Purdue University Graduate School
Overton Dissertation.pdf (2.09 MB)

Maleic acid as a versatile catalyst for biorefining

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posted on 2021-10-12, 14:59 authored by Jonathan Christopher OvertonJonathan Christopher Overton

Producing bio-based commodity chemicals, such as polymers and fuels, is of significant interest as petroleum reserves continue to decline. A major roadblock to bio-based production is high processing costs. These costs are associated with the need for highly-specialized catalysts to produce bio-based commodity chemicals from agricultural products and wastes. This prevents bioprocessing facilities from fully taking advantage of commodities of scale, where purchasing materials in greater quantities reduces the material cost. Discovering catalysts capable of being used in multiple production pathways could reduce the per unit processing of a biorefinery.
Recent works have shown that maleic acid can be used for multiple conversion reactions of plant material to valuable products: xylose to furfural, glucose to hydroxymethylfurfural (HMF), and the pretreatment of lignocellulosic material for second generation biofuel production. This work evaluates the use of maleic acid as a catalyst for producing HMF from corn starch, with a specific focus on reducing operating costs. Additionally, the use of maleic acid as a liquefaction catalyst for producing corn stover slurries is tested.

To evaluate HMF production from starch, a combined computational and experimental approach is used. Through modelling and experimental validation, molar HMF yields of ~30% are reached by incorporating dilute dimethylsulfoxide and acetonitrile into the reaction mixture. However, HMF yield was limited by low stability in the reaction media. The addition of activated carbon to the reactor overcomes challenges with second order side reactions, resulting in HMF selling prices that are competitive with similar petroleum-derived chemicals. The key technical roadblocks to commercialization of HMF production are identified as solvent recycling and HMF separation efficiency in a sensitivity analysis. During liquefaction of corn stover, maleic acid was found to reduce the yield stress required to begin slurry flow through a pipe. However, a reduction in the free water content of the reactor through binding of water in the matrix of biomass limited liquefaction, resulting in solids concentrations not financially feasible at scale. To overcome this, maleic acid treatment was performed at solids contents of 25%, followed by a water removal step and enzymatic liquefaction at 30% solids. Yield stress was reduced from >6000 Pa for untreated samples to ~50 Pa for samples treated with maleic acid and enzymes sequentially. Such treatment reduces the challenges associated with feeding solid biomass into a pretreatment reactor. Additionally, reduced slurry yield stress results in lower capital costs, since smaller pumps can be used in the production facility.

This work provides a step forward in transitioning away from a petroleum-based economy to a bio-based economy without significant disruptions in product pricing and availability.


Degree Type

  • Doctor of Philosophy


  • Agricultural and Biological Engineering

Campus location

  • West Lafayette

Advisor/Supervisor/Committee Chair

Nathan S. Mosier

Additional Committee Member 2

Abigail Engelberth

Additional Committee Member 3

Eduardo Ximenes

Additional Committee Member 4

Jeffrey Miller