Progress 07/01/22 to 09/30/23
Outputs
Target Audience:Låkril Technologies is developing new processes for manufacture of bio-based industrial chemicals. Our lactic-to-acrylic technology provides corn-derived drop-in bio-based acrylic acid and acrylates at cost parity to today's petrochemical acrylics while providing at least 35% reduction in CO2 emissions. Once commercialized, our process technology will be constructed and provide high-quality, well-paying STEM jobs in rural locations near corn fields, similar to ethanol plants. Commercializing our high yield lactic-to-acrylic technology helps grow the industrial chemicals portion of corn utilization to provide societal impact and high paying jobs across rural America, and economic competitiveness in global markets. Two dramatic shifts are occurring in the coming decade: (1) The shift away from gasoline to electric vehicles will reduce the need for oxygenate blending in fuels, which has been fulfilled with ethanol in the past 20 years, and (2) the shift towards plant-derived synthetic beef products will reduce the need for corn/maize, which is the primary use of starch-derived sugars. Commercializing our high yield lactic-to-acrylic technology thereby provides resilience for farm families across rural America and helps economic competitiveness in global markets through new industrial uses for the US' largest crop. Through our relationships with Corn Growers Associations, we will educate the public and prepare for new sustainable economic opportunities through communication of key issues related to emerging technologies in sustainable energy and chemicals economies, and the impact of process systems. These publications/presentations will cover the core issues including the mechanisms by how these technologies function, their methods of implementation, and impact on local economies and labor markets. Engaging rural America in a new future of agriculture for materials is critical to the farming industry, with special importance to maize production, the primary crop in the Midwestern United States. Our technology and company connect rural Minnesota and Illinois (~1/2 state population), urban Minneapolis/Chicago (~1/2 the state population), and the Midwest farm and agricultural states in general. Communications target rural and underrepresented groups with limited access to urban museums and science events. In a future where food, materials and energy are supplied by rural agricultural and distributed bio-systems, opportunity exists for rural-urban economic development. Producing sustainable acrylic acid and acrylates brings significant health and welfare benefits through increased sustainability to the $10 billion, 6.5 million metric ton per annum acrylics value chain used throughout the superabsorbent polymer, paints, coatings, and adhesives markets while increasing economic competitiveness in global markets through new industrial uses for the US' largest crop. Changes/Problems:Performance took longer than the expected 8 months due to a combination of factors. First, funds were not available until late August 2022 due to Congressional appropriation difficulties. Second, equipment delivery delays at the beginning of the project meant that catalysts were available to test, buta testing backlog needed to be worked through. Our subawardee, the University of Minnesota had similar difficulties due to an equipment maintenance period. We therefore requested a no-cost extension to 9/30/23 for this award and finished all of the tasks. We pivoted away from tasks 2/3 - the investigation of calcium and ammonium lactate sources - due to the shockingly poor dehydration selectivity obvserved and focused on the impacts of task 4 - the high water content feeds. Very good results were observed here, and we discovered the autocatalytic hydrolysis of alkyl lactates in aqueous solutions. What opportunities for training and professional development has the project provided?The 2nd year graduate student working on the project at the University of Minnesota has had mentoring not only from her official mentor, but also from industrial experts at Lakril Technologies. How have the results been disseminated to communities of interest?Through our relationships with Corn Growers Associations, several educational and informative pieces have been released to connect with rural America. With Minnesota Corn, we put together a blog post to help communicate the importance of bioderived chemicals to customers and consumers in Minnesota. https://www.mncorn.org/2023/02/07/mn-corn-supported-bioacrylic-acid-effort-reports-milestone/ We have communicated to the general public through an interview with the AZO Materials network: https://www.azom.com/article.aspx?ArticleID=22333 What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
1) During this Phase I project we discovered that high water content feeds are preferred; these are significantly lower in cost than 88wt% lactic. 2/3)To evaluate the impact of Ca and/or NH4 containing lactate feeds on catalytic performance, aqueous alkyl lactate feed was tested over Na-FAU, NH4-FAU and Ca-FAU catalysts.Both NH4-FAU varieties tested showed a strong preference for lactate decarbonylation compared to Na-FAU, with little to no methyl acrylate or acrylic acid generated, although lifetime is long. We hypothesize that at reaction temperature (300°C) the NH4 cation decomposes partially in-situ to NH3 and H+.Both Ca-FAU varieties tested yielded the same preference towards decarbonylation using 30 weight percent ethyl lactate in water, with little to no ethyl acrylate or acrylic acid generated. We suspect that utilizing a divalent cation such as calcium may generate some number of sites where one of two sites becomes H+ while the other is charge balanced by Ca(OH)+ through splitting of a water molecule. 4) We then focused our efforts on determining the appropriate water concentration in the feed. Our study primarily aimed to assess the impact of (1) varying the concentration of lactate in the liquid aqueous feedstock via variation of the water content and (2) varying the flowrate of nitrogen diluent gas. In general, reactants in hydrolysis reactions which produce ethanol, such as ethyl lactate, ethyl acrylate, and ethyl 2-ethoxypropanioate, have lower selectivity during higher water content runs. This is expected given that greater partial pressures of water in the catalyst bed should promote hydrolysis reactions which produce ethanol. Differences in acrylate speciation shows this effect clearly, where increasing water content in the feed led to a greater proportion of total acrylate species as acrylic acid versus ethyl acrylate. While continuing our studies of the catalytic dehydration of alkyl lactates,we observed that aqueous 6.9 mol% (30 wt%) solutions of methyl lactate slowly accumulated significant amounts of alcohol and lactic acid when kept at room temperature. The same was true with 6.2 mol% (30 wt%) solutions of ethyl lactate. No acid catalyst is intentionally present in these solutions, nor is lactic acid observed by gas chromatography in the freshly prepared samples.The early stages of the ester hydrolysis should be described as uncatalyzed hydrolysis. The methyl lactate or ethyl lactateproceeded to form alcohol and lactic acid with time, but the observed reaction kinetics exhibited complex behavior. All of the reactions at 6 °C and room temperature along with some of the high concentration ethyl lactate samples at 40 °C exhibited an initial period of stability with negligible change in lactate concentration within experimental error.. The duration of this initial stable period varied with both temperature and lactate concentration in water; lower temperatures and higher lactate concentrations increased this period of initial stability. We also note the difference in reactivity between the methyl and ethyl lactate samples at high concentrations, particularly at lower temperatures. Despite being at a lower lactate molar concentration, i.e. greater reactivity as shown by Figures 2 and 3, 80wt% ethyl lactate remains stable for two weeks longer than 80wt% methyl lactate at 22 °C. This effect also persistsfor other concentrations of ethyl lactate, though not in as pronounced a fashion, suggesting that size of alkyl chain may have an impact on rate of initiation/neutral hydrolysis.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2023
Citation:
Sustainable pathways to acrylic acid: Our progress on the lactic-to-acrylic route
Abstracts of Papers, 265th ACS National Meeting, Indianapolis, IN, March 26-30, 2023 CATL-3804521
- Type:
Journal Articles
Status:
Submitted
Year Published:
2023
Citation:
Reaction Kinetics of the Autocatalytic Hydrolyses of Alkyl Lactates
https://doi.org/10.26434/chemrxiv-2023-0qf21
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Progress 07/01/22 to 02/28/23
Outputs
Target Audience:Commercializing our high yield lactic-to-acrylic technology helps grow the industrial chemicals portion of corn utilization to provide societal impact and high paying jobs across rural America, and economic competitiveness in global markets.Two dramatic shifts are occurring in the coming decade: (1) The shift away from gasoline to electric vehicles will reduce the need for oxygenate blending in fuels, which has been fulfilled with ethanol in the past 20 years, and (2) the shift towards plant-derived synthetic beef products will reduce the need for corn/maize, which is the primary use of starch-derived sugars. Commercializing our high yield lactic-to-acrylic technology thereby provides resilience for farm families across rural America and helps economic competitiveness in global markets through new industrial uses for the US' largest crop. Through our relationships with Corn Growers Associations, we will educate the public and prepare for new sustainable economic opportunities through communication of key issues related to emerging technologies in sustainable energy and chemicals economies, and the impact of process systems. These publications/presentations will cover the core issues including the mechanisms by how these technologies function, their methods of implementation, and impact on local economies and labor markets. Engaging rural America in a new future of agriculture for materials is critical to the farming industry, with special importance to maize production, the primary crop in the Midwestern United States.Our technology and company connect rural Minnesota and Illinois (~1/2 state population), urban Minneapolis/Chicago (~1/2 the state population), and the Midwest farm and agricultural states in general. Communicationstarget rural and underrepresented groups with limited access to urban museums and science events. In a future where food, materials and energy are supplied by rural agricultural and distributed bio-systems, opportunity exists for rural-urban economic development. Production facilities using our technology will be built in proximity to the corn- or other bio-derived feedstock. These plants provide high-quality, well-paying STEM jobs in rural locations similar to the existing lactic acid and ethanol production facilities spread across the Midwest. Our R&D facilities and many colleges and universities to teach the necessary skills are in urban centers, enhancing the interaction and promotion of rural-urban economic development. Changes/Problems:Work has begun on testing of project goals 3 and 4, but full results are not yet available.Performance has been delayed due to a combination of factors. First, funds were not available until late August 2022 due to Congressional appropriation difficulties. Second, equipment delivery delays at the beginning of the project have meant that catalysts are available to test, but we have a testing backlog at the current time. Our subawardee, the University of Minnesota has had similar difficulties due to an equipment maintenance period. We have requested a no-cost extension to 9/30/23 for this award. What opportunities for training and professional development has the project provided?
Nothing Reported
How have the results been disseminated to communities of interest?Through our relationships with Corn Growers Associations, several educational and informative pieces have been released to connect with rural America. With Michigan Corn, we put together a blog post to help communicate the importance of bio-derived chemicals to customers and consumers in Michigan. https://micorn.org/news-and-media/blog/article/2022/11/research-update-converting-corn-to-paints-and-coatings-via-bio-based-acrylic-acid Iowa Corn led investment in our recently completed pre-seed round and have been communicating about the investment and the overall technology area to their constituents. https://www.iowacorn.org/about/news/iowa-corn-supports-lakril-technologies-with-500000-investment-in-corn-to-chemicals What do you plan to do during the next reporting period to accomplish the goals?During the next and final reporting period (01/23-09/23), we will run through the testing backlog to determine the best concentration of water in the feedstock to our process. Personnel are in place and equipment is operational. Water content is directly linked to cash cost of production of bio-based acrylic acid. Running through the testing queue will also allow determination of the appropriate cation and link to product selectivity. Near the end or slightly after the end of the award, a publication will be written on work performed at the University of Minnesota during their subaward. We will continue to interact with our Corn Growers partners; a blog post is being constructed currently for publication in the Minnesota Corn network.
Impacts
What was accomplished under these goals?
We have begun work on this program and have built out two catalytic reactors and associated gas chromatographs using non-project funds. We attended the American Chemical Society National Meeting in August 2022 when it was held here in Chicago and presented a talk and a poster on research results.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
(18) Dehydration of C3 Oxygenates to Biobased Acrylics over Inorganic Organic Composites C. P. Nicholas, Y. Pang, and P. Dauenhauer
Abstracts of Papers, ACS National Meeting Fall 2022, Chicago, IL, August 21-25, 2022, CATL-3741830.
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