Source: MISSISSIPPI STATE UNIV submitted to NRP
CATALYTIC CONVERSION OF BIOMASS-DERIVED CARBOHYDRATES TO GREEN FUELS AND CHEMICALS USING A NOVEL COST-EFFECTIVE NANOCATLYSTS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
ACTIVE
Funding Source
AFRI COMPETITIVE GRANT
Reporting Frequency
Annual
Accession No.
1031564
Grant No.
2024-67021-42038
Cumulative Award Amt.
$610,759.00
Proposal No.
2022-08626
Multistate No.
(N/A)
Project Start Date
Apr 1, 2024
Project End Date
Mar 31, 2027
Grant Year
2024
Program Code
[A1511]- Agriculture Systems and Technology: Nanotechnology for Agricultural and Food Systems
Recipient Organization
MISSISSIPPI STATE UNIV
(N/A)
MISSISSIPPI STATE,MS 39762
Performing Department
(N/A)
Non Technical Summary
At present, we heavily depend on finite petroleum resources for our fuels and chemicals. It is estimated that over 90% of all the energy consumed worldwide, particularly in transportation, comes from fossil fuels like oil, coal, and gas. Considering the diminishing petroleum supplies, fluctuating prices, and growing concerns about the environment, finding alternatives becomes crucial. Producing fuels and chemicals from biomass and agricultural byproducts can play a pivotal role in reducing our reliance on fossil fuels, addressing energy shortages, and being more environmentally sustainable. It offers tangible benefits for the general public, including reducing our dependence on fossil fuels, which could lead to more stable and affordable fuel and product prices. It can also contribute to cleaner air and a healthier environment, translating into improved public health and overall quality of life. By making use of millions of tons of biomass that would otherwise go to waste from farming and forestry activities, we could potentially replace a significant portion of our transportation fuel with more sustainable alternatives by the year 2030.This project's aim is to utilize nanotechnology to create innovative catalysts that can efficiently transform cheap biomass into useful substances which can be used as building blocks for fuels and chemicals. The project's approach involves creating and optimizing the nanocatalysts, refining conversion processes, and exploring the potential of furan-based chemicals as biofuel additives. These chemicals, derived from sugars present in the biomass, can serve as starting points for a wide range of valuable products, from plastics and adhesives to flavorings and biofuels. Ultimately, this research could lead to a significant reduction in fossil fuel dependence, greater energy sustainability, and economic benefits for both rural areas and the nation as a whole.
Animal Health Component
70%
Research Effort Categories
Basic
10%
Applied
70%
Developmental
20%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
12306502000100%
Knowledge Area
123 - Management and Sustainability of Forest Resources;

Subject Of Investigation
0650 - Wood and wood products;

Field Of Science
2000 - Chemistry;
Goals / Objectives
This proposal aims to achieve several goals: reduce U.S. dependence on non-renewable petroleum, enhance energy security, facilitate the shift to a low-carbon economy, and create a new income source for forest-rich regions and farmers by making agricultural and forest residues more economically viable. The long-term objective is to expand the application of nanotechnology in the production of green fuels and chemicals from biomass through the development of novel nanocatalysts for efficient conversion processes. The team proposes to convert agricultural and forest-residue-derived carbohydrates into furfural, 5-hydroxymethylfurfural (HMF), and 1,2-diols (such as 1,2-pentanediol and 1,2-butanediol) by using novel cost-effective and efficient multifunctional bimetallic magnetic nanocatalysts. Furthermore, the team proposes to use the same nanocatalysts for the conversion of furfural and HMF into high-value chemicals and biofuel additives, such as 5-(alkoxymethyl) furans (AMFs), 5-alkoxymethylfurfuryl alcohol (AMFAs), and 2,5-bis(alkoxymethyl) furans (BAMFs). The following supporting objectives will be accomplished in pursuit of the project goals and the long-term objective: 1) preparation and characterization of different novel multifunctional bimetallic magnetic nanocatalysts; 2) production of furfural and diols from biomass hydrolysate sugars (xylose and arabinose) and optimization of the conversion processes; 3) production of HMF from cellulose and optimization of the conversion processes; and 4) production of different furan based chemicals and biofuel additives from furfural and HMF and optimization of the conversion processes.
Project Methods
The following methodologies will be used to perform the proposed activities:Threecost-effective bimetallic magnetic nanocatalysts (NiO-Fe3O4/SiO2,CuO-Fe3O4/SiO2, and ZrO-Fe3O4/SiO2) will be prepared according to the standard published methods. The prepared catalysts will be characterized using different analytical techniques such as FTIR, XRD, TGA, HRTEM/EDX, XPS and surface analysis.Hydrothermal treatment of agricultural residues such as corn Stover to extract the hydrolysate (xylose and arabinose) will be conducted in450 mL high-pressure Parr batch reactor 5500 series (Parr Instrument Company, Moline, IL). The process will be performed at different temperatures (160-180°C) and time range (15- 75 mins) with constant stirring at 500 rpm. After ending of theexperiment, the resulting hydrolysate will be filtered to remove the solid (cellulose and lignin) residues. Response Surface Methodology (RSM) will be applied to optimize the hydrothermal pretreatment process. Lignin will be isolated from cellulose fraction, then cellulose will bedried for 12 h and hydrolyzed with the sulfonic acid functionalized silica nanocatalyst (SiO2-SO3H) to produce glucose. The reaction will proceed at different conditions of temperature (130- 150 °C), time (4- 8 hrs), and cellulose to catalystratios (1:2 - 2:1) with constant stirring at 500 propitiation of the cellulose hydrolysis process to glucose will be performed using the Response Service Methodology(RSM) as well.The conversion of hydrolysate to furfural will be performed by mixing different ratios of MIBK and hydrolysate (3:1- 5:1)with the nanocatalysts in a 100 mL Parr reactor. The concentrations of the nanocatalysts will be varied between 25-75 wt% of xylose concentration in the biphasic system. The reactor will be heatedat different temperatures (100-150 oC)and time range (6- 24 hr) with constant stirring at 500 rpm. After each run, the magnetic catalyst (NiO-Fe3O4/SiO2) will be removed from the reaction mixture by a magnet and the biphasic solution will be filtered with Whatman 42 filter paper to separate the sulfonated silica nanoparticles (SiO2-SO3H) from the solution. The filtered biphasic solution will be poured into a measuring cylinder to determine the volume of both organic and aqueous layers. The two layers will be separated by using a separating funnel and filtered again with a 0.2 µl syringe nylon membrane (Millex-GN). Optimization of the furfural production process will be the Response Service Methodology(RSM).Production of diols from biomass hydrolysate will proceed through the hydroxyketones as follows. Biomass hydrolysates will be produced under flow conditions using dilute sulfuric acid. The hydrolysate will be hydrotreated under acidic conditions using a Ni/Beta catalyst that gives high yields of 1-hydroxy-2-pentanone along with hydroxy-2-propanone and 1-hydroxy-2-butanone. This solution of hydroxyketones will then be hydrogenated to the analogous diols. The second hydrogenation step will initially be performed at different temperatures (160-180 °C), time (1-4 hrs), and catalyst loading (2-8 wt%) using activated carbon modified with Ni and Fe to enhance carbonyl hydrogenation while reducing hydrogenolysis chemistry.All statistical methods and calculations will be performed using the Response Service Methodology (RSM).Conversion of glucose solution to HMF and analysis of the products will be performed similar to the activity 3a. Degradation of HMF into levulinic acid and other byproducts will be the major pitfall in this step. All statistical methods and calculations will be performed using the Response Service Methodology (RSM).One-pot hydrogenation and etherification experiments of furfural (activity 5a) or HMF (activity 5b) will be conducted in a 100 mL cylindrical stainless-steel reactor (Parr, USA) connected to an external temperature, pressure, and stirring controllers. Furfural or HMF (50 mg) will be hydrogenated and etherified by dissolving the bimetallic magnetic nanocatalyst (25 - 100 mg) in 15 mL n-alcohol in the pressure reactor. The reactor will then be sealed and purged with nitrogen (N2) gas for 1 min, and then the reactor will be pressurized with nitrogen gas to 300 psi. Then, the reactor controller will be adjusted at a speed of 500 rpm and heated to a known temperature (150°C - 200°C) and time (4 -12 h). At the end of the experiment, the reaction will be terminated by immersing the reactor in ice-water bath. Then, the catalyst will be separated by external magnet and the product solution will be filtered to remove any solid particles. Identification of the products will be determined by GC/MS analysis. A Hewlett Packard 5971 series mass spectrometer connected with fused silica capillary column (VF-Xms, Agilent technologies, Inc.) with dimensions of (30 m × 0.25 mm ID × 0.25 μm film thickness) will be used in this study. The initial column temperature (40 oC) will maintained for 1 min, and then, the column temperature will be programed at a heating rate of 5 oC/min to 205 oC and hold at 205 oC for 1 min. Both injector and detector temperatures will be adjusted at 280 °C and Helium carrier gas with 99.99% purity will be used. The m/z values, which represent the fragment ions of the compounds, will recorded for each compound. 1 µL of each sample will be injected in the column and the concentration of all chemicals in the mixture will be calculated based on standard calibration curve obtained with standard prepared solutions. All statistical methods and calculations will be performed using the Response Service Methodology (RSM).

Progress 04/01/24 to 03/31/25

Outputs
Target Audience:The target audiences I reached throughout the project are: Research institutions and Universities Graduate and undergraduate students Agricultural technology companies focused on producing green fuels and chemicals. Individuals interested in food systems and sustainable bioproducts Changes/Problems:No changes or problems were encountered during the first year, so there were no delays that could significantly impact the expenditure rate. What opportunities for training and professional development has the project provided?The project provided an opportunity for training for one Ph.D. graduate student and one postdoctoral researcher who was recently promoted to Assistant Research Professor. Their work on the project dramatically enhanced their skills and abilities to help others achieve greater proficiency. How have the results been disseminated to communities of interest?No, the results and knowledge gained from this project have not yet been shared with communities of interest. What do you plan to do during the next reporting period to accomplish the goals?We plan to complete the following activities: Activity 3a- Production of furfural from hydrolysate sugars and optimization of the process, Activity 3b- Production of diols and triols from hydrolysate sugars, Activity 4: Production of HMF from glucose and optimization of the process. We also plan to start working on the following activities: Activity 5a: Conversion of furfural into different biofuel additives and process optimization. Activity 5b: Conversion of HMF into different biofuel additives and process optimization. We plan to publish two or three manuscripts and present our findings at domestic and international conferences.

Impacts
What was accomplished under these goals? During this period, we synthesized and characterized three different cost-effective bimetallic magnetic nanocatalysts: (NiO-Fe3O4/SiO2), (Co3O4-Fe3O4/SiO2), and (ZrO2-Fe3O4/SiO2). We conducted hydrothermal pre-treatment of corncob biomass to extract hydrolysate sugars (glucose, xylose, galactose, arabinose, and mannose), followed by acidic hydrolysis. We also started producing furfural from hydrolysate sugars and optimizing the process. The following major activities were completed. Activity 1: Preparation and characterization of the bimetallic magnetic nanocatalysts Preparation of SiO2 nanoparticles: 27.6 mL of ammonia, 16.4 mL of water, and 156.3 mL of methanol were added to a conical flask and stirred together for 5 minutes. Then, 36 mL of TEOS (tetraethyl orthosilicate) was mixed with 164 mL of methanol in another flask and added dropwise to the ammonia solution while maintaining constant magnetic stirring at room temperature for 24 hours. After that, the solution was sonicated for 30 minutes at 35 ?, and the colloidal solution was filtered and washed with methanol three times to remove excess ammonia; it was then dried in an oven at 100 ? for 2 hours. Preparation of sulfonic acid (SiO2-SO3H-S) and chlorosulfonic acid (SiO2-SO3H-Cl) silica nanocatalyst: A sulfonic acid functionalized silica (SiO2-SO3H-S) nanocatalyst was prepared by adding 0.5 g of silica nanoparticles to a 100 mL round-bottom flask. Then, 10 mL of H2SO4 was added and heated at 140 ? for 20 hours. After completion, the sulfonated sample was washed with deionized (D.I.) water, filtered, and dried in an oven. Chlorosulfonic acid functionalized silica (SiO2-SO3H-Cl) nanocatalyst was prepared by adding 0.5 g of silica nanoparticles to a 100 mL round-bottom flask. Subsequently, 5 mL of chlorosulfonic acid (HSO3Cl) was added dropwise at room temperature for 30 minutes. The mixture was shaken for an additional 30 minutes after completion. The SiO2-SO3H catalyst was then washed with ethanol and dried overnight. Preparation of cost-effective bimetallic magnetic nanocatalysts (ZrO2-Fe3O4/SiO2), (Co3O4-Fe3O4/SiO2), and (NiO-Fe3O4/SiO2) To prepare the (Co3O4-Fe3O4/SiO2) catalyst, 1.2 g of silica nanoparticles and 100 mL of deionized water were added to a 200 mL beaker and sonicated for 1.5 h at 50 ?. Next, 1.98 g of Co(NO3) 2·6H2O and 2.898 g of Fe(NO3) 3·9H2O were dissolved in 50 mL of deionized water, sonicated for 5-10 min at 40 ?, and then slowly added to the silica solution with continuous stirring. The Co3O4-Fe3O4/SiO2 catalyst solution was sonicated for one hour at 80 ?, then covered with aluminum foil and placed in an oven at 80 ? overnight. The dried mixture was transferred into a crucible and placed in a muffle furnace at 550 ? for five hours. The Co: Fe: SiO2 percentages were 20%, 20%, and 60%, respectively. The prepared bimetallic magnetic nanocatalyst was stored in a closed vial for further use. The other two catalysts ZrO2-Fe3O4/SiO2 and NiO-Fe3O4/SiO2 were prepared using the same method mentioned above but using different salt weights (1.413g of ZrOCl2·8H2O + 1.936 g of FeCl3·6H2O) and (1.982 g of Ni(NO3) 2·6H2O + 2.898 g of Fe(NO3) 3·9H2O). The metal (Zr, Co, or Ni): Fe: SiO2 ratios were kept constant (1:1:3) in all the prepared catalysts. Characterization of the prepared nanocatalysts The characterization of SiO2-nanoparticles, SiO2-SO3H-S, SiO2-SO3H-Cl nanocatalysts, and bimetallic magnetic nanocatalysts was performed to study the physicochemical characteristics of the prepared catalysts. The functional groups were analyzed by using FTIR spectrometer (Thermo Scientific Nicolet IS50) in the range from 400 to 4000 cm-1. FTIR spectra of the three prepared nanocatalysts ZrO2-Fe3O4/SiO2, NiO-Fe3O4/SiO2, and Co3O4-Fe3O4/SiO2 show two weak absorption peaks at 2975 cm-1 and 1634 cm-1, which are due to OH bending and stretching vibrations of absorbed water on the silica surface. High intensity broad peak at 1076 cm-1 and sharp peak at 454 cm-1 indicate Si-O-Si asymmetric stretching and O-Si-O bending vibrations, respectively. The peak at 559 cm-1 represents Fe-O bending vibrations. The thermal stability of the prepared catalysts was studied using the thermogravimetric analyzer (SDT Q600 series) at a heating rate of 10 ?/min, from 25? to 800 ?, under a nitrogen atmosphere. The obtained chromatogram represented the weight loss of the catalyst within the following temperature ranges: 25-150 ? for moisture loss, and 250-350 ? for the decomposition of organic compounds. For ZrO2-Fe3O4/SiO2 catalyst, no loss occurred after 350 ?, indicating the stability of ZrO2. In the case of NiO-Fe3O4/SiO2, weight loss occurs in the temperature range of 500-600 ? due to the reduction of NiO to Ni metal. For the Co3O4-Fe3O4/SiO2 catalyst, Co3O4 was reduced to CoO around 500-600 ?, and CoO is further reduced to Co metal above 600 ?. X-ray photoelectron spectroscopy (XPS) analysis was performed using the Kratos Axis Ultra X-ray photoelectron spectrometer to assess the prepared material's surface's elemental composition and chemical state. The study of XPS indicates all three bimetallic nanocatalysts (ZrO2-Fe3O4/SiO2, NiO-Fe3O4/SiO2, and Co3O4-Fe3O4/SiO2) surfaces consisted of the Metal (zirconium, Nickel, and Cobalt), Iron, Oxygen, Carbon, and Silicon. The textural properties of the catalysts, including pore size distribution and surface area, were analyzed using nitrogen adsorption-desorption isotherms. The BET and BJH methods were employed to determine these characteristics for silica nanoparticles and all catalysts. The adsorption isotherms exhibited a typical type III pattern, confirming the non-porous nature of the prepared nanocatalyst. The results of BJH-derived values for surface area, pore size, and pore radius were determined. XRD is used to determine the composition and crystallinity of the synthesized NiO-Fe3O4/SiO2, ZrO2-Fe3O4/SiO2, and Co3O4-Fe3O4/SiO2 bimetallic nanocatalysts. The observed diffraction peaks indicated the presence of a crystalline structure in all prepared catalysts. Activity 2a: Hydrothermal treatment and extraction of the biomass hydrolysates. The corncobs biomass was mixed with deionized water in various ratios (5, 10, and 15g biomass per 100 mL H2O) and transferred to 450 mL high-pressure Parr batch reactor 5500 series (Parr Instrument Company, Moline, IL). The reactor was purged with nitrogen to eliminate air and heated to different temperatures (150, 160, and 170 ?) for varying times (30, 60, and 90 min) at a constant stirring speed of 500 rpm. Twenty-seven experiments were conducted to optimize the hydrothermal pretreatment step for preparing hydrolysate from corncobs. The concentrations of sugars (glucose, xylose, galactose, arabinose, and mannose) before and after acidic hydrolysis were determined using high-performance liquid chromatography HPLC. The concentrations of HMF and furfural before and after acidic hydrolysis were also determined using an HPLC instrument. Response Surface Methodology (RSM) was employed to optimize hydrothermal pretreatment. The Box-Behnken design (BBD) was utilized to explore optimal experimental conditions for maximizing the yield of xylose and arabinose. Activity 3a: Production of furfural from hydrolysate sugars Hydrolysate was converted to furfural by mixing different ratios of corcobs hydrolysate with the catalysts in a 100 mL Parr reactor. This work is still under investigation, and the complete results will be published soon and reported next year. Activity 3b: Production of diols and triols from hydrolysate sugars This work is still under investigation, and the results for this activity will be published soon and reported next year.

Publications