Low temperature synthesis of multi-layer graphene-encapsulated copper nanoparticles from kraft lignin, in preparation for submittal to Materials Letters.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2016
Citation:
Bruno Marcoccia, Executive Opening Panel on Emerging Bioeconomy Opportunities, PaperWeek Canada, Montreal, Canada, February 1-5, 2016.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2016
Citation:
Zhiyong Cai, Engineered Sustainable Carbon-Based Nano Materials from Kraft Lignin for Energy Storage, Renewable Fuel Production, and Environmental Processes, Graphene and 2D Materials USA, Santa Clara CA, November 16-17, 2016.
|
Progress 05/01/11 to 04/30/16
Outputs
Target Audience:Target audiences included elected officials, personnel, and their delegates at local, state, and federal levels; students, scientists, and professionals in related technologies; and companies interested in lignin and derivative products. Many were reached via journal articles and conference presentations and proceedings (reported in the Publications section). Also, extensive global outreach was carried out to industry through sales and marketing activities for BioChoiceTM lignin and its potential derivative products. Instances of reaching out to target audiences included: Ribbon Cutting Ceremony and Various Domtar Outreach Some USDA staff participated in the June 7, 2013, ribbon-cutting ceremony, along with staff from the Congressional Delegation. In August 2013, Secretary Vilsack received a comprehensive tour of the BioChoice facility, and several local dignitaries were on hand to join Domtar senior leadership in welcoming the Secretary. In the fall of 2013 Domtar Domtar's Plymouth BioChoice Lignin was granted the "BioPreferred" designation by the USDA, allowing Domtar to market BioChoice as 100% biobased. Traditional and Internet News Coverage The News & Observer published an article on the Domtar biorefinery in both print and on-line on June 8, 2013, "Domtar Unveils New Technology." The article described how the Plymouth mill was converting black liquor, a liquid by-product of paper production, into a solid form for use as a valuable commodity and alternative to fossil fuels and petroleum-based products. Domtar issued a press release on March 12, 2013, titled Domtar inaugurates commercial lignin production with the caption: "Plymouth Mill to produce bio-material with wide range of industrial applications as petro-chemical alternative." The press release appeared in dozens of internet news sources. A subsequent Domtar press release, Lignin from Black Liquor to Green Products, was similarly picked up by many media sites worldwide in summer 2013. In March 2014 Adhesives and Sealants magazine published an article about BioChoice as an option in the adhesives industry. In July 2014 Domtar announced a partnership with UPM in Europe via a news release, picked up by many media sources such as prnewswire.com. The news release highlights Domtar's agreement with UPM to be the exclusive distribution of BioChoiceTM lignin in Europe. In November 2014, the American Forest and Paper Association (AF&PA) announced sustainability awards to Domtar, including an "Innovation in Sustainability" related to lignin. In 2014 Domtar broadly promoted BioChoiceTM lignin via a marketing ad, which appeared in major printed and on-line publications and other venues. The article Plastics to Dust - Dream about to Come True highlighted the work by Professor Emeritus Wolfgang Glasser at Virginia Tech, to turn Domtar lignin into biodegradable plastics. Originally appearing online in Virgina Tech's http://www.vtnews.vt.edu/articles/2014/05/ 051214-cnre-biodegradableplastics.html, the story was picked up by international news outlets such as NewsBank InfoWeb. The article Domtar starts LignoBoostTM lignin separation based on Metso's technology appeared in http://bioplasticsnews.com/2014/05/19/domtar-starts-up-commercial-scale-lignoboost-lignin-separation-plant-based-on-metsos-technology/. The article describes the successful start-up of the commercial-scale LignoBoostTM lignin separation plant at the Plymouth Mill, the first of its kind in the world. Other News On November 12, 2014, Domtar received the Innovation in Sustainability Award for BioChoice™ Lignin in Montreal, Canada, from the American Forest & Paper Association as a leader in sustainability. An article by GreenBiz Group Inc., Domtar Rewrites Rules for Paper and Pulp Production, was published on July 21, 2015, highlights Domtar's R&D focus on turning waste into a marketable commodity through the first commercial-scale lignin separation plant in Plymouth, NC. Dr. Marcoccia, BRDI Project Director, addressed an open session of the Canadian parliament's Natural Resources Committee on May 14, 2015. The speech cited both the USDA-DOE BRDI demonstration project and another demonstration project supported by the Canadian government, highlighting the central importance of government support towards revitalizing the declining pulp and paper industry. Domtar was credited as a leading company for global lignin sales in the report, Global Lignin Market Growth of 3.2% CAGR by 2020 - Analysis, Technologies & Forecast Report 2015-2020, released February 25, 2016, by Research and Markets, the world's largest market research firm. Research and Markets released an additional report on February 26, Global Kraft Lignin Market Assessment Report, by Application & by Geography 2015-2021. Domtar's lignin sales are the primary, immediate outcome of the BRDI project. Domtar created an on-line video on their lignin biorefinery operation at the Plymouth Mill at http://www.domtar.com/en/pulp/lignin/10607.asp. The brief video highlights the state-of-the-art operation of the commercial production facility for high quality BioChoiceTM lignin. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Training and professional development were ongoing features of the BRDI project. Personnel and their associated training activities are summarized below for each organization. Cross-training was a common feature as well, such as the two-day NCSU course attended by both NCSU and Domtar personnel. Domtar. No project funds were used to support Domtar personnel, although a number of Domtar personnel support the project. Domtar project managers and process engineers received on-the-job training and updates on the LignoBoost process. Approximately 10 new, permanent positions at the mill were added to run the Lignoboost operation, plus five new positions for advancing biomaterials production and sales were added at the corporate office. In addition: Post Doctorate Industrial Research Fellow, Dr. Shabnam Sanai, was hired for the 2-year project: "Evaluation and Development of Lignin Valorization Opportunities." As the two years is coming to a close, a new fulltime position has been created in Domtar to hire her permanently to continue this work. Brian Ranson, Harshad Pande, and Jim Freiberg were added to project management teams and received on-the-job training in the LignoBoost process. Mill E&I personnel were trained on the new system, and O&M personnel were trained in the lignoboost process. Matt Thomas, a senior in Paper Science Engineering and Chemical Engineering at NCSU, was trained as an intern at Domtar in summer 2012, where he carried out lab and pilot scale work in lignin precipitation, carbonization, acidification, and analysis. Greg Fullenwider was named the plant operations lead for the biorefinery operation. Joshua Armstrong commenced a 1 year Entry-Level Engineer (ELE) assignment on lignin plant operations, optimization, and characterization. Melvin Platt commenced a 6 month project lead assignment on final optimization and evaluation of the plant. NCSU. The overall project leader for NCSU was Prof. Hasan Jameel, who also researches lignin as a fuel additive and process simulation. Other Co-PIs include Dimitri Argyroupolous (lignin as a thermoplastic polymer and biomaterial, Hou-min Chang (lignin as a fuel addition, lignin as an adhesive, and lignin characterization), Orlando Rojas (lignin as a surfactant), Richard Venditti (life cycle analysis and lignin as a polymer), and T. Fang (lignin as a fuel additive). Four graduate research associates and four post-doctoral researchers supporting these efforts included Shuai Li, Grant Culbertson, Trevor Treasure, Dolanimi Zogunkoya, Sidd Pawar, Zhoujian Hu, H. Sadeghifar, and T. Typelo. All were trained in lignin chemistry, product development, and utilization. A two-day course was presented on lignin chemistry by Prof. Hou-Min for participants in the lignin utilization project, also attended by Domtar personnel (a total of 15 faculty, researchers and graduate students, plus Domtar personnel). Additional training was offered on the new lignin extruder, purchased in part with project funds. Metso/Valmet. The initial project design and install was carried out by Metso under Domtar's direction, supported by 15 Metso/Valmet employees. Professional development for Metso personnel was based on on-the-job training, developed following several detailed working meetings to review the process and the layout concepts. Training was carried out using the LignoSize Program with several of our team members to better understand the design conditions for the project. Input from the Bäckhämmar Demo Plant and Collaboration with Innventia on their experience also was helpful in the design. FPL/MSU. FPL and MSU each trained and supported one post-doctoral researcher during portions of the project. The FPL post-doc was trained in the operation and analysis of DMA and TGA equipment, as well as in modification of Kraft lignin, adhesives production, experimental design, and PF-3 resin production. The MSU post-doc was trained in catalytic-thermal conversion methods to convert lignin into graphene materials, and the relevant testing and analysis methods. KAS. Summer interns, Courtney Chun and William McQuiston, were trained in how to perform analytical tests and carried out work in the same to assist the scientists. BC. Mark Conlon, Vice President Sector Development, was the project lead for BC, supported by Phil Sheridan, Director Industry Development. Following closure of the BC, work by Conlon and Sheridan continued under contract to Conlon. CSI. For the reporting period, the majority of the work was conducted at CSI's labs by Dr. Rajai Atalla, Dr. Steve Edwards, and Rowan Atalla. CSI hired two summer undergraduate student interns to work on pilot-scale implementation. How have the results been disseminated to communities of interest?Please see section on Target Audiences. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
Overview On behalf of the BRDI project team, The Domtar Paper Company is pleased to submit the Final Report for the USDA-NIFA award for the "Integrated Biorefinery at the Domtar Plymouth, North Carolina Pulp Mill." The main outcome is achieving an integrated demonstration biorefinery that can be widely duplicated across pulp and paper mills, towards achieving the objectives of the BRDI program: (1) abundant commercial production of biofuels at prices competitive with fossil fuels; (2) develop high-value biobased products that are economically viable, replace petroleum-based feedstocks and products, and enhance the value of coproducts; and (3) develop diverse domestic sources for renewable biomass. The Domtar biorefinery is recognized as the first of its kind in the world. The roles of the collaborating organizations, including changes in partners during the duration of the project, were: Domtar hosted the biorefinery, provides the feedstock, develops and refines unit operations, evaluates opportunities for further lignin valorization, and manages the overall project. Valmet (formerly Metso) provided LignoBoost technology/process equipment to separate the lignin from the black liquor produced by the mill, enabling extraction of a high BTU value fuel out of a relatively inefficient boiler and upgrading of this material into higher-value biofuels and bioproducts. Cellulose Sciences International (CSI) and Kuehnle AgroSystems (KAS) demonstrated the production of value-added sugars, fuels, and biomaterials via hydrolysis and subsequent fermentation of underutilized regional biomass. North Carolina State University (NCSU), in collaboration with CSI and KAS, developed lignin-derived biofuels and/or additives (such as aromatics and phenolic-type compounds) and the required technical specifications for the corresponding feedstocks, intermediates, and final fuel products. Also NCSU developed lignin-based biomaterial products and corresponding technical specifications, and investigated process modeling and life cycle analyses. Biofuels Center of North Carolina (BC/Conlon) contributes expertise in regional biomass supply development and economic analyses in the production of biofuels and bioproducts. Although BC ceased operations on 10/31/13 due to elimination of state funding, work continued under the leadership of former BC project leader, Mark Conlon. U.S. Forest Products Laboratory (FPL) developed methods to convert the lignin into (a) an adhesive for wood bonding and (b) a thermoplastic substitute for fiber plastic composites. In both cases the lignin replaces petroleum based products. Under a 2015-2016 CRADA with FPL and Domtar, Mississippi State University (MSU) is synthesizing carbon-based nanomaterials from Domtar's kraft lignin under a contract continuance from Domtar. ITECS Consulting assisted Domtar with management support to meet USDA project deliverables, managed subcontractors, and compiled and prepared technical reports to NIFA. The scope of work for the project included installation, testing and semi-works demonstration of the Valmet LignoBoost system for lignin removal from pulp mill black liquor, in order to generate >70 odmt/d of clean, dry lignin. Work further involved the engineering and techno-economic analysis of the CSI process for production of fermentable sugars, lignin, and high-value biofuels and bioproducts from underutilized regional biomass. Other activities included development of new, high-value biofuel/bioproduct applications from the high-purity intermediates generated by both systems; biofuels/bioproduct development (NCSU, FPL, MSU) for sugars and lignins; Life Cycle Analyses (NCSU); and broad economic analyses (BC/Conlon), including alternative feedstocks for the CSI and KAS processes. To minimize risk while applications and economics were developed, Domtar used the lignin to power its manufacturing processes. Major Outcomes/Impacts The major project outcomes and impacts are provided below, as summarized by the NIFA-appointed Site Visit Team in their July 2016 report: 1. Research, processes, products, or start-up companies that will be transferred/commercialized: The project commercialized the Valmet LignoBoost system at the Plymouth, NC Domtar for lignin production, generating >10,000 dry metric tonnes/year of product. Production of lignin is continuing, with 100% of the produced lignin being sold, primarily to Asian and European markets. In addition, value-added products in a range of markets, arising from BRDI-sponsored R&D, are in active development with dozens of partners and customers in the lignin and derivative markets. Research into new lignin products by NCSU, FPL, and MSU could enable adoption for additional lignin product and higher value products. The sugar platform demonstrated that low cost hydrolysates could be used as a sugar source for supporting heterotrophic algae growth, which produced high valuable food additives, such as carotene. This component of the project is still at the lab scale but remains nonetheless promising. The production of carotenoids, which commands a sufficiently high selling price, could be economically attractive if market shares warrants production. No products were directly commercialized from the sugar platform on this grant but research work is planned for the future, especially on the algal derived products. 2. Quantity and value of energy and/or products produced: The project commercialized the Valmet LignoBoost system at the Plymouth, NC Domtar for lignin production, generating >10,000 dry metric tonnes/year of product, with installed capacity up to 30,000 dry metric tonnes/year. This material was originally intended to be used for solid fuel, but has found success in replacing petroleum based chemicals for a variety of global customers. 3. Jobs created: Domtar created more than 60 new jobs directly associated with this project in North Carolina. Specifically, they created approximately ten new, permanent jobs to operate the Lignoboost plant, five new direct jobs, for the purpose of market and applications development, and an approximately fifty new jobs to harvest and transport additional woody feedstock from the increased pulp production allowed from the debottlenecking of the process. All of these new jobs are continuing to enhance the rural economy. Furthermore this new revenue is further contributing to the mill's profitability toward the retention of the existing mill employment of 352 hourly jobs with total employment of 448, as well as 1,750 indirect jobs. Beyond the permanent jobs created by Domtar, North Carolina State University hired 8 graduate students/post-doctoral students for this project and MSU hired 2 graduate students/post-doctoral students, training them in bioprocessing and bioproducts. 4. Quantified environmental benefits compared to alternatives: The project performed a life cycle assessment (LCA) using ISO 14044 standards to determine the environmental effects of lignin extraction on the pulp production process with decreases in GHG emissions due to the reduced throughput in the chemical recovery loop. Additionally, modelling was done to determine the environmental impacts of purified lignin as (1) a biomaterial to replace phenolic resin or (2) as a biofuel product. The analysis showed significant reductions in GHG emissions from the production of lignin which was used to offset either phenolic resin or natural gas consumption.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Perez, Michael, Norie Anne Nolasco, Amit Vasavada, Martin Johnson, and Adelheid Kuehnle. "Algae-mediated valorization of industrial waste streams." Industrial Biotechnology 11, no. 4 (2015): 229-234.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Cui, Chengzhong, Runkun Sun, and Dimitris S. Argyropoulos. "Fractional precipitation of softwood kraft lignin: isolation of narrow fractions common to a variety of lignins." ACS Sustainable Chemistry & Engineering 2, no. 4 (2014): 959-968.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Argyropoulos, Dimitris S. "The Emerging Bio-Refinery Industry Needs to Refine Lignin Prior to Use." Journal of Biotechnology & Biomaterials 2014 (2014).
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Argyropoulos, Dimitris S. "Towards Thermoplastic Lignin Polymers: Progress in the Utilization of Kraft Lignin for the Synthesis of Heat Stable Polymer Melts." Journal of Biotechnology & Biomaterials 2013 (2013).
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Argyropoulos, Dimitris S., Hasan Sadeghifar, Chengzhong Cui, and Sanghamitra Sen. "Synthesis and characterization of poly (arylene ether sulfone) kraft lignin heat stable copolymers." ACS Sustainable Chemistry & Engineering 2, no. 2 (2013): 264-271. ACS Sustainable Chem. Eng., 2014, 2 (2), pp 264271.
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Sen, Sanghamitra, Hasan Sadeghifar, and Dimitris S. Argyropoulos. "Kraft lignin chain extension chemistry via propargylation, oxidative coupling, and Claisen rearrangement." Biomacromolecules 14, no. 10 (2013): 3399-3408.
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Cui, Chengzhong, Hasan Sadeghifar, Sanghamitra Sen, and Dimitris S. Argyropoulos. "Toward thermoplastic lignin polymers; part II: thermal & polymer characteristics of kraft lignin & derivatives." BioResources 8, no. 1 (2013): 864-886.
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Sadeghifar, Hasan, and Dimitris S. Argyropoulos. "Correlations of the antioxidant properties of softwood kraft lignin fractions with the thermal stability of its blends with polyethylene." ACS Sustainable Chemistry & Engineering 3, no. 2 (2015): 349-356.
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Sen, Sanghamitra, Shradha Patil, and Dimitris S. Argyropoulos. "Methylation of softwood kraft lignin with dimethyl carbonate." Green Chemistry 17, no. 2 (2015): 1077-1087.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Ayoub, Ali, Richard A. Venditti, Hasan Jameel, and Hou?Min Chang. "Effect of irradiation on the composition and thermal properties of softwood kraft lignin and styrene grafted lignin." Journal of Applied Polymer Science 131, no. 1 (2014).
- Type:
Journal Articles
Status:
Published
Year Published:
2016
Citation:
Culbertson, Charles, Trevor Treasure, Richard Venditti, Hasan Jameel, and Ronalds Gonzalez. "Life Cycle Assessment of lignin extraction in a softwood kraft pulp mill." Nordic Pulp & Paper Research Journal, 31, no. 1 (2016): 30-U247
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Cui, Chengzhong, Hasan Sadeghifar, Sanghamitra Sen, and Dimitris S. Argyropoulos. "Toward thermoplastic lignin polymers; part II: thermal & polymer characteristics of kraft lignin & derivatives." BioResources 8, no. 1 (2013): 864-886.
- Type:
Conference Papers and Presentations
Status:
Submitted
Year Published:
2015
Citation:
Charles Culbertson, Trevor Treasure, Richard Venditti, Hasan Jameel, and Richard Phillips, Life Cycle Assessment of Lignin Extraction in a Kraft Pulp Mill, TAPPI PEERS 2015, Atlanta, GA, October 25-28, 2015.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2015
Citation:
Siddesh Pawar, Richard Venditti, Hasan Jameel, Hou-min Change, Ali Ayoub, Synthesis and Characterizaion of fatty acid esters of softwood kraft lignin, 18th International Symposium on Wood, Fiber and Pulping Chemistry, Vienna, Austria, September 2015.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2013
Citation:
Ali Ayoub and Richard A. Venditti, The Effect of Irradiation on the Processability of Lignin for Carbon Fiber Applications, Paper 339792, 13th AIChE Annual Meeting, San Francisco, CA, November 3-8, 2013.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
Tiina Nypel�, Bruno Marcoccia, Orlando J Rojas, Lignin as precursor for functional particles, Paper 321, 247th ACS National Meeting and Exposition, Dallas, Texas, March 16-20, 2014.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2016
Citation:
Bruno Marcoccia, Executive Opening Panel on Emerging Bioeconomy Opportunities, PaperWeek Canada, Montreal, Canada, February 1-5, 2016.
- Type:
Journal Articles
Status:
Published
Year Published:
2012
Citation:
Sadeghifar, Hasan, Chengzhong Cui, and Dimitris S. Argyropoulos. "Toward thermoplastic lignin polymers. Part 1. Selective masking of phenolic hydroxyl groups in kraft lignins via methylation and oxypropylation chemistries." Industrial & Engineering Chemistry Research 51, no. 51 (2012): 16713-16720.
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Mun, Sung Phil, Zhiyong Cai, and Jilei Zhang. "Fe-catalyzed thermal conversion of sodium lignosulfonate to graphene." Materials Letters 100 (2013): 180-183.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
Marcoccia, B. and Barfield, M., Update on the Integrated Biorefinery at Domtars Plymouth, NC Pulp Mill, PaperWeek Canada 2014, 100th Annual Conference of the Canadian Pulp and Paper Industry, February 3-6, 2014, Montreal, QC, Canada. ?
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2016
Citation:
Zhiyong Cai, Engineered Sustainable Carbon-Based Nano Materials from Kraft Lignin for Energy Storage, Renewable Fuel Production, and Environmental Processes, Graphene and 2D Materials USA, Santa Clara CA, November 16-17, 2016.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
Wimby, M., Commercialization of the LignoBoost Process, 5th Nordic Wood Biorefinery Conference, March 25-27, 2014, Stockholm, Sweden.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
Argyropoulos, D., Towards Thermoplastic Lignin Polymers; Progress in the utilization of kraft lignin for the synthesis of heat stable polymer melts, 5th Nordic Wood Biorefinery Conference, March 25-27, 2014, Stockholm, Sweden. ?
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2013
Citation:
Chen, Y., Frihart, R.C., Cai, Z., Lorenz, L.F., Stark, N.M.., and Ibach, R.E., Characterization of industrial kraft pine lignin for the production of adhesives, Proceedings in International Conference on Wood Adhesives, 2013 Oct. 9-11, Toronto, Ontario Canada. ?
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2013
Citation:
Chen, Y., Frihart, R.C., Cai, Z., Lorenz, L.F., and Stark, N.M, Lignin-based Phenol-Formaldehyde Resins from PurifiedCO2 Precipitated Kraft Lignin (PCO2KL), Proceedings in International Conference on Wood Adhesives, 2013 Oct. 9-11, Toronto, Ontario Canada.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2013
Citation:
Chen, Y., Oral Presentation, International Conference on Advancements in Fiber-Polymer Composites: Wood Fiber, Natural Fibers, and Nanocellulose, May 6-7, 2013, Milwaukee, WI.
|
Progress 05/01/14 to 04/30/15
Outputs
Target Audience: In Year 3 target audiences included elected officials, personnel, and their delegates at local, state, and federal levels; students, scientists, and professionals in related technologies; and companies interested in lignin and derivative products. Many persons were reached via journal articles and conference presentations and proceedings (reported in the Products section). Also, extensive global outreach was carried out to industry through sales and marketing activities for BioChoiceTM lignin and its potential derivative products. News Coverage In March 2014 Adhesives and Sealants magazine published an article about BioChoice as an option in the adhesives industry: http://www.adhesivesmag.com/articles/92688-lignin-in-the-laboratory In July 2014 Domtar announced a partnership with UPM in Europe via a news release: http://www.prnewswire.com/news-releases/upm-to-become-exclusive-distributor-of-domtars-biochoice lignin-in-europe-266588641.html In November 2014, the American Forest and Paper Association (AF&PA) released news about sustainability awards for Domtar, including an "Innovation in Sustainability" related to lignin: http://www.prnewswire.com/news-releases/2014-afpa-sustainability-award-winners-announced-at annual-meeting-282134311.html Changes/Problems: CSI, Conlon, KAS, and NCSU completed all deliverables in Year 4, and do not plan to participate in the project under BRDI auspices in Year 5. In February 2015, an additional one-year, no-cost extension through Year 5 (ending 4/30/16) was granted by NIFA. The time extension will allow completion of the remaining FPL scope of work, requested due to the departure of the FPL post-doctoral researcher and the replacement of that work by MSU through a joint CRADA. As described in the request for extension, this work will improve the understanding to convert lignin to high value-added grapheme material. Graphene materials are attracting significant attention due to their potential application such as transistors, conductors, batteries, catalysts and biosensors. The research objectives are to: (1) characterize and understand the mechanism of converting lignin to graphene, (2) pilot production of lignin-graphene and process optimization, and (3) explore some commercial applications of the produced graphene. To accomplish these research objectives a lab scale setup will be built with a daily capacity of producing 1-lb of high purity graphene material from lignin, which is a by-product of the pulping and biomass conversion processes. The process and lignin-based graphene will be characterized to understand the conversion mechanism. Also the commercial applications of the produced graphene will be explored. What opportunities for training and professional development has the project provided? Domtar. Domtar project managers and process engineers continued to receive on-the-job training in the LignoBoost process. During the past year: Post Doctorate Industrial Research Fellow, Dr. Shabnam Sanai, was hired for the 2-year project: "Evaluation and Development of Lignin Valorization Opportunities". Lesley Cook completed a 6 month Entry-Level-Engineer (ELE) assignment on lignin plant start up, troubleshooting, and optimization. Brantley West completed 6 month ELE assignment on lignin plant operations, optimization, and characterization. Jonathan Dunn commenced a 6 month ELE assignment on lignin plant operations, optimization, and characterization. Melvin Platt commenced a 6 month project lead assignment on final optimization and evaluation of the plant. FPL. Work planned for Year 4 is deferred to Year 5 and will be carried out through a CRADA with MSU. KAS. Summer interns, Courtney Chun and William McQuiston, were arranged for summer 2014 to carry out occasional work assisting the scientists, such as performing certain analytical tests. NCSU. Six graduate research associates and post-doctoral researchers continued training in lignin chemistry, product development, and utilization. How have the results been disseminated to communities of interest? See section on "Target Audiences." What do you plan to do during the next reporting period to accomplish the goals? All deliverables are expected to be met and the project is on-budget. Overall, the top priority in year 5 and beyond is to build out the BioChoiceTM brand and business: Create organizational platform Perform, Grow, Breakout Increase capacity, reliability, reduce costs,including evaluation and development of new system installations Increase market breadth and depth, including development of lignin valorization opportunities. Additionally, the BioChoice™ brand and business is being used as a platform for further development and evolution of the integrated Bio-Refinery in Year 5 and beyond, with plans to: Extend several high promise BRDI projects (lignin valorization, subject to reaching agreement on JDA's); Re-visit sugar platform and sugar valorization opportunities, develop mid- to long-term proposal for R&D investment and framework; and Supplement lignin, polysacharides, and sugars with advanced fibers/particles. The following activities by task are planned over the next reporting period (Year 5). Task 1. Economic Analysis. Completed in Year 4. Task 2. Lignin Removal Demonstration Project. Domtar will continue to refine and improve the Lignoboost operation with the goal of continuous operations, culminating with evaluation and recommendation on a permanent install for Plymouth and other Domtar mills. The short to intermediate term priority will be continued process optimization for Lignin removal, product upgrading and packaging, and market/applications development. We will carry out an evaluation and recommendation for additional lignin removal systems. Task 3. Hydrolysis Demonstration Project. Completed in Year 4. Task 4. Lignin as Fuel Additive/Extender Study. Completed in Year 4. Task 5. Lignin as a Biomaterial Study. NCSU work was completed in Year 4. FPL work will continue through a CRADA with MSU to convert lignin to high value-added grapheme material. Several high potential lignin valorization projects have been identified, and we are presently working on possible extension arrangements. Task 6. Sugar for Algae Nutrient Study. Completed in Year 4. Task 7. Process Engineering and Life Cycle Analysis. Completed in Year 4.
Impacts
What was accomplished under these goals?
Task 1. Economic Analysis (Conlon/Domtar) Based on the input data provided, Conlon (formerly with BC) determined that the KAS process to algae and carotenoids recovery would provide excellent returns and opportunity for equity investors. The CSI process to cellulosic sugars is not yet economically viable. Sugars production from switchgrass was considerably higher and much closer to providing for returns required by equity investors. We recommend CSI focus additional process research on switchgrass and other non-woody energy crops. For the conversion technologies and sugar applications, economic analysis and the accompanying assessment of outcomes and impacts have been completed. The BioChoice lignin brand is a successful, rapidly growing new commercial product line for Domtar and is being sold globally. Further, as an indirect and unanticipated result of this marketing work, Domtar has discovered a significant market opportunity for another bio-based pulp mill by-product; namely crude tall oil and its derivatives. Domtar completed a techno-economic evaluation of expanding the Plymouth Bio-Refinery to include a tall oil acidulation plant and a subsequent separation and upgrading system for tall oil fatty acids, resins and pitch. As a result of this exercise, Domtar has initiated the first phase of this expansion and is in progress on a $3MM capital project that is scheduled to be completed by Q4 2015. Task 2. Lignin Removal Demonstration Project (Domtar/Valmet) As a direct result of the capital project (which was a first of its kind for the lignoboost process), both Domtar and Valmet have significantly advanced their process, mechanical, and operational knowledge of this system. This enhanced knowledge and experience will be of great value in achieving future widespread commercialization of the technology. In particular, the operating experience is the first of its kind in the world for a complete, commercial scale system and specifically, for a southeastern U.S. softwood-derived feedstock. At the end of 2014 a proposal to upgrade and/or replicate the semi-works plant to a larger commercial scale was prepared and evaluated. It was concluded that additional optimization is required to reduce cash costs of manufacturing, and more importantly, additional market and applications development is required in order to justify capacity expansion. Both of these initiatives are presently being worked and the results and projections to date look very promising. Present estimates and projections call for a capacity expansion in late 2017 to early 2018, although the possibility exists for large demand increases much sooner than that. Optimization and troubleshooting continue. To date, the plant is very close to design production rates, target availability and reliability metrics, and target operating costs. The progress towards these goals was slower than anticipated, due to the need for numerous process and mechanical changes during start up and troubleshooting. This process evolution continues to date and is expected to continue to the end of 2015. Results to date from operating the commercial scale demonstration plant have quantitatively confirmed that lignin removal has de-bottlenecked the recovery boiler (resulting in increased capacity, productivity and efficiency for the mill). Further, the anticipated impact (or lack of impact) on other mill unit operations has also been confirmed. Operating and unit costs continue to decline but must improve further, thus process optimization continues. Sales results to date suggest that external sales margins and volumes can justify additional lignin removal projects if projected demand growth is realized. Task 3. Hydrolysis Demonstration Work (CSI/Domtar) Cellulose Sciences International (CSI) completed production and delivery of the second of two syrup types for larger scale testing of algae growth. Some additional study of accessibility of cellulose in biomass was conducted using staining techniques detailed in publications from the Institute of Paper Chemistry. Substantial effort was focused on a literature review with respect to the differences between lignin-carbohydrate linkages in woody materials and those in herbaceous biomass, in an effort to determine the relatively low yield seen during enzymatic hydrolysis of the woody biomasses. Task 4. Lignin as a Fuel Additive/Extender Study (NCSU/Domtar) Hydrocarbon and carbon monoxide emissions were lower for the blends containing phenol derivative with an increase in both carbon dioxide and NOx emissions observed for these same blends. Reduced soot and slightly higher exhaust gas temperatures were observed for both blends containing phenol derivative. Phenol derivative blends had the highest heat release rate and cumulative heat release with the ethyl acetate blend containing phenol derivative also having the highest peak in- cylinder pressure. Task 5. Lignin as a Biomaterial Study (NCSU/FPL/Domtar) Lignin studies by NCSU emphasized understanding the role of the various fractions, towards affecting kraft lignin/synthetic polymer blends and novel avenues for the commercial exploitation of this abundant resource (such as developing lignin fractions that will be more reactive for use in adhesives). Thermal processability was imparted to lignin via chemical modification - saturated FA esters such as lignin stearates show melting behavior. To improve mechanical properties (lower brittleness), unsaturated esters such as oleate were prepared. Lignin oleate was a sticky solid material that is soluble in polar solvents such as hexane. Several technologies have been identified to modify lignin and make it more suitable for use as adhesives and polymer applications. Adhesive testing started and preliminary results have been collected. FPL activities in Year 4 been deferred to Year 5 through a CRADA with Mississippi State University (MSU). MSU received the subaward notification 1/9/15. A kickoff meeting was held at FPL on 2/10/15 with MSU, FPL, and Domtar to review the lignin-to-graphene patent application, the project plan/timeline/ spending plan, and market analysis/freedom to practice. An MSU Ph.D. student is expected to complete the study and research work by December 2016. Task 6. Sugar for Algae Nutrient Study (KAS/Domtar/CSI) For productivity and scalability, Kuehnle AgroSystems (KAS) determined the productivity of 3 algal strains in SHC and SPBK model sugars at 3L fermentor scale with BSP and SHC hydrolysates. Excellent biomass productivities, sugar utilization patterns, glucose utilization and phospholipid content were demonstrated. Enhanced carotenoid content was achieved through further processing by light finishing. The feed value was determined by chemical analysis using different nutrient media. Task 7. Process Engineering and Life Cycle Analysis (NCSU) The information from the process simulation is being used by the mill to optimize their operations. The LCA on Lignoboost was completed. The pulp mill system demonstrates improved environmental performance (significant reductions in both greenhouse gas emissions and ecotoxity) with the addition of a lignin co-product due to reduced stack emissions from the recovery boiler.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Argyropoulos, D. S., The Emerging Bio-Refinery Industry Needs to Refine Lignin Prior to Use . J Biotechnol. Biomater. (2014) S6: e001. doi:10.4172/2155-952X.S6-e001.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Chengzhong Cui, Runkun Sun, Dimitris S. Argyropoulos, Fractional Precipitation of Softwood Kraft Lignin; Isolation of Narrow Fractions Common to a Variety of Lignins ACS Sustainable Chem. Eng., Articles DOI: 10.1021/sc400545d, 2014 2 (4), 959-968.
- Type:
Conference Papers and Presentations
Status:
Submitted
Year Published:
2015
Citation:
Charles Culbertson, Trevor Treasure, Richard Venditti, Hasan Jameel, and Richard Phillips, Life Cycle Assessment of Lignin Extraction in a Kraft Pulp Mill, TAPPI PEERS 2015, pending.
- Type:
Journal Articles
Status:
Submitted
Year Published:
2015
Citation:
Charles Culbertson, Trevor Treasure, Richard Venditti, Hasan Jameel, and Richard Phillips, Life Cycle Assessment of Lignin Extraction in a Kraft Pulp Mill, Nordic Pulp and Paper Journal, pending.
- Type:
Journal Articles
Status:
Other
Year Published:
2015
Citation:
Siddhesh N. Pawar, Richard A. Venditti, Hasan Jameel, Hou-Min Change and Ali S. Ayoub, Properties and Applications of Fatty Acid Esters of Softwood Kraft Lignin, in preparation, 2015.
- Type:
Other
Status:
Other
Year Published:
2013
Citation:
Invention Disclosure, North Carolina State University, File No. 13214 by Richard A. Venditti, with Ali Ayoub, Hou-Min Chang, and Hasan Jameel, Fatty acids and other unsaturated compounds combined with lignin to produce thermoplastics biomaterials, conceived 3/15/13.
|
Progress 05/01/13 to 04/30/14
Outputs
Target Audience: In Year 3 target audiences included local, state, and federal elected officials, personnel, and their delegates; students, scientists, and professionals in related technologies; and companies interested in lignin and derivative products. Many attended the ribbon cutting ceremony at the Plymouth, NC mill and were informed via traditional and internet news coverage, reported in this section. In addition, many were reached via journal articles and conference presentations, posters, and proceedings. Finally, extensive outreach was carried out to industry through sales and marketing activities for BioChoiceTM lignin and its potential derivative products. Ribbon Cutting Ceremony and Various Domtar Outreach During early 2013 attention was focused on working with the North Carolina Congressional delegation, including Senators Burr and Hagan, but especially with Congressman Butterfield, to invite U.S. Secretary of Agriculture Tom Vilsack to attend a June 7 ribbon cutting. Secretary Vilsack accepted Congressman Butterfield’s invitation. Tropical Storm Andrea prevented our Washington based dignitaries from attending, and under very threatening conditions we elected to proceed with our event. North Carolina USDA staff were able to participate in the ribbon-cutting, along with in-state staff from the Congressional Delegation. A ribbon made from lignin based polymers was cut by Domtar CEO John Williams, and just as the ribbon was cut, bright sunshine burned through the clouds and (temporarily) ended the rain for a successful event. Later in the summer, Secretary Vilsack made true on his commitment to visit with a comprehensive tour of the BioChoice facility on August 15. Several local dignitaries were on hand to join Domtar senior leadership in welcoming the Secretary. Secretary Vilsack was able to spend a couple of hours gaining an in-depth understanding of the lignin removal process, through both briefings and seeing firsthand how it works. In the fall of 2013 Domtar was informed that the USDA granted Plymouth BioChoice Lignin its “BioPreferred” designation, allowing Domtar to market BioChoice as 100% biobased. Shortly thereafter marketing materials for BioChoice incorporated the “BioPreferred Labeling.” Traditional and Internet News Coverage The News & Observer published an article on the Domtar biorefinery, “Domtar unveils new technology,” in both print and on-line. A press release and a Domtar web article on “Lignin from Black Liquor to Green Products” were picked up by dozens of .com media sites worldwide in summer 2013. Some of the web publications included: www.biomassmagazine.com/articles/8721/domtar-inaugurates-commercial-lignin-production www.biofuelsdigest.com/bdigest/2013/03/14/domtar-inaugurates-commercial-lignin-production/ www.compositesworld.com/news/domtar-inaugurates-commerical-lignin-production www.agra-net.com/portal2/isj/home.jsp?template=newsarticle&artid=20018039037&pubid=ag043 www.thebioenergysite.com/news/12531/first-commercial-lignin-plant-in-25-years-opens www.hydrocarbons-technology.com/news/newsdomtar-launches-commercial-lignin-production-plant-in-us www.biofuels-news.com/industry_news.php?item_id=6054 www.pulpandpapercanada.com/news/domtar-affirms-commitment-to-lignin-products/1002388857/ www.specialchem4polymers.com/resources/latest/displaynews.aspx?id=8950 www.nonwovens-industry.com/contents/view_breaking-news/2013-03-13/domtar-inaugurates-commercial-lignin-production/ www.greenbiz.com/blog/2013/03/22/domtar-rewrites-rules-paper-and-pulp-production?page=0%2C0. www.risiinfo.com/techchannels/pulping/Innventias-LignoBoost-technology-in-operation-at-Domtars-pulp-mill-in-Plymouth-NC.html www.forconstructionpros.com/topics/sustainable www.paperadvance.com/index.php/mills-a-technologies/technologies/1890-domtar-launches-into-commercial-lignin-production.html www.newsobserver.com/2013/06/08/2946499/domtar-unveils-new-technology.html http://wraltechwire.com/u-s-agriculture-secretary-vilsack-visiting-n-c-for-domtar-ribbon-cutting/12525453/ Many additional publications published and Twittered the story as well. Changes/Problems: In year 3 a one-year, no-cost extension was granted by NIFA, required due to delays in issuing the original subcontracts. Other contract changes in year 3 included: (a) terminating the contract with BC due to their closure and issuing a new contract to Mark Conlon to carry out remaining work; and (b) modifying the contract with FPL due to departure of their post-doc, to permit subaward with Mississippi State University to complete their work (contract changes pending). No modifications to the scope of work were required. What opportunities for training and professional development has the project provided? Domtar. Domtar project managers and process engineers continued to receive on-the-job training in the LignoBoost process. Domtar continues to support a part-time NCSU student intern at NCSU laboratories. A new post-doc was hired and trained for lignin applications development. An additional new, dedicated fulltime process engineer was hired and trained to help staff round-the-clock Lignoboost operations. A rotational training program was established for Lignoboost shift leaders at the mill. CSI. An undergraduate Chemical Engineering student from Michigan Tech was hired as a summer intern to work on pilot-scale implementation. FPL. Several FPL scientists continued to provide hands-on scientific and experimental training and guidance to a post-doctoral resesarcher. NCSU. Eight graduate research associates and post-doctoral researchers continued to be trained in the study of lignin chemistry, product development, and utilization. A course was presented on lignin chemistry for participants in the lignin utilization project, also attended by Domtar personnel. How have the results been disseminated to communities of interest? See "Target Audience" section of report. What do you plan to do during the next reporting period to accomplish the goals? The following activities are planned over the next reporting period. Task 1. Economic Analysis. Mark Conlon (formerly BC) will complete economic analyses on biomass feedstocks, while Domtar will complete economic analyses of conversion technologies for sugar and lignin applications. Task 2. Lignin Removal Demonstration Project. Domtar will continue to refine and improve the Lignoboost operation with the goal of continuous operations, culminating with evaluation and recommendation on a permanent install for Plymouth and other Domtar mills. Task 3. Hydrolysis Demonstration Project. CSI will complete pilot demonstration work towards a final report on pilot process efficiency and reliability, develop specifications and a budget for a demonstration project, and offer recommendations on a permanent installation at Plymouth and other Domtar mills. Task 4. Lignin as Fuel Additive/Extender Study. NCSU will complete work to demonstrate and assess the technical and economic viability of lignin as a fuel extender. Task 5. Lignin as a Biomaterial Study. NCSU will complete work to demonstrate and assess the technical and economic viability of lignin as a biomaterial in phenol substitutions and wood products. Task 6. Sugar for Algae Nutrient Study. KAS will complete work to demonstrate and assess the technical and economic viability of sugar as an algae nutrient. Task 7. Process Engineering and Life Cycle Analysis. Finally, NCSU will complete process engineering and life cycle analysis for various feedstocks towards biofuels and bioproducts.
Impacts
What was accomplished under these goals?
Task 1. Economic Analysis (BC/Conlon/Domtar) Feedstock analysis demonstrated that the Domtar Plymouth pulp mill has opportunity and access to source abundant cost advantaged lignocellulosic biomass, a critical element in developing profitable advanced cellulosic biofuels and bioproducts projects. Economic analysis is underway for the conversion technologies and sugar applications. As part of the market development work, Domtar has contacted and had preliminary interactions with over 20 high promise, potential commercial end users of lignin. Further, as an indirect and unanticipated result of this marketing work, Domtar has discovered a significant market opportunity for another bio-based pulp mill by-product; namely crude tall oil and its derivatives. Domtar is presently conducting a techno-economic evaluation of expanding the Plymouth Bio-Refinery to include a tall oil acidulation plant and a subsequent separation and upgrading system for tall oil fatty acids, resins and pitch. Task 2. Lignin Removal Demonstration Project (Domtar/Metso/Valmet) As a direct result of the capital project (which was a first of its kind for the lignoboost process), both Domtar and Metso/Valmet have significantly advanced their process, mechanical, and operational knowledge of this system. This enhanced knowledge and experience will be of great value in achieving future widespread commercialization of the technology. Start up and operations of the system have further enhanced the process, mechanical and operational knowledge of this system for both Domtar and Metso/Valmet. In particular, the operating experience is the first of its kind in the world for a complete, commercial scale system and specifically, for a southeastern U.S. softwood-derived feedstock. By the end of 2014 a proposal to upgrade and/or replicate the semi-works plant to a larger commercial scale will be prepared, submitted and evaluated. Optimization and troubleshooting continue. To date, the plant is very close to design production rates, target availability and reliability metrics, and target operating costs. As part of the process modeling and validation exercise (i.e. the very first stage of the evaluation process), Domtar has developed a more comprehensive understanding of the Plymouth mill's sodium/sulfur balance. This has led to a new and improved method for controlling the purchase and use of make-up chemicals, leading to greater re-use of caustic soda and lower emission of waste salts from the mill. Results to date confirm that the removal of lignin has de-bottlenecked the recovery boiler (thus resulting in increased productivity and efficiency for the mill). Operating and unit costs continue to decline as ramp up and process optimization continue. Results to date suggest overall cash and product unit costs will be very close to design. Further, preliminary market development and sales results suggest that external sales margins can justify additional lignin removal projects, especially if and when improved mill efficiencies can be achieved. Task 3. Hydrolysis Demonstration Work (CSI/Domtar) Cellulose Sciences International (CSI) replaced HCL early in the project. For purposes of designing and evaluating the demonstration scale design, it was important to determine whether biomass after treatment would respond better to enzymes than untreated biomass, and similarly, to determine how much of the biomass would be removed in processing, before conversion to sugars. It was determined that 56-93% of the biomass remains after the CSI treatment protocol is applied, but before enzyme hydrolysis, depending on the type of biomass. The highest treatment yield of 93% was obtained for softwood pine at 0.4 mm (this is the biomass used at the Plymouth Mill). It was found that a smaller particle size results in more successful hydrolysis of woody materials. Preliminary heat and material balance flowsheets and cost estimated have resulted in novel proposals for process design and integration into the Plymouth Mill. Task 4. Lignin as a Fuel Additive/Extender Study (NCSU/Domtar) Domtar provided lignin samples to NCSU to test and evaluate, as well as to potential commercial users. NCSU characterized the samples and developed diesel/biodiesel blends containing phenol derivatives, and Domtar is using the information to evaluate potential applications. Hydrocarbon, soot, NOx, and carbon monoxide emissions were found to be much lower for blends containing the phenol compound. Task 5. Lignin as a Biomaterial Study (NCSU/FPL/Domtar) In lignin characterization by NCSU, Domtar lignin samples have been characterized and the information provided to Domtar to evaluate potential uses. Several technologies have been identified to modify lignin and make it more suitable for use in adhesives and polymer applications. FPL continues to evaluate the lignin for use in durable composites and polymeric adhesives. The results of this investigation show promise for partially replacing phenol by PCO2KL in phenol formaldehyde resin, designed for application as an adhesive in the production of plywood. The search for an economic lignin-based wood adhesive continue. Tests showed that composites containing modified lignin presented lower water uptake with the time exceeding 500 hours. Chemical modification of lignin by means of anhydrides was beneficial to increase flexural properties (MOE and MOR) as compared to the control composites made with unmodified PCO2KL. Overall, composites with PA modified lignin display better mechanical properties than those with MA or SA modified lignin. In weathering tests, it was found that the presence of lignin in composites retards the photo degradation of WPCs and increases the modulus of elasticity. Task 6. Sugar for Algae Nutrient Study (KAS/Domtar/CSI) KAS replaced GA early in the project. Three target strains of algae were selected, based on performance using model sugars for growth studies on the wood hydrolysates provided by CSI. Three wood hydrolysates: southern wood hydrolysate, southern pine bleached kraft pulp, and southern pine finer chips were received from CSI. Initial growth studies for all three strains were performed by KAS using the 96-well plate assay with varying wood hydrolysate concentrations. Further validation of microbial growth was performed at 25-50 ml flask scale. Optimal algae strains and growth parameters were determined. To establish methods and logistics specific for each of the target strains to produce biomass, each of three strains was individually grown at 3 L in a medium containing glucose as the carbon source. Phospholipids and other essential fatty acids are value-added products from microalgae for animal nutrition and aquaculture. There is a strong potential for at least one of the strains to produce phospholipids. To further validate the feasibility of a potential downstream process for this value-added product, crude oleoresin extract was obtained and the phospholipids were extracted and analyzed. Fatty acid profile showed the presence of two essential fatty acids, gamma-linolenic acid (GLA), an omega-6 fatty acid; and alpha-linolenic acid (ALA), an omega 3-fatty acid. Both fatty acids are used for animal nutrition: GLA to stimulate appetite and digestion, and ALA to stimulate physiological functions. Task 7. Process Engineering and Life Cycle Analysis (NCSU) The information from the process simulation is being used by the mill to optimize operations when the new lignin separation will be fully implemented. The process modeling and validation has led to an improved understanding of the Plymouth Mill's sodium/sulfur balance. This in turn is leading to improved make up in chemical controls, lower costs and less waste.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Argyropoulos, D.S., Towards Thermoplastic Lignin Polymers; Progress in the Utilization of Kraft Lignin for the Synthesis of Heat Stable Polymer Melts, Journal of Biotechnology & Biomaterials, 2013, 3, 3, DOI: 10.4172/2155-952X.1000e123.
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Argyropoulos, D. S., Sadeghifar, H., Cui, C., and Sen, S., Synthesis & Characterization of Poly(arylene ether sulfone) Kraft Lignin Heat Stable Copolymers, ACS Sustainable Chemistry & Engineering, October 2013, DOI http://dx.doi.org/10.1021/sc400085a.
- Type:
Journal Articles
Status:
Under Review
Year Published:
2014
Citation:
Chen, Y., Stark, N.M., Cai, Z., Frihart, R.C., Lorenz, L.F., and Ibach, R.E., Synthesis of esterified Kraft lignins for durable composites: Chemical and thermal properties, Bioresource Technology (under peer review).
- Type:
Journal Articles
Status:
Under Review
Year Published:
2014
Citation:
Chen, Y., Stark, N.M., Cai, Z., Frihart, R.C., Lorenz, L.F., and Ibach, R.E., Effect of chemical modification of Kraft lignin on the physical and mechanical properties of HDPE/Kraft lignin composites, (under FPL internal review).
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Cui, C., Sun, R., and Argyropoulos, D.S., Fractional Precipitation of Softwood Kraft Lignin; Isolation of a Narrow Fractions Common to a Variety of Lignins, ACS Sustainable Chem. Eng., Articles ASAP (As Soon As Publishable) Publication Date (Web): January 30, 2014 (Research Article), DOI: 10.1021/sc400545d.
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Sen, S., Sadeghifar, H., and Argyropoulos, D.S., "Kraft Lignin Chain Extension Chemistry via Propargylation, Oxidative Coupling & Claisen Rearrangment, Biomacromolecules, dx.doi.org/10.1021/bm4010172 (2013), 2013, 14 (10), pp 33993408 DOI: 10.1021/bm4010172.
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Ayoub, A., Venditti, R.A., Jameel, H., and Chang, H.-M., The effect of gamma-irradiation on the composition and thermal properties of kraft lignin and styrene grafted lignin, Journal of Applied Polymer Science, 131(1), DOI: 10.1002/app.39743, 2013.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
Argyropoulos, D., Towards Thermoplastic Lignin Polymers; Progress in the utilization of kraft lignin for the synthesis of heat stable polymer melts, 5th Nordic Wood Biorefinery Conference, March 25-27, 2014, Stockholm, Sweden.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2013
Citation:
Ayoub, A. and Venditti, R.A., The Effect of Irradiation On the Processability of Lignin for Carbon Fiber Applications, American Institute of Chemical Engineers Annual Meeting, November 3-8, 2013, San Francisco, CA.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2013
Citation:
Chen,Y., Frihart, R.C., Cai, Z., Lorenz, L.F., Stark, N.M.., and Ibach, R.E., Characterization of industrial kraft pine lignin for the production of adhesives, Proceedings in International Conference on Wood Adhesives, 2013 Oct. 9-11, Toronto, Ontario Canada.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2013
Citation:
Chen,Y., Frihart, R.C., Cai, Z., Lorenz, L.F., and Stark, N.M, Lignin-based Phenol-Formaldehyde Resins from Purified CO2 Precipitated Kraft Lignin (PCO2KL), Proceedings in International Conference on Wood Adhesives, 2013 Oct. 9-11, Toronto, Ontario Canada.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2013
Citation:
Chen, Y., Oral Presentation, International Conference on Advancements in Fiber-Polymer Composites: Wood Fiber, Natural Fibers, and Nanocellulose, May 6-7, 2013, Milwaukee, WI.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
Marcoccia, B. and Barfield, M., Update on the Integrated Biorefinery at Domtars Plymouth, NC Pulp Mill, PaperWeek Canada 2014, 100th Annual Conference of the Canadian Pulp and Paper Industry, February 3-6, 2014, Montreal, QC, Canada.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
Nypel�, T., Marcoccia, B., and Rojas, O.J., Lignin as precursor for functional particles, 247th ACS National Meeting & Exposition, Chemistry and Materials for Energy, March 16-20, 2014, Dallas, Texas.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
Wimby, M., Commercialization of the LignoBoost Process, 5th Nordic Wood Biorefinery Conference, March 25-27, 2014, Stockholm, Sweden.
|
Progress 05/01/12 to 04/30/13
Outputs
Target Audience: Domtar's presentation at the International lignin conference in June 2012 attracted the scientific community engaged in lignin applications research and development, including R&D staff of several large potential customers. Follow-up calls and emails ensued from around the world. In product applications and market development, target audiences are potential customers and end users of lignin, including chemical and materials companies, solid fuel producers and users, wood product companies, emulsion applications, commercial users of phenol-based materials, etc. Dr. Marcoccia, the project director, was an invited speaker at the March 27-28, 2013, Workshop on Greening Thermoplastics with Lignin, sponsored by Canada's National Research Council (NRC). Held at NRC facilities in Boucherville, Canada, the two-day forum focused on the integration of lignin into thermoplastic processing for automotive makers and building material suppliers. Dr. Marcoccia's presentation was titled, “BioChoice™ lignin: the launch of a new bio-products product platform.” In print and web-based publications, Metso ran an advertisement in the March 2013 issue of PaperAge Magazine, while Domtar issued a press release on March 12, 2013, announcing the start of commercial lignin production: DOMTAR INAUGURATES COMMERCIAL LIGNIN PRODUCTION Plymouth Mill to produce bio-material with wide range of industrial applications as petro-chemical alternative - the first of its kind in over quarter century Montreal, March 12, 2013 – Domtar Corporation (NYSE: UFS) (TSX: UFS) today announced that it has successfully installed a commercial-scale lignin separation plant at its Plymouth, North Carolina mill, the first U.S. facility of its type in over 25 years. The production of BioChoice™ ligninbegan in February, with a targeted rate of75 tons a day, destined for a wide range of industrial applications as a bio-based alternative to the use of petroleum and other fossil fuels. The successful installation of commercial-scale lignin removal capacity at the Plymouth Mill is the culmination of a research and engineering project launched by Domtar in 2010. This project was further boosted when the U.S. Department of Agriculture and the U.S. Department of Energy awarded the company a grant through the Biomass Research and Development Initiative. Domtar’s lignin operation sets a new path for the industry and also marks the latest sustainability milestone for a company that has long been recognized as an industry leader in forest certification and environmental stewardship. “Our vision is to be a global leader in fiber-based innovation,” said Bruno Marcoccia, Domtar’s director of research and development. “A big part of this is our focus on partnering with best-in class collaborators to develop new products and markets for a wide portfolio of initiatives, like BioChoice.” “The possibilities for making a real difference in terms of offering manufacturers a bio-based alternative to the use of petro-chemicals is truly exciting,” said Hasan Jameel, a professor in North Carolina State University’s Department of Forest Biomaterials. “This is a big win for sustainability on two counts - Domtar improves the efficiency of its pulp-making process, and at the same time the market gets a reliable, high-quality source of this underused material with so much potential.” A wide range of potential applications for BioChoice lignin exists, including fuels, resins and thermoplastics, described at www.domtar.com. The press release was picked up by dozens of .com media sites worldwide. Examples include: March 14, 2013 - "Domtar inaugurates commercial lignin production," http://www.biofuelsdigest.com/bdigest/2013/03/14/domtar-inaugurates-commercial-lignin-production/ March 22, 2013 - "Domtar launches commercial lignin production plant in US," March 25, 2013 - "Domtar rewrites rules for paper and pulp production," http://www.hydrocarbons-technology.com/news/newsdomtar-launches-commercial-lignin-production-plant-in-us http://www.greenbiz.com/blog/2013/03/22/domtar-rewrites-rules-paper-and-pulp-production NCSU presented its work on lignin utilization to Air Liquide, a French multinational company that supplies industrial gases and services to various industries. NCSU also presented work on lignin characterization and utilization at the University of Tokyo. Changes/Problems: Early in Year 2, Domtar replaced two of the partners in the original proposal with CSI and KAS. However, this delay resulted in a 6 to12 month lag in the schedule for tasks lead by subawardees (tasks 1.1, 3.1, 4, 5, 6, and 7) due to the interdependence of their work. All Domtar-lead tasks remain on schedule. In addition, CSI's fermentation and filtration system acquisitions were an approved departure from the original plan. These modifications were decided on after consideration of the larger amount of sugars needed for the algae study than was previously anticipated. What opportunities for training and professional development has the project provided? Domtar. Three current Domtar personnel were added to project management teams and received on-the-job training in the LignoBoost process. Three new positions for process manufacturing engineers were created and filled, and the engineers are in training. Mill E&I personnel were trained on the new system, O&M personnel were trained in the lignoboost process, and a current staff member assumed a new role in fulltime marketing and sales for the new BioChoiceTM lignin. A senior student in Paper Science Engineering and Chemical Engineering at NCSU was trained as an intern at Domtar in summer 2012, where he carried out lab and pilot scale work in lignin precipitation, carbonization, acidification, and analysis. The student continues as a part-time intern for Domtar this year at NCSU laboratories. Domtar also retained an intern in Canada (Ph.D. candidate) to perform in-depth technical and market evaluations for lignin and lignin derivatives. FPL. Project personnel were trained to perform DMA and TGA tests and in PF-3 resins production. NCSU. NSCU offered a two-day course on the chemistry of lignin for all of the project participants (as well as additional graduate students) for a total of 15 faculty, researchers and graduate students. Further training was offered on the new lignin extruder, which was partly purchased using project funds. How have the results been disseminated to communities of interest? The biorefinery project has been cited by Domtar’s CEO John Williams during publicly broadcasted analyst calls. In government audiences, Domtar has continuously advocated before Congress for mandatory funding of the BRDI program.This advocacy has included letters to Capitol Hill, contact with Congressional staff and work within trade associations. On August 20, 2012, Domtar hosted Congressman G.K. Butterfield (1-NC) at the Plymouth facility. The Congressman was given a personal briefing on the lignin removal project, then toured the construction to see progress on the project.On June 28, 2012, Domtar spent a day on Capitol Hill explaining the project to Congressional staff for Senators Burr and Hagan, along with staff for Representatives Butterfield and Jones. While the focus was on the immediate impact this project would have in eastern North Carolina, Domtar also used the opportunity to stress the criticality of BRDI toward making the project happen. Before ending the day, the Domtar delegation visited Carmela Bailey and relevant staff at NIFA to introduce key Domtar players and to provide a face-to-face update on the project. In upcoming events, Domtar is planning a celebration to mark the start of production at the Plymouth Mill. Currently planned for June, the team is working with members of the North Carolina Congressional Delegation to attract attention to the opening from the President’s Administration.Local, state and federal officials will be invited. The event also will be an opportunity to showcase the process for current and potential customers. In another event, FPL plans to present their findings at the International Conference on Wood Adhesives, which will be held on October 9-11, 2013 at Toronto, Ontario Canada. What do you plan to do during the next reporting period to accomplish the goals? The following activities are planned over the next reporting period. Task 1. Economic Analysis. BC will continue economic analyses on biomass feedstocks, while Domtar will continue economic analyses of conversion technologies for sugar and lignin applications. Task 2. Lignin Removal Demonstration Project. Domtar will carry out further demonstration trials with the goal of continuous operations, culminating with evaluation and recommendation on a permanent install for Plymouth and other Domtar mills. Task 3. Hydrolysis Demonstration Project. CSI will continue pilot demonstration work towards a final report on pilot process efficiency and reliability, develop specifications and a budget for a demonstration project, and offer recommendations on a permanent installation at Plymouth and other Domtar mills. Task 4. Lignin as Fuel Additive/Extender Study. NCSU will continue work to demonstrate and assess the technical and economic viability of lignin as a fuel extender. Task 5. Lignin as a Biomaterial Study. NCSU will continue work to demonstrate and assess the technical and economic viability of lignin as a biomaterial in phenol substitutions and wood products. Task 6. Sugar for Algae Nutrient Study. KAS will continue work to demonstrate and assess the technical and economic viability of sugar as an algae nutrient. Task 7. Process Engineering and Life Cycle Analysis. Finally, NCSU will continue work in process engineering and life cycle analysis for various feedstocks towards biofuels and bioproducts.
Impacts
What was accomplished under these goals?
By way of introduction to the activities of the project in Year 2, two of the project team organizations were replaced following NIFA approval: Cellulose Sciences International (CSI) replaced HCL CleanTech for leading the hydrolysis demonstration project (Task 3); and Kuehnle Agrosystems (KAS) replaced General Atomics for the sugar for algae nutrient study (Task 6). Task 1. Economic Analysis (BC/Domtar) Sustainable and cost effective biomass supply chain assessment is a critical component to developing a commercially viable and financeable biofuels project. The delivered cost of biomass is the largest variable cost associated with advanced biofuels production. Connecting the completed lignocellulosic biomass cost and supply options from the proximal forest resources and farm/forage acreage to the biofuels processing options under development by the project team will allow BC to complete a thorough economic analysis including return on investment for defined equity participants, consistent with the project timeline. Task 2. Lignin Removal Demonstration Project (Domtar/Metso) As a direct result of the capital project (which was a first of its kind for the lignoboost process), both Domtar and Metso have significantly advanced their process, mechanical, and operational knowledge of this system. This enhanced knowledge and experience will be of great value in achieving future widespread commercialization of the technology. Start up and operations of the system have further enhanced the process, mechanical and operational knowledge of this system for both Domtar and Metso. In particular, the operating experience is the first of its kind in the world for a complete, commercial scale system and specifically, for a southeastern U.S. softwood-derived feedstock. As part of the process modeling and validation exercise (i.e. the very first stage of the evaluation process), Domtar has developed a more comprehensive understanding of the Plymouth mill's sodium/sulfur balance. This has led to a new and improved method for controlling the purchase and use of make-up chemicals. This will result in greater re-use of caustic soda and lower emission of waste salts from the mill. Task 3. Hydrolysis Demonstration Work (CSI/Domtar) CSI acquired two new pieces of equipment during this quarter: a bioreactor/fermentor unit and a molecular filtration device. The bioreactor, an Eppendorf BioFlo 115 with a 3 liter vessel, allows hydrolysis of larger sample quantities than was possible previously, and operates in a fashion closer to a full-scale commercial facility. The control system simplifies operation by providing automatic pH control and fluid level control. The molecular filtration device provides the capability to remove enzymes from the hydrolyzate for a purer end product. While there were some initial problems with fouling, a pre-filtration using a beverage filtration system has resolved them. CSI also found that filtered sugar solutions are much less susceptible to mold growth once filtered. Biomass samples were received from BC and Domtar. BC samples were dry, but not chipped or ground, requiring Wiley milling at FPL. Domtar samples were not dried; for the pulps this is not an obstacle as they have already been reduced to fiber. For the knotter rejects and CTS rejects, samples must be dried prior to Wiley milling. Work to date that has led to the preliminary heat and material balances and preliminary flowsheets has resulted in significant insights into the CSI process. These insights, in turn, have resulted in a number of novel proposals for process design and integration into an existing pulp mill. Task 4. Lignin as a Fuel Additive/Extender Study (NCSU/Domtar) Domtar provided lignin samples to NCSU to test and evaluate, as well as to potential commercial users. NCSU characterized the samples and Domtar is using the information to evaluate potential applications. Preliminary results show the potential to blend lignin with liquid fuels in an emulsion form have led to an internal Domtar study that is evaluating the opportunity to use blended mixtures of fossil and bio-derived fuels in our rolling stock. Task 5. Lignin as a Biomaterial Study (NCSU/FPL/Domtar) The extensive characterization of BioChoice™ lignin that has been performed by both NCSU and FPL has indirectly helped Domtar’s market development efforts, by providing prospective customers with valuable information about this feedstock. Once work on this project is complete, Domtar will perform techno-economic evaluations of the proposed lignin modification processes and targeted applications with the aim of identifying new business and investment opportunities. NCSU continues to develop information on the suitability of the lignin for different applications. Recent work on fractionating kraft lignin will offer a means of arriving at a consistent and reproducible lignin fraction irrespective of manufacturing details such as cooking conditions, H factor, and other pulping details and natural line upsets. New uses of lignin are being developed as a fuel additive, biopolymer, and surfactant. FPL continues to evaluate the lignin for use in durable composites and polymeric adhesives. The structure and composition of the lignin restrict its subsequent applications in phenolic-formaldehyde resins. It was found that the lignin can only substitute for a small portion of phenol in PF or other resins due to the low number of lignin functional groups capable of reacting with formaldehyde under alkaline-catalyzed conditions. Because of the extremely low reactivity, direct use of lignin in PF resins would require long press time and high press temperature. To overcome this disadvantage, it is necessary to modify the chemical structure of the lignin to increase its potential reactive sites toward formaldehyde. Finally, the use of lignin as a compatibilizer in wood flour-polyethylene composites was found to improve physical (water absorption) and mechanical properties (flexural modulus, flexural strength and impact strength). However, the mechanical properties deteriorate with lignin proportion because of very low compatibility/ miscibility of polar lignin in nonpolar polymer matrix. This opens new area to use modified lignin in polymer matrix which may increase compatibility/miscibility of lignin in polymer matrix. Task 6. Sugar for Algae Nutrient Study (KAS/Domtar/CSI) Preliminary testing by KAS on both hydrolysates at 1% (5 mM) concentration demonstrated higher growth with both algal and non-algal microorganisms than in the 50 mM glucose control samples. Higher concentrations of the MCC hydrolysate (5-10%) inhibited growth of some strains, suggesting the inhibitory effects of toxic compounds. None of the cultures showed any growth at 20% MCC (~100 mM glucose equivalent). Overall, the heterotrophic cultures outperformed the phototrophic cultures in total biomass and lipid production when growth metrics were factored in. Task 7. Process Engineering and Life Cycle Analysis (NCSU) The information from the process simulation is being used by the mill to optimize their operations when the new lignin separation will be fully implemented. The process modeling and validation has led to an improved understanding of the Plymouth Mill's sodium/sulfur balance. This in turn is leading to improved make up chemical controls, lower costs and less waste.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2012
Citation:
Sadeghifar, H., Cui, C., and Argyropoulos, D. Toward Thermoplastic Lignin Polymers. Part I. Selective Masking of Phenolic Hydroxyl Groups in Kraft Lignins via Methylation and Oxypropylation Chemistries; Ind. Eng. Chem. Res., 2012, 51 (51), pp 1671316720 Publication Date (Web): December 4, 2012 (Article) DOI: 10.1021/ie301848j.
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Cui, C., Sadeghifar, H., Sen, S., and Argyropoulos, D. S. Toward thermoplastic lignin polymers; Part II: Thermal and polymer characteristics of kraft lignin and derivatives," BioResources 8(1), 864-886, (2013).
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2012
Citation:
Marcoccia, Bruno. "A New Commercial Scale Source of Lignin based on Metso's LignoboostTM Technology," International Lignin Biochemicals Conference, Toronto, Ontario, June 21, 2012.
- Type:
Journal Articles
Status:
Under Review
Year Published:
2013
Citation:
US Forest Products Laboratory: Characterization of Industrial Kraft pine lignin for the production of adhesives.
- Type:
Journal Articles
Status:
Under Review
Year Published:
2013
Citation:
US Forest Products Laboratory: Anhydrides modification of Kraft lignin for synthesis of durable composites: Chemical and thermal studies.
|
Progress 05/01/11 to 04/30/12
Outputs
OUTPUTS: The main output of the project is an integrated demonstration biorefinery that can be widely duplicated across pulp and paper mills to achieve the objectives of the BRDI program. The scope of work for the three-year demonstration project includes installation, testing, and semi-works demonstration of the Metso LignoBoost system for lignin removal, to generate clean, dry lignin; and a system for production of fermentable sugars, lignin and high-value biofuels and bioproducts. Other activities include development of new, high-value biofuel/bioproduct applications from the high-purity intermediates generated by both systems; biofuels/bioproduct development for sugars and lignins; Life Cycle Analyses; and broad economic analyses. Most of the project activity during the first year centered on the lignin removal project. This project will extract lignin from the existing black liquor feeding the recovery boiler, and sell it as a binding agent for wood pellets and as a feedstock for production of various biochemicals and biomaterials. The project milestones/deliverables are structured via a series of tasks; only those with activity in Year One are reported here. Task 1.2: Economic Analysis of Conversion Technologies/Sugar Applications (50% complete) - Domtar arranged nondisclosure agreements and meetings with companies to review and evaluate a range of wood-to-fermentable sugars conversion technologies and their economics. Task 1.3: Conversion Technologies/Lignin Applications (33% complete) - Domtar is currently dialoguing with project partners and looking at other To Be Determined collaborators for applications in fuel briquettes, fuel pellet additives, and polyurethane foams. Task 2.1: Pre-Engineering Study for the Lignin Removal Demonstration Project (100% complete) - it was decided to go with a new system having two stages, rather than refurbishing the existing presses; and the feed logistics were finalized, which will use hard pipe for the existing feed train rather than trucking in. Task 2.2: Detailed Engineering, Estimates, and Scheduling for the Lignin Removal Demonstration Project (100% complete) - the detailed engineering, specifications, budget and master schedule are complete, the process design is being finalized, and the demonstration equipment is being purchased. Task 2.3: Procure and Assemble for Demonstration of the Lignin Removal Demonstration Project (40% complete) - all purchase orders for equipment and materials have been issued, the engineering is being finalized, a detailed project schedule has been issued and is being followed, with startup planned for the first quarter of 2013, ahead of schedule. Task 3.1: Conversion Process Demonstration Project: Identify TBD Collaborator(s) (90% complete) - as discussed in Task 1.2, a range of conversion technologies and their economics is under review, with identification of the final conversion technologies and TBD partner(s) expected soon. PARTICIPANTS: The project closely integrates efforts by a number of partners. Domtar is hosting the demonstration biorefinery and providing the feedstock, and will burn the solid lignin biofuel initially as part of its manufacturing process, develop and refine unit operations, and manage the overall project. Metso's LignoBoost technology/process equipment will separate the lignin from the black liquor produced by the mill, taking a high BTU value fuel out of a relatively inefficient boiler and upgrading this material into higher-value biofuels and bioproducts. To Be Determined Partners will demonstrate the production of sugars and/or fuels and/or biomaterials from underutilized biomass. We are nearing final selection after investigation of organizations on alternative methods of hydrolyzing waste wood and other biomass to create clean fermentable sugars, lignin, and high-value biofuel and bioproducts. North Carolina State University (NCSU), in collaboration with the To Be Determined Partner(s), will develop lignin-derived biofuel (such as aromatics and phenolic-type compounds) and the required technical specifications for the corresponding feedstocks, intermediates, and final fuel products. NCSU will further develop lignin based biomaterial products and corresponding technical specifications, plus carry out overall process modeling and life cycle analyses. The Biofuels Center of North Carolina will contribute expertise in regional biomass supply development and economic analyses of production of biofuels and bioproducts. The U.S. Forest Products Laboratory will isolate and convert the lignin into an adhesive for wood bonding to replace petroleum-based products. Finally, ITECS Consulting will assist Domtar with management support to meet USDA project deliverables, develop and manage subcontractors, and develop the technical reports to the USDA. In Year One, over 25 individuals from Domtar, Metso, and ITECS worked on the project. The following individuals were billed over 160 hours to federal funds, all from Metso: Gene Christiansen, Business Development and Innovations, pre-project work, project and North America product development, and LignoBoost coordinator; Anders L. Larsson, Global LignoBoost Sales/Product Manager, pre-project work, project and global product development; Martin Wimby, Global Technology Manager-Recovery overall process performance of LignoBoost; Henrik Wallmo, LignoBoost, research and development, lab work, filterability and the LignoSize program; Anders Littorin, Lead Process Engineer; John Weikmann, Process Engineer for Recovery/LignoBoost, process and environmental permit support; and Daniel Barry, Project Engineer LignoBoost, pre-project and project coordination with Domtar. Other project personnel were either cost-shared or worked less than 160 hours each in the first year. TARGET AUDIENCES: One presentation was given in Year One and at least two presentations are planned for Year Two of the project. These presentations feature the first LignoBoost Plant with target audiences in the Pulp & Paper Market: (1) presentation at the American Forest & Paper Association (AF&PA), the national trade association of the forest, pulp, paper, paperboard, and wood products industry, at their Annual Meeting on February 8, 2012, in Atlanta, Georgia; (2) presentation to be given at the International BioEnergy Conference - June 13-15, 2012 in Prince George, British Columbia; and (3) presentation to be given at the Second International Lignin Biochemicals Conference - June 21, 2012 - Toronto, Canada. Metso plans to work with the Plymouth mill to set up a Pilot Unit to make Lignin for prospective Lignin End User Companies. Tours of the Plant will be coordinated with the Mill and hopefully an open house tied to a conference can be planned after a successful start-up. PROJECT MODIFICATIONS: We are nearing selection of the To Be Determined collaborators for Task 3: Conversion Process Demonstration Project, Task 4: Lignin as a Fuel Additive/Extender Study, and Task 6: Sugar for Algae Nutrient Study. We are in communication with NIFA personnel regarding additional reporting and/or forms that may be required for these collaborators.
Impacts
The main outcome of the pre-engineering work for the lignin removal project was the decision to install a significantly more expensive system than originally envisioned, with the additional cost funded by Domtar. The new system is comprised of two stages, it does not require the use of temporary logistics, and it is hard-piped. The new system will lower risk and cost in the long range, and is in full environmental compliance. The second outcome of the lignin removal project was realizing that the pre-engineering portion of the work to develop the project requires over a year, and that the basis of design needs to be an outcome of a full mill impact study to optimize the size. We learned that the liquor testing and pilot work should be done at the mill on fresh liquor, in part because the environmental permit data requires the plant to be designed to have the correct flows for Design, Normal Operations and Upset Conditions. The third outcome from the Value Engineering process was the identification of methods of engineering that will save project costs for this demonstration project, as well as future installations. The fourth and last outcome to date of the lignin removal project was the environmental assessment, including evaluating impacts to air quality, wastewater treatment and solid waste. The NC DAQ has issued a permit to construct the lignin dewatering process and is progressing to issue a revised air permit to operate the process, which is likely forthcoming during the third or fourth quarter of this year. There was no need to revise the wastewater treatment system permit to accommodate this project. The lignin process is not expected to generate any new solid waste streams.
Publications
|
|