Advanced Environmentally Relevant Functionalized Membranes and - - PowerPoint PPT Presentation

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Advanced Environmentally Relevant Functionalized Membranes and - - PowerPoint PPT Presentation

Jul 28, 2023 161 likes •392 views

Advanced Environmentally Relevant Functionalized Membranes and Hybrid Technologies D. Bhattacharyya (DB), Professor, Chemical and Materials Engineering and Director Center of Membrane Sciences Students and Faculty Collaborators : Students: A.

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Advanced Environmentally Relevant Functionalized Membranes and Hybrid Technologies *email: db @uky.edu; phone: 859-312-7790

  • D. Bhattacharyya (DB), Professor, Chemical and Materials

Engineering and Director Center of Membrane Sciences

Students and Faculty Collaborators : Students: A. Saad, H. Wan, M. Detisch, S. Islam, R. Mills, F. Leniz, S. Schwab, R. J. Vogler, Faculty: L. Ormsbee (Civil Eng), Zach Hilt and Isabel Escobar (Chemical Eng),Todd Hastings (Electrical and Computer Eng), Yinan Wei (Biological Chemistry), University of Kentucky, Lexington, KY USA

ZOOM Webinar (for SG Mem) Wednesday, June 24, 8:30 pm (EST USA) 2020

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Some Questions and possible answers

  • Can we use existing membranes to functionalize surface or pore? What benefits?
  • Membranes could be thin or many microns thick, symmetric to asymmetric pores, to

spongy or fingerlike structure; Why waste pore space?

  • How about Adsorptive/ion exchange and recognition -based membranes with

Responsive Properties

  • What can we learn from life sciences field ? Responsive to Biomimetic to Enzymes
  • Water virus (rotavirus in water) vs. corona virus (COVID-19 is about 125 nm)
  • Easy conversion from open structured water filtration membrane to air filtration

membrane (what’s needed)

Integrating knowledge from membrane, environmental, and biological chemistry field

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Membrane Technology (Background)

Dense Membranes

Reverse Osmosis(RO) Forward Osmosis (FO) Pervaporation(PV) Electrodialysis(ED)

Nanofiltration (NF) Ultrafiltration (UF)

Advanced Functionalized Membranes: Responsive and Adsorptive Membranes, Catalytic-Nanoparticles, Bioinspired, GO-GQD

How about extension to PPE Materials (such as Mask)?

CDI, EDI, MD, SLM, etc.

Microfiltration (MF)

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4

Automated cross-flow NF and Functionalized MF membranes System (4 cross flow cells, one spiral module) with temperature control, etc.)

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5

Fast throughput Membrane Solute PERMEABILITY ANALYSIS

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Hybrid Water Treatment/Reuse Scenarios for Power Plant FGD Water and Converting Retentate to solids (joint work with Southern Company, Birmingham, AL)

Iron (Fe/FexOy) Functionalized PVDF Membrane Positively charged NF for Selective Sep

FGD water

TDS (Ca2+, Mg2+, Na+, Cl-, SO4

2-)

and lselenate High Pressure RO

Recycle to FGD unit (A) (B) (C)

TDS Se<10ppb Permeate with low Ca2+, Mg2+) Retentate

Positively-charged NF Iron (Fe/FexOy) Functionalized PVDF Membrane

FGD water

Permeate Recycle to FGD unit (B) (A)

Retentate

Crystallizer, Spray Drying

(D)

(1) (2)

TDS (Ca2+, Mg2+, Na+, Cl-, SO4

2-)

and selenate

Need Total Solution

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Functionalization of Porous membranes with Polyelectrolytes/Polypeptides (metal capture to adsorptive to reactive membranes)

Me

2+

Me

2+

Me

2+

Me

2+

Me

2+

Me

2+

Helix Random Chain Ion Exchange Chelation Electrostatically Bound

Note: conformation change (helix-coil)

++ + + + + + + + + + + + + + + + + + + + + + +

LBL assembly in pores

Stacked Membranes

Ultra high capacity metal capture

Porin Channels Nanoparticle

Learning from life sciences field

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SLIDE 8

100 200 300 400 500 600 700 5 10 15 20 25 30

Pure water flux, Jw (L/m2 h) Time (min)

200 400 600 800 1000 1200 1400 1 2 3 4 5 6 7 8 9 10

Pure water permeability, A (L/m2 h bar) pH

(A) (B)

3.0 5.5 7.3

ΔP=0.48 bar

pH 3.0 5.5 7.3 3.0 5.5

pH responsive flux for Full-scale PVDF400HE- PAA Membranes (Sepro/Solecta, Oceanside, CA)

Compact state

PAA

Ionized state

  • OOC

COO- COO- COO- COO-

  • OOC
  • OOC
  • OOC

Na+ Na+ Na+ Na+ Na+ Na+ Na+ Na+

  • M. Gui, L. Ormsbee and D. Bhattacharyya.

Special issue honoring Enrico Drioli, I&EC Res. May, 2013

  • J. Membrane science (2015)
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≈ 1.2 x 0.7 nm

Converting commercial 0.1 micron PVDF MF membrane pores to Nanochannel Membranes: Selective small molecule Separations

Hernandez, Cassandra Porter, Zhang, Wei, Bhattacharyya, RSC Advances (2017) Functionalizing Solecta PVDF MF membranes with precise channels to remove low MW valuable organics Can we make nanochannel Membranes from commercial PVDF to remove low MW organics but not salts!!

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30

High value metal recovery and toxic Metal Sorption by Thiol Functionalized Membrane Pores

Membrane Adsorption Bed >> conventional ion exchange ; Joint work with Chevron

  • No pore diffusion issues
  • Convective flow
  • High dynamic capacity
  • > 90% sorption site utilization
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36

Hybrid Treatment of Industrial Process Water containing toxic Metal Sulfide Nanoparticles and dissolved Hg by MF-UF-Thiol Functionalized Membrane

Extremely high efficiency With thiol funcionalized PVDF membranes

We have also demonstrated Very high efficiency Silver Recovery from water

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PNIPAm (Poly(N-isopropylacrylamide) Functionalized Responsive Membranes and hydrogels for temperature swing perfluoro-

  • rganics Sorption/desorption

(Emerging Pollutants in water)

Saad, A., Mills, R., Wan, H., Mottaleb, MA., Ormsbee, L., & Bhattacharyya, D.

  • J. Membrane Science (January 2020)

US Patent Pending, 2020, Bhattacharyya, Saad, et al

PFOA:

Converting lower value MF membranes to high value temperature responsive separations

Why not carbon Adsorption? High T regeneration and Corrosive gas potential

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Temperature Responsive Polymer Sorption/desorption applications

PNIPAm

  • LCST behavior
  • Controllable LCST value
  • Controlled flux
  • Gating character
  • Conformational changes

T < LCST T > LCST Hydrophilic functional group of PNIPAm Hydrophobic functional group of PNIPAm Hydrophobic contaminant (PFOA, PFOS) Water

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pNIPAM Hydrogel-Based PFOA Adsorption/Desorption

Adsorption and desorption kinetics of PFOA onto PNIPAm hydrogels (15wt% NIPAm, 3 mol% BIS crosslinker, 2 mol% APS) in water.

10 20 30 40 50 60 5 10 15 20 25 30

PFOA Adsorbed (mg/g) Time (hrs) Desorption Adsorption PSO Desorption Model PSO Adsorption Model

50 20 40 60 80 100 PFOA Adsorbed (mg/g) Time (minutes) Adsorption Desorption

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PFOA sorption-desorption from water over multiple cycles: Temp Responsive PVDF membranes Pressure= 3.5 bar

Membrane Water Permeability Sorption Above LCST Desorption below LCST

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Direct Synthesis of catalytic nanoparticles in membranes (Take advantage of MF pores)

Polyacrylic acid (PAA) Functionalized Membrane Fe0 Iron Oxide (FexOy)

PA A PA A H2O2/Persulfate Oxidation potentials: OH•: 2.7 V SO4-•: 2.6 V

Reduction (NaBH4

  • r polyphenols)

16

Fe/Pd

  • COONa
  • COOH

Na+ Fe2

+

Fe2+

e-

H2O RH + Cl-

Fe0

Pd0 H2 H* RCl

Fe2O3 Fe3O4 OH• H2O2

Reductive pathway Oxidative pathway PCB s TCE Model compounds

COO- COO- Fe2+ Fe2+ Fe0 FexOy

L-Fe2+/Fe3+

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 10 20 30 40 50 60

[Biphenyl]/[Biphenyl]max [PCB]/[PCB]0 Residence Time (s)

2-Chlorobiphenyl Biphenyl Carbon balance

Mass (Fe)=6.1 mg (size: 80 nm, ρm=58.5 g/L), Pressure varied between 5 and 11 bar. Membrane external area: 13.2 cm2. Pd loading: 0.9 wt% 0f Fe, [PCB]0= 31 µM, pH=7.5-8.0

Gui, Bhattacharyya, et al, JMS (2015); Hernandez, Orsmbee, Wang, Bhattacharyya, ACS journal on Sustainable Chemistry and Engineering (2016); Wan, et al, JMS (2020) One can use MF membrane pores to synthesize highly controlled size Nanoparticles or directly use it for catalysis

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Functionalized Membranes/enzymes/biomolecules to Corona Virus PPE and surface disinfection approaches

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In situ generation of H2O2 (LbL assembly of Glucose oxidase enzyme) to oxidize pollutants or detoxify a surface by hydroxy radicals

Lewis, Datta, Gui, Huggins, Daunert, Bachas,

  • Bhattacharyya. PNAS (2011)

Stacked-Nanocomposite Hybrid Membranes

GOX enzyme in LbL assembly

Fe(II, III) or Iron Oxide Nanoparticles

Is it possible make dilute hydrogen peroxide directly in a membrane mat Or even in a porous sponge (we just need small amount sugar and an inexpensive Enzyme?) Glucose oxidase enzyme

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SLIDE 19

Binding between CoV spike protein to human cellular receptor ACE2. (Ref: Vaduganathan, M., et al, Renin–Angiotensin– Aldosterone System Inhibitors in Patients with Covid-19. New England Journal of Medicine, 2020.

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Other approaches include very thin surface coating of 2D thin layer of GO Or lignin-sulfonate based materials on existing mask

Air Air

virus in droplets 0.5-2 µm virus in aerosols 120-130 nm

deactivated virus enzyme

  • uter layer

inner layer

Membrane functionalized enzyme/antibody

Functionalized Membrane Mask Approach Ex enzyme Subtilisin is a protease (a protein-digesting enzyme) Our Lab data: 0.1 micron pore PVDF 400 membrane Air Flow=37,000 LMH/bar Water Flow = 417 LMH/bar For a mask: 100 liter/hr air flow even at 0.1 bar

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  • NIH-NIEHS –SRC program
  • NSF- EPSCoR program; NSF-EAGER
  • NSF RAPID (Corona Virus Mask and Enclosed space air filtration)
  • Southern Co.
  • Chevron Corp
  • Dr. Scott Lewis, Dr. S. Hernandez, Dr. V. Smuleac, Doug Davenport, Dr.

Xiao, Dr. Gui, Dr. Colburn, Dr. Sikdar (US EPA), Ben Weaver, Solecta Membranes, Dr. Evan Hatakyama, Chevron co.

Acknowledgement

NIH-NIEHS-SRC