Source: ITACONIX, LLC submitted to
DEVELOPMENT OF INTEGRATED PRODUCTION OF POLYITACONIC ACID FROM NORTHEAST HARDWOOD BIOMASS
 
PROJECT DIRECTOR: Durant, Y. G.
 
PERFORMING ORGANIZATION
(N/A)
ITACONIX, LLC
HAMPTON FALLS,NH 03844
 
NON TECHNICAL SUMMARY: In a 2004 report to the Office of Biomass Program (DOE-EERE), Itaconic acid was identified as one of the top 12 value added chemicals from biomass. Yet its polymerization was identified as a key barrier to commercial development. This technical barrier was recently overcome by the University of New Hampshire and licensed to Itaconix. The resulting biobased material polyitaconic acid (PIA) is a water soluble polymer with a wide range of applications including superabsorbents (SAP), anti-scaling agents in water treatments, co-builders in detergents, and dispersants for minerals in coatings. Polyitaconic Acid is also being evaluated by as an amendment for soil retention and nutrient delivery. It is an attractive replacement to the well established polyacrylic acid (PAA), a petrochemical. To penetrate the commodity market, PIA must have a target cost competitive to PAA. Recently, PIA has been produced by Itaconix using commercial itaconic acid obtained by the fermentation of dextrose typically derived from corn or rice. Under such non integrated structure, PIA can be produced at a cost of $3/Kg. In order to displace PAA it must reach a production cost below $1.5/Kg. An integrated approach is proposed using a low cost raw material such as xylan, produced by a biorefinery of the type encountered in the Kraft wood pulp manufacturing process. The investigating collaborative team has preliminary data indicating the strong likelihood of such an integrated approach being successful.
 
OBJECTIVES: This project aims at developping a stream-integrated approach to the low cost production of a large industrial commodity water soluble polymer: polyitaconic acid. The project is broken down in 22 tasks, each having a duration of 3 to 6 months. The first four tasks have the objective to produce "minimally treated carbohydrate" from wood biomass for Microbial Conversion to Itaconic Acid. Task 1. Hemicellulose Extraction from Hardwood Biomass. Task 2. Experiments Designed to Upgrade the Quality of the Crude Extract Task 3. Analysis of Final Extract Composition. Task 4. Preliminary Process Design and Economic Analysis for Processing to Produce Xylan Extract from Northeast Woody Biomass. Tasks 5 to 10 focus on Strain Development and Fermentation. Task 5: Shake flask experiments to determine the effects of xylan extract pre-treatment and potential inhibitors on growth and itaconic acid production by A. terreus. Task 6: Lab scale fermentation experiments: Phase 1 will optimize conversion of xylose to itaconic acid. Phase 2 will to optimize conversion of xylan hydrolysate to itaconic acid. Task 7: Experiments with minimally pretreated xylan extract. Task 8: Strain optimization: Xylose conversion. Task 9: Generation of material for recovery and polymerization experiments. Task 10: Large scale sporulation optimization. Tasks 11 to 16 are focused on the recovery of itaconic acid from fermentation broth. Task 11: Impurities analysis. Task 12: Liquid-liquid Equilibrium (LLE) Data Acquisition. Task 13: Bench Scale Trials with Model and Real Broths. Task 14: Transfer Kinetics of Extraction & Stripping with Real Broths: Task 15: Scale Up/Modeling. Task 16: Recovery Skid Development. Tasks 17 to 22 are focused on process integration and polymerizations of itaconic acid. Task 17: Potential Impurity assessment with "spiked" solutions. Task 18: Synthesis and polymerization of esters of itaconic acid. Task 19: Recovery Skid trials, operation and polymerization integration. Task 20: Life cycle analysis (LCA). Task 21: Economic analysis of Integrated Process. Task 22: Biodegradability testing of polyitaconic acid. The total project duration is 24 months.
 
APPROACH: We are developping a stream-integrated approach to the production of a large industrial commodity water soluble polymer: polyitaconic acid. The University of Maine with expertise in the area of hemi-cellulose extraction is optimizing the hydrolysis and extraction parameters for the production of xylan (or polyxylose)from hardwood within a kraft pulping processing plant. Microbia is bioengineering a fungi, such as Aspergillus terreus to ferment carbohydrates such as xylose into itaconic acid. Itaconix is optimizing extraction of itaconic acids from the fermentation broth and purifying the extract to a polymerizable grade. Last, Itaconix is polymerizing itaconic acid into polyitaconic acid. Each stream associated with a processing step is being optimized in order to provide maximum efficiency, productivity and performance to yield a total value chain that is competitive with petrochemical production. This project includes a cradle to grave differential analysis for the substitution of petrochemical based polyacrylic acid with biobased polyitaconic acid. Parameters such as CO2 balance, energy requirements and by-products are key to this system approach. The economic analysis of this process is also essential for early adoption as cost performance is essential to the transfer of this technology into commercial practice.
 
CRIS NUMBER: 0220209 SUBFILE: CRIS
PROJECT NUMBER: NHW-2009-04732 SPONSOR AGENCY: NIFA
PROJECT TYPE: OTHER GRANTS PROJECT STATUS: EXTENDED MULTI-STATE PROJECT NUMBER: (N/A)
START DATE: Sep 1, 2009 TERMINATION DATE: Feb 29, 2012

GRANT PROGRAM: BIO MASS RES. AND DEV. SEC 9008
GRANT PROGRAM AREA: Biomass Research and Development

CLASSIFICATION
Knowledge Area (KA)Subject (S)Science (F)Objective (G)Percent
511242010002.1100%

CLASSIFICATION HEADINGS
KA511 - New and Improved Non-Food Products and Processes
S2420 - Noncrop plant research
F1000 - Biochemistry and biophysics
G2.1 - Expand Domestic Market Opportunities


RESEARCH EFFORT CATEGORIES
BASIC (N/A)%
APPLIED (N/A)%
DEVELOPMENTAL 100%

KEYWORDS: biomass~pulp~itaconic acid~northern hardwood~xylan~hemicellulose~fermentation~recovery~esters of itaconic acid~polymerization~polyitaconic acid~intergrated production

PROGRESS: Sep 1, 2010 TO Aug 31, 2011
OUTPUTS: Our collaborators, the University of Maine and University of Massachusetts are 95% complete on their tasks and will be done by August 31. Our most intensive tasks, Recovery of Itaconic Acid from A. Terreus and Engineering Integration are both around the 75-80% mark. We are making great strides and have quantified the inhibitors to the fungi, and have found the optimum methodology for esterification of the polymer for creating biolatexes by emulsion polymerization. We have been giving presentations on our work at a number of national and international Biomass Symposia as well as receiving a patent on the discoveries made during this project. Patent Title: Emulsion Polymerization Of Esters Of Itaconic Acid Document Type and Number: U.S. Patent Application 20110144265 Kind Code: A1 Inventors: Durant, Yvon (Lee, NH, US) Publication Date: 06/16/2011 Filing Date: 12/16/2010 Abstract: Esters of itaconic acid are polymerized in aqueous medium in the presence of seed particles. The seed particles may absorb the monomer and provide for polymerization to a desired particle size. The polymers that are produced may be employed in adhesives, paints, and paper formulations. Seminar : University of New Hampshire. Materials Science program Title: Making a Wood Varnish out of Wood Date: 10-06-2010 Presenter: Yvon Durant. Seminar : University of New Hampshire. Chemistry Department Title: From wood to wood coatings Date: 02-08-2011 Presenter: Yvon Durant. Speaker: 2nd Annual Next Generation Bio-Based Chemicals Summit, San Diego, CA. Title: From wood to detergents and paints Date: 02-16-2011 Presenter: Yvon Durant. Invited speaker: 94th Canadian Chemistry Conference, Montreal, Canada. Title: From wood to wood coatings Date: 06-06-2011 Presenter: Yvon Durant. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Seminar : University of New Hampshire. Materials Science program Title: Making a Wood Varnish out of Wood Date: 10-06-2010 Presenter: Yvon Durant. Seminar : University of New Hampshire. Chemistry Department Title: From wood to wood coatings Date: 02-08-2011 Presenter: Yvon Durant. Speaker: 2nd Annual Next Generation Bio-Based Chemicals Summit, San Diego, CA. Title: From wood to detergents and paints Date: 02-16-2011 Presenter: Yvon Durant. Invited speaker: 94th Canadian Chemistry Conference, Montreal, Canada. Title: From wood to wood coatings Date: 06-06-2011 Presenter: Yvon Durant. PROJECT MODIFICATIONS: The original objective of Task 1 was to extract northeast hardwood to maximize dissolution of hemicellulose polymers for hydrolysis to monomer sugars, predominantly xylose, while producing the minimum amount of impurities that inhibit fermentation of the sugars to itaconic acid. During the course of the research the initial objective was broadened to include mixed northeastern softwoods as well as corn gluten feed. Both the northeastern softwood and the corn gluten feed are high in 6-carbon sugars such as glucose and mannose which we found to be more readily converted to Itaconic acid during fermentation by Aspergillus terreus than the 5-carbon sugars such as xylose and arabinose.

IMPACT: 2010-09-01 TO 2011-08-31 Goal/Objective The University of Maine was responsible for producing extracts from biomass that have a high concentration of sugars (100 grams per liter) suitable for the conversion to itaconic acid by fermentation using the fungus (mold) Aspergillus terreus. The process investigated consists of the extraction of carbohydrates or complex sugar polymers from the biomass source by using water or dilute acid. The polymeric sugars in the raw extract solution are first concentrated, and then the molecular weight of the sugar polymers is reduced by acid hydrolysis or cleavage of the carbohydrate macromolecules into component sugars. Finally, the extract is purified by removal of substances that are toxic to the Aspergillus terreus fungus used in fermentation. Substances known to be toxic to Aspergillus terreus are lignin and organic acids such as acetic acid as well as furfural. The original objective of Task 1 was to extract northeast hardwood to maximize dissolution of hemicellulose polymers for hydrolysis to monomer sugars, predominantly xylose, while producing the minimum amount of impurities that inhibit fermentation of the sugars to itaconic acid. During the course of the research the initial objective was broadened to include mixed northeastern softwoods as well as corn gluten feed. Both the northeastern softwood and the corn gluten feed are high in 6-carbon sugars such as glucose and mannose which we found to be more readily converted to Itaconic acid during fermentation by Aspergillus terreus than the 5-carbon sugars such as xylose and arabinose. Figure 1. Laboratory and Pilot Scale Extraction Reactors (not shown) Findings/Conclusions Sugars are readily removed by extracting biomass with either water or dilute acid. Depending upon the final pH of the extract, the sugars are removed in the polymeric (or macromolecular form) and as simple sugars. An attractive biomass material evaluated as a possible carbohydrate source was never-dried corn gluten feed which could be readily extracted with dilute acid. These conditions result in raw extracts with high concentrations of 6-carbon sugars, predominately glucose and mannose. During the extraction and hydrolysis processes, substances are formed in the extract such as soluble lignin, acetic acid, and furfural that are toxic to Aspergillus terreus. Thus, to use the extract as a source of sugars these substances must be removed by purification of the extract.

PUBLICATION INFORMATION: 2010-09-01 TO 2011-08-31
No publications reported this period

PROJECT CONTACT INFORMATION
NAME: Durant Yvon
PHONE: 603-988-9354
FAX: 603-617-4581