Synthesis and Characterization of Inorganic Sorbents, Beads, Polymer Resins, and Biosorbents; Inorganic Sorbent Bead Platform Technologies; Sorbent-based Separation Processes

The existing BETO-funded program laid some ground work on new sorbent materials and process development. The novel materials-based sorbents become a keystone to further advance of sorptive separation technologies and provide support to the mission applications of the separations consortium. The sorbents capability supports the consortium tasks in organic acid carbon recovery, in improving the bio-oil feedstock for upgrading (carbonyl removal and de-nitrogenation), and in preserving catalysts. 

Capability Title Synthesis and Characterization of Inorganic Sorbents Beads, Polymer Resins, and Biosorbents;  Inorganic Sorbent Bead Platform Technologies; Sorbent-based Separation Processes
Laboratory  Oak Ridge National Laboratory (ORNL)
Capability experts Michael Z. Hu (hum1@ornl.gov), Rodney Hunt, Jack Collins, and Mi Lu
Description

ORNL has the unique capability in synthesis production of inorganic sorbent beads via internal and external gelation processes. The inorganic beads can be made to be nanoporous or mesoporous oxides so that large specific surface areas can be achieved. The composition of inorganic beads ranges from oxides, carbides, sulfides, and their mix. We can molecularly functionalize the surfaces and inner pore surfaces of the inorganic beads.  Many other active ingredients (in the powder or molecular form) can be also dispersed, encapsulated, immobilized, or embedded inside the platform inorganic beads. These uniform sized spherical beads (typically 0.1-10 mm in diameter) can be easily packed into a fixed bed for process characterization (adsorptive separations and regenerations). The inorganic sorbents are mechanically strong and particularly good to tolerate high-temperature thermochemical processing/separation conditions

Secondly, ORNL has the hands-on experience in synthesizing and testing of whole suite of polymer resins and functionalized resins (both self-synthesized and commercial). Besides the in-house capabilities, ORNL has been working with a few major industry companies on evaluating various polymer resins for separations relevant to applications of processing biofuels and bio-products. Examples include weak basic ion-exchange sorbents to selectively remove carbonyl molecules and carboxylic acids from bio-crude oils and aqueous fractions.

Lastly, ORNL has strong expertise in highly selective separations based on the high-affinity biosorbents and unique bio-synthetic hybrid sorbents. Besides biomass-based biosorbents, biomolecules can be encapsulated or grafted in immobilization matrices of oxide beads or polymer beads to serve as hybrid biosorbents, which can separate organic compounds and inorganic mineral/metal ions as well.

Limitations 

No limitation on ORNL’s synthesis capability for different types of sorbents/resins and functionalization: inorganic, polymeric, biogenic, and hybrids (inorganic-polymeric, bio-inorganic, bio-polymer).

Current project application interest is limited to sorption removal of carbonyls and heterocyclic nitrogen compounds from crude bio-oils and aqueous streams. However, we are open to evaluation other new sorbent-based separation applications.

Unique aspects 
  • Legacy ORNL inorganic gel beads (micro spheres) used to remove cesium, strontium, and actinides from nuclear waste; they could be also used for organic or mineral/ions recovery and separations
  • Amine-functionalized silica or polymer sorbents for carbonyl molecular removal
  • Unique bio-polymer hybrid sorbents for mineral/metal ions recovery and separations
Availability 

We make availability to work with industrial partners for either government-funded projects or industry-sponsored projects.

We can evaluate industrial separations problems using ORNL’s in-house bench-scale testing facilities including batch and continuous column sorption separation processes.

We can also fabricate custom sorbents and deliver them to industrial lab for their testing on site for their process separation needs.

Citations/references
  1. Michael Z. Hu*, David W. Depaoli, Tanya Kuritz, and Ogbemi O. Omatete, “Electric-Field-Oriented Growth of Long Hair-Like Silica Microfibers and Derived Functional Monolithic Solids,” Recent Patent on Nanotechnology (NanoTec) 11, 243-251 (2017).
  2. Invention on Sorbent Selective Removal/Reduction of Carbonyls and Carboxylic Acids for Bio-Oil Stabilization and Down-Stream Catalyst Preservation,” Invention Disclosure 201704033, DOE S-138,698, Dec. 14, 2017. Inventors: Michael Z. Hu*, Mi Lu.
  3. Sayan Bhattacharyya, Yitzhak Mastai, Rabi Narayan Panda, Sun-Hwa Yeon, and Michael Z. Hu*, “Advanced Nanoporous Materials: Synthesis, Properties, and Applications,” Journal of Nanomaterials, Article ID275796 (2014).
  4. Michael Z. Hu*, Lubna Khatri, Michael T. Harris, “Preparation of Monodispersed Ultrafine Zeolite Nanocrystal Particles by Microwave Hydrothermal Synthesis”, Ceramic Transactions 208, 89 (2009).
  5. David W. DePaoli, Michael Z. Hu*, Saed Mirzadeh, and John W. Clavier, US Patent “Inorganic Resins for Clinical Use of 213Bi Generators (for targeted cancer therapy),” US 7,914,766 B1, filed 2004-06-03, issued March 29, 2011.
  6. Michael Z. Hu*, “Method for Making Fine and Ultrafine Spherical Particles of Zirconium Titanate and Other Mixed Oxide Systems,” US Patent Application Publication, US7049347, filed 2003-07-18, issued 2006-05-23. 
  7. R.D. Hunt, J.L. Collins, K. Adu-Wusu, M.L. Crowder, D.T. Hobbs, and C.A. Nash.  2005. “Monosodium Titatnate in Hydrous Titanium Oxide Spheres for the Removal of Strontium and Key Actinides from Salt Solutions at the Savannah River Site,” Separation Science and Technology, 40 (14), 2933–2946 (2005).
  8. Michael Z. Hu* and M. Reeves, “Ligand-Grafted Biomaterials for Adsorptive Separations of Uranium in Solution,” AIChE Journal, 45(11), 2333-2345 (1999).
  9. J.-H. Koh, B. S. Broyles, H. Guan-Sajonz, Michael Z. Hu*, and G. Guiochon, “Consolidation and Column Performance of Silica and Alumina Packing Materials for Liquid Chromatography in a Dynamic Axial Compression Column,” Journal of Chromatography A, 813, 223-238, 1998.
  10. Michael Z. Hu* and Mark E. Reeves. “Biosorption of Uranium by Pseudomonas aeruginosa Strain CSU Immobilized in a Novel Matrix,” Biotechnology Progress, 13, 6070 (1997).
  11. Michael Z. Hu*, John M. Norman, Brendlyn D. Faison, and Mark E. Reeves. “Biosorption of Uranium by Pseudomonas aeruginosa Strain CSU: Characterization and Comparison Studies,” Biotechnology and Bioengineering, 51, 237247 (1996).
  12. Y.X., Gu, Z.C. Hu*, and Roger Korus. “Effects of Adsorption on Mass Transfer in Polymeric Immobilization Materials,” The Chemical Engineering Journal & The Biochemical Engineering Journal, 54, B1B8 (1994).
ORNL’s Legacy Synthesis (Internal Gelation Method) for Producing Inorganic Sorbent Beads
Various Inorganic (Oxides) Sorbent Beads Historically and Currently Synthesized at ORNL
ORNL’s Polymer Resins and Biomass-Loaded Sorbent Beads for High-Affinity Separations