<<  Religious Studies 2812: Religion and Popular Culture Renault z.e. decouverte renault zoe  >>
Removing Heavy Metals from Water: Self-Assembled Monolayers on
Removing Heavy Metals from Water: Self-Assembled Monolayers on
Collaborators
Collaborators
Clean Water
Clean Water
Advantages of nanomaterials for heavy metal separations
Advantages of nanomaterials for heavy metal separations
Self-assembly is the spontaneous, ordered, organized assembly of
Self-assembly is the spontaneous, ordered, organized assembly of
Examples of self-assembly in Nature
Examples of self-assembly in Nature
A brief history of synthetic self-assembly
A brief history of synthetic self-assembly
Similar self-assembly forces contribute to micelle formation
Similar self-assembly forces contribute to micelle formation
Nanoporous Ceramic Substrates
Nanoporous Ceramic Substrates
Nanoporous Ceramics Substrate
Nanoporous Ceramics Substrate
So the way that we get the surface chemistry we need is
So the way that we get the surface chemistry we need is
SAMMSTM: Self-Assembled Monolayers on Mesoporous Supports
SAMMSTM: Self-Assembled Monolayers on Mesoporous Supports
SAMMSTM in a Nutshell
SAMMSTM in a Nutshell
Global Mercury Emissions
Global Mercury Emissions
Thiol-SAMMS overview
Thiol-SAMMS overview
Mercury Adsorption Kinetics: Thiol SAMMS
Mercury Adsorption Kinetics: Thiol SAMMS
TCLP Data for Hg-loaded thiol-SAMMS
TCLP Data for Hg-loaded thiol-SAMMS
Actual Hg waste clean-up
Actual Hg waste clean-up
INL/SES demonstration/deployment
INL/SES demonstration/deployment
The well had been treated using carbon type adsorbents to remediate
The well had been treated using carbon type adsorbents to remediate
Case Study 1: Results of 10 gpm Field Test on Well Water
Case Study 1: Results of 10 gpm Field Test on Well Water
Case Study 2: 10 gpm Field Test on Well Water with High Concentration
Case Study 2: 10 gpm Field Test on Well Water with High Concentration
Case Study 2: 10 gpm Field Test on Well Water with High Concentration
Case Study 2: 10 gpm Field Test on Well Water with High Concentration
Case Study 3: SAMMS for Mercury Reduction to Ultra Low Concentration:
Case Study 3: SAMMS for Mercury Reduction to Ultra Low Concentration:
Case Study 3: SAMMS for Mercury Reduction to Ultra Low Concentration:
Case Study 3: SAMMS for Mercury Reduction to Ultra Low Concentration:
Overview of different flavors of SAMMS chemistry
Overview of different flavors of SAMMS chemistry
Arsenic in Drinking Water Supplies
Arsenic in Drinking Water Supplies
The Anion Problem
The Anion Problem
Cu-EDA SAMMS Mechanism
Cu-EDA SAMMS Mechanism
Tailoring SAMMS to bind cesium
Tailoring SAMMS to bind cesium
Cesium SAMMS Summary
Cesium SAMMS Summary
Ligand Design Strategy for Actinide SAMMS
Ligand Design Strategy for Actinide SAMMS
Actinide-specific ligand synthesis
Actinide-specific ligand synthesis
Summary of Actinide SAMMS Studies
Summary of Actinide SAMMS Studies
Tailoring SAMMSTM interfacial chemistry to the periodic table
Tailoring SAMMSTM interfacial chemistry to the periodic table
Life-cycle considerations
Life-cycle considerations
Commercializing SAMMS
Commercializing SAMMS
Steward Environmental Solutions
Steward Environmental Solutions
Perry Equipment Corp
Perry Equipment Corp
SAMMSTM  Current Applications
SAMMSTM Current Applications
Functional nanomaterials can make analytical tools faster, more
Functional nanomaterials can make analytical tools faster, more
Functional nanomaterials enhance analytical sensitivity/selectivity
Functional nanomaterials enhance analytical sensitivity/selectivity
SAMMS enhances electrochemical detection of heavy metals
SAMMS enhances electrochemical detection of heavy metals
Summary
Summary
Removing Heavy Metals from Water: Self-Assembled Monolayers on
Removing Heavy Metals from Water: Self-Assembled Monolayers on
Extra slides
Extra slides
Mercury Emissions
Mercury Emissions
Electrochemical detection system
Electrochemical detection system
10 gpm unit
10 gpm unit
Run this through ERICA
Run this through ERICA

: Removing Heavy Metals from Water: Self-Assembled Monolayers on Mesoporous Supports (SAMMS). : Staff. : Removing Heavy Metals from Water: Self-Assembled Monolayers on Mesoporous Supports (SAMMS).ppt. zip-: 25553 .

Removing Heavy Metals from Water: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

Removing Heavy Metals from Water: Self-Assembled Monolayers on Mesoporous Supports (SAMMS).ppt
1 Removing Heavy Metals from Water: Self-Assembled Monolayers on

Removing Heavy Metals from Water: Self-Assembled Monolayers on

Mesoporous Supports (SAMMS)

Glen E. Fryxell and Richard Skaggs March 11, 2008 WA Dept. Ecology Olympia, WA Funded by DOE glen.fryxell@pnl.gov

Highlight article JMC 2007.

2 Collaborators

Collaborators

Xiangdong Feng and Jun Liu (early thiol SAMMS) Shas Mattigod, Yuehe Lin, Hong Wu, Sandy Fiskum, Kent Parker, Wassana Yantasee (SAMMS testing) Ken Kemner and Shelly Kelly (EXAFS at ANL) Kenneth Raymond and Jide Xu (UC-Berkeley, HOPO ligands) Tom Zemanian, Oleksiy Ustyugov, Leo Fifield, Rose Galhotra (SCF) Shane Addleman, Tim Bays, Shari Li and Brad Busche (analytical) Jerry Birnbaum, Rob Wiacek (ligand synthesis) Theresa Hauser, Richard Champion (materials synthesis and testing) Richard Skaggs (business development), Jim Toth (crude oil)

3 Clean Water

Clean Water

Clean-up technologies must address a wide variety of targets and needs.

Water quality, and access to clean drinking water, is emerging as one of the global issues of the 21st century.

4 Advantages of nanomaterials for heavy metal separations

Advantages of nanomaterials for heavy metal separations

Nanomaterials provide:

High surface area (capacity) Well defined structure High reactivity Readily tailored for application in different environments, applications

Not all nanomaterials are nanoparticles!

5 Self-assembly is the spontaneous, ordered, organized assembly of

Self-assembly is the spontaneous, ordered, organized assembly of

molecules (or particles), driven by a favorable interaction with an interface and between the components

What is self-assembly?

6 Examples of self-assembly in Nature

Examples of self-assembly in Nature

Micelles and vesicles Cell membranes DNA ?-helix Protein folding

7 A brief history of synthetic self-assembly

A brief history of synthetic self-assembly

Agnes Pockels, first monolayers on the air-water interface (1890s) Langmuir (air-water interface) films (1917) Blodgett (long chain fatty acids on solids) (1930s) Interest in monolayer chemistry was rekindled in the 1980s: Sagiv, Whitesides, Ulman, Nuzzo, Alara, et al. (thiols on gold, and silanes on oxides) Explosion of activity in the 1990s (ribbons, tapes, sheets, etc.)

Excellent reference: An Introduction to Ultrathin Organic Thin Films: From Langmuir-Blodgett to Self-Assembly by A. Ulman; Academic Press; 1991.

8 Similar self-assembly forces contribute to micelle formation

Similar self-assembly forces contribute to micelle formation

Surfactant-Oil-Water Phase Diagram

9 Nanoporous Ceramic Substrates

Nanoporous Ceramic Substrates

Sol-gel

Surfactants R-N+-(CH3)3X-

Template removal

10 Nanoporous Ceramics Substrate

Nanoporous Ceramics Substrate

~5 10 grams

Bigger on the inside than it is on the outside.

Controlled pore channels: 1.5 - 40 nm

Large surface area: ~600 - 1000 m2/g

11 So the way that we get the surface chemistry we need is

So the way that we get the surface chemistry we need is

Molecular self-assembly

Self-assembly driven by Van der Waals interactions between chains, as well as the interaction between the headgroup and the surface.

Monolayer Advantages Well-established silanation chemistry Stabilized surface High ligand density Easily tunable chemistry

Designing Surface Chemistry in Mesoporous Silica in Adsorption on Silica Surfaces; pp. 665-687, Marcel-Dekker, 2000.

Pore Surface

12 SAMMSTM: Self-Assembled Monolayers on Mesoporous Supports

SAMMSTM: Self-Assembled Monolayers on Mesoporous Supports

+

http://samms.pnl.gov/

First reported in: Science 1997, 276, 923-926.

A. Self-assembled monolayers

B. Ordered mesoporous oxide

13 SAMMSTM in a Nutshell

SAMMSTM in a Nutshell

Extremely high surface area = high binding capacity Rigid, open pore structure provides for fast sorption kinetics Chemical specificity dictated by nanopore interface, easily modified for new target species Proximity effects can allow multiple ligand/cation interactions Particle size generally on the order of 50-100 micron (but can be tailored either larger or smaller) Engineered forms (canisters, cartridges, membranes, etc.) Regenerable

Environmental and Sensing Applications of Molecular Self-Assembly in Encyclopedia of Nanoscience and Nanotechnology; Dekker, 2004, pp. 1135-1145.

14 Global Mercury Emissions

Global Mercury Emissions

Recent estimates of total global mercury emissions (per year) from all sources are roughly 6,000 metric tons emitted per year (range from 4,400 to 7,500). These emissions are split into 3 roughly equal parts:

Source: United Nations Environment Programme Global Mercury Assessment, 2002, using J. Pacyna 1995 data, as presented by the Arctic Monitoring and Assessment Programme http://www.epa.gov/mercury/control_emissions/global.htm

15 Thiol-SAMMS overview

Thiol-SAMMS overview

Thiols have high affinity for soft heavy metals (e.g. Hg, Cd, Au, etc.). High Kd values for Hg binding (e.g. 10,000,000). No competition from common ions (e.g. Na, Ca, Fe, etc.). Thiol SAMMS even out-competes a variety of complexants. High saturation binding capacity (as much as 2/3 of its own weight in Hg, depending on conditions).

Journal of Materials Chemistry 2007, 17, 2863 2874.

Mercaptopropyl siloxane monolayer lining the pore surface of mesoporous silica. The mercury (shown in blue) binds to the sulfur atoms (sulfur atoms are shown in yellow).

16 Mercury Adsorption Kinetics: Thiol SAMMS

Mercury Adsorption Kinetics: Thiol SAMMS

GT-73

SAMMS

17 TCLP Data for Hg-loaded thiol-SAMMS

TCLP Data for Hg-loaded thiol-SAMMS

18 Actual Hg waste clean-up

Actual Hg waste clean-up

Case #1

Case #2

Case #3

10L of lab waste (146 ppm Hg) Est. disposal cost $2000 86 g of Thiol SAMMS used (final Hg conc. 0.04 ppm) Treatment cost $180 10-fold reduction in cost.

200L of EVS scrubber waste (4.64 ppm Hg) Est. disposal cost $3400 Thiol SAMMS used (final Hg conc. 0.05 ppm) Est. treatment cost $210 15-fold reduction in cost.

Mixed waste oils (0.8-50 ppm Hg) Thiol SAMMS used (final Hg conc. <0.2 ppm) Only method proven effective in hydrophobic media.

Ref: Klasson et al. 1999, 2000 ORNL

19 INL/SES demonstration/deployment

INL/SES demonstration/deployment

Idaho National Laboratory V-9 Wastes Complex slurry of aqueous, heavy metals, radionuclides (e.g. Cs-137, Co-60, Eu-152), solids, halogenated solvents (TCE, TCA, PCE, etc.), etc. Hg concentration 1.57%, speciation unknown (mixed?) Planning to solidify the waste using Waterworks SP-400 (10% by weight). Problem: Hg still leachable Viable strategy in place for the other hazards, needed the ability to immobilize the Hg in situ such that the final wasteform would pass TCLP. Tests showed that Thiol-SAMMS could effectively immobilize the Hg in place and that the resultant wasteform could pass TCLP by an order of magnitude.

Successfully treated the entire contents of tank V-9 with thiol-SAMMS.

20 The well had been treated using carbon type adsorbents to remediate

The well had been treated using carbon type adsorbents to remediate

mercury but was experiencing frequent adsorbent fouling problems and was unable to meet potential future low mercury reduction targets ? 12 ppt output. The well water contained over twenty inorganic species. Stewards conducted bench testing (batch) and demonstrated SAMMS was able to reduce [Hg] from input ~25 ppb down to ~14 ppt. Steward conducted a field test using 10 gpm SAMMS filtration system with four contactor tanks.

Case Study 1: Well Water Remediation Field Test

21 Case Study 1: Results of 10 gpm Field Test on Well Water

Case Study 1: Results of 10 gpm Field Test on Well Water

Field test ran 1,300 hours and processed over 450,000 gallons of well water. SAMMS reduced [Hg] from input ~25 ppb down to below detection limits (EPA 245.7) at output (~ 5ppt), well below 12 ppt mercury reduction goal. Field test verified the high mercury adsorption capacity of SAMMS (~ 40 pounds of SAMMS used). Mercury laden SAMMS from the field test was tested and passed TCLP.

Results provided by Steward Environmental Solutions

22 Case Study 2: 10 gpm Field Test on Well Water with High Concentration

Case Study 2: 10 gpm Field Test on Well Water with High Concentration

of Dissolved Solids:

Well water was very dark brown in color (humic acid) and contained high concentrations of total dissolved solids and organics. Activated carbon failed repeated tests due to fouling. The water contained more than twenty known species, such as sulfide, iron and chlorobenzene. A batch bench with SAMMS demonstrated reduction [Hg] to meet an initial target of 90% reduction. A field test was conducted using a 10 gpm SAMMS contactor tank system and ozone pretreatment to reduce organics

23 Case Study 2: 10 gpm Field Test on Well Water with High Concentration

Case Study 2: 10 gpm Field Test on Well Water with High Concentration

of Dissolved Solids:

SAMMS reduced [Hg] in over 40,000 gallons of well water from input ~2,000 ppt down to ~ 10 ppt output, well below 90% mercury reduction goal. Mercury laden SAMMS from the field test was tested and passed TCLP.

Results provided by Steward Environmental Solutions

24 Case Study 3: SAMMS for Mercury Reduction to Ultra Low Concentration:

Case Study 3: SAMMS for Mercury Reduction to Ultra Low Concentration:

An existing water treatment system, could not reach the mercury reduction target of 1.3 ppt or lower and SAMMS was tested as an alternative. 2. A SAMMS batch bench test was performed

25 Case Study 3: SAMMS for Mercury Reduction to Ultra Low Concentration:

Case Study 3: SAMMS for Mercury Reduction to Ultra Low Concentration:

SAMMS reduced [Hg] from input 4.5 ppt to 0.7 ppt within 6 minutes.

Results provided by Steward Environmental Solutions

26 Overview of different flavors of SAMMS chemistry

Overview of different flavors of SAMMS chemistry

27 Arsenic in Drinking Water Supplies

Arsenic in Drinking Water Supplies

Arsenic contamination of drinking water is commonly natural, due to the local geology.

US-EPA has a new drinking water standard as of Jan. 1, 2006 (down to 10 ppb from 50 ppb).

28 The Anion Problem

The Anion Problem

Existing anion exchange resins are generally based on quaternary ammonium salts and dont allow for direct interaction between ion pair Need a stereoselective receptor to bind tetrahedral oxoanions

Chemistry of Materials 1999, 11, 2148-2154.

29 Cu-EDA SAMMS Mechanism

Cu-EDA SAMMS Mechanism

Kds for chromate are very high (commonly 100,000) Kds for arsenate are moderately high (commonly 5,000-10,000) Kinetics are fast (minutes) While sulfate does compete, it is readily displaced

Journal of Physical Chemistry B, 2001, 105, 6337-6346.

Chemistry of Materials 1999, 11, 2148-2154.

30 Tailoring SAMMS to bind cesium

Tailoring SAMMS to bind cesium

Anchoring an anionic ferrocyanide complex inside the pores of MCM-41 makes a very efficient cesium sorbent, even in the presence of large excesses of Na or K.

Env. Sci. & Tech. 2001, 35, 3962-3966.

31 Cesium SAMMS Summary

Cesium SAMMS Summary

Kds for Cs binding are >100,000, even in the presence of 3M Na or K Excellent selectivity [Na] is more than 100,000 times higher than [Cs] and yet 99.8+% of the Cs is still sequestered Good kinetics (minutes) Can strip Cs and regenerate the sorbent activity via oxidation/reduction of the Fe center

32 Ligand Design Strategy for Actinide SAMMS

Ligand Design Strategy for Actinide SAMMS

Protic ligand -- a hard anionic Lewis base (e.g. carboxylate, phosphonate, etc.) Synergistic ligand -- amide carbonyl or phosphine oxide Synthesize a silane molecule containing both the desired protic and synergistic ligands in a geometry suitable for chelation (CMPO analog) Proximity effects in the monolayer interface will allow multiple ligands to interact with the actinide cation

Environmental Science & Technology 2005, 39, 1324-1331.

33 Actinide-specific ligand synthesis

Actinide-specific ligand synthesis

Hydrogen bonding between amide N-Hs helps to drive self-assembly.

Ligand proximity allows for multiple metal-ligand interactions

34 Summary of Actinide SAMMS Studies

Summary of Actinide SAMMS Studies

Kds are pH dependant and typically 10,000-100,000 Excellent selectivity is possible Phosphonate esters show a dependance on nitrate No competition from common cations (e.g. Na, Ca, etc.) Phosphonic acids show no competition from transition metals or complexants Excellent sorption kinetics (minutes) HOPO ligands provide excellent actinide affinity, even for Np(V)

Environmental Science & Technology 2005, 39, 1324-1331.

Environmental Science & Technology 2005, 39, 1332-1337.

35 Tailoring SAMMSTM interfacial chemistry to the periodic table

Tailoring SAMMSTM interfacial chemistry to the periodic table

.all by varying the monolayer ligand field.

Cu-EDA

Thiol

Cu-FC-EDA

Cs

HOPO Prop-Phos

Env. Sci. & Tech. 2001, 35, 3962-3966.

Chemistry of Materials 1999, 11, 2148-2154 J. Physical. Chem. B. 2001, 105, 6337-6346. J. Synchrotron Radiation, 2001, 8, 922-924

Radiochimica Act 2003, 91, 539-545

Env. Sci. & Tech. 2005, 39, 1324-1331 . Env. Sci. & Tech. 2005, 39, 1332-1337 . J. Materials Chemistry 2004, 14, 3356-3363 Chem. Comm. 2002, 1374-1375.

Science, 1997, 276, 923-926. J. Synchrotron Radiation, 1999, 6, 633-635 Sep. Sci. & Technol. 1999, 3411, 2329-2345 Mat. Tech. Adv. Perf. Mat. 1999, 14, 183-193 Surf. Sci. & Catalysis, 2000, 105, 729-738.

36 Life-cycle considerations

Life-cycle considerations

What happens after the heavy metals are captured?

Direct disposal Hg laden SAMMS passes TCLP leachate test Landfill, hazardous waste (minimal volume) Treatment followed by disposal Grouting Cement monolith Vitrification (only viable for certain heavy metals) Strip the toxic metal and recycle SAMMS Regeneration has been demonstrated Recycling holds down materials costs, but increases labor costs and potential worker exposure

37 Commercializing SAMMS

Commercializing SAMMS

Teaming with private industry to make high performance sorbents for heavy metal removal

TM

A Path Forward

38 Steward Environmental Solutions

Steward Environmental Solutions

Carrier bead powders, iron silicides, ferrites, custom ceramic design and processing Based in Chattanooga, Tennessee Well connected in the power industry (coal and nuclear) Has licensed the SAMMS patents, including SCF methodology Currently targeting Hg capture in coal-fired power plant emissions

SES contacts: Bob Jones -- rjones@stewardsolutions.com John Higley -- jhigley@stewardsolutions.com

Ferrite powders

39 Perry Equipment Corp

Perry Equipment Corp

A leading player in industrial filtration (oil/gas, chemical, food/beverage, etc.) Based in Mineral Wells, Texas (with facilities in US, Canada, Mexico, Europe, Middle East, Asia). Purchased by Clarcor Corp in 2007. Aggressively interested in incorporating nanotechnology (SAMMS) into filtration technology Filter elements, vessels, engineering services Currently targeting Hg removal from produced water in the petroleum industry

Industrial filtration elements

40 SAMMSTM  Current Applications

SAMMSTM Current Applications

Flue Gas

Produced Water

Mining impoundments

Sensors

Coal gasification

41 Functional nanomaterials can make analytical tools faster, more

Functional nanomaterials can make analytical tools faster, more

sensitive

High surface areas Open pore structure High functional density Easily tailored to conform to analytical interface. Ceramic nanosorbents Highly versatile silane chemistry Easily templated, processed

E-chem

XRF

High-performance preconcentrators

UV-Vis

GC

IR

Radiocounting

42 Functional nanomaterials enhance analytical sensitivity/selectivity

Functional nanomaterials enhance analytical sensitivity/selectivity

High-performance pre-concentrators

Sensor

Electrochemical sensors

Nanoparticles

Nanopores

Radiochemical assay

Nanorods

Spectroscopic detection

Functional nanomaterial interface

43 SAMMS enhances electrochemical detection of heavy metals

SAMMS enhances electrochemical detection of heavy metals

Lead

Environmental Health Perspectives, 2007, 115, 16831690.

PNNL sensor uses SAMMS: Incorporate high surface area, chemically specific sorbent material into working electrode Sorbent can be tailored for different target analytes - Small headspace size and variable flow volumes allow sample size to be varied over wide ranges

First level of discrimination provided by the chemical selectivity of the SAMMS Second level of discrimination provided by the electrochemical response of the analyte during stripping voltametry Ppb sensitivity with multiple metals (Pb, Cd, Cu, etc.) Response is linear to concentration Efficient preconcentration Works in environmental water samples, blood, urine, etc.

Lunch-box sized field test system

44 Summary

Summary

SAMMS is a very effective method for separation and sequestration of environmentally problematic species Rapid sorption kinetics and high binding capacity SAMMS can be readily tailored for a variety of environmental target species Chemistry can be tailored to capture heavy metals, oxometallate anions, actinides, cesium, etc. SAMMS are now being made commercially by Steward Environmental Solutions Same chemistry can be used to enhance sensing technologies

Available at amazon.com

45 Removing Heavy Metals from Water: Self-Assembled Monolayers on
46 Extra slides

Extra slides

47 Mercury Emissions

Mercury Emissions

EPAs Clean Air Mercury Rule (CAMR) (3/15/05) Current estimated US power plant emissions are about 48 tons Hg/year (158 tons anthropogenic Hg/year total)

Current air pollution control devices can capture some Hg, but this varies widely depending on a number of variables Current baseline estimates: $50,000-$70,000 per pound Hg removed ($4.3B to $6.7B) Near-term goal: 50-70% Hg capture, at 25-50% reduction in cost (2010) Longer-term goal: 90+% capture (2018)

We are currently developing new classes of SAMMS (and related materials), specifically tailored for application to high temperature, vapor phase applications (IGCC and CTL).

48 Electrochemical detection system

Electrochemical detection system

Uses magnetic nanomaterials to enhance analytical speed/sensitivity Cheap, lunchbox sized Field portable Measures heavy metal content of aqueous samples, blood, urine and saliva ppb sensitivity for multiple metals in 3-4 minutes

Environmental Health Perspectives, 2007, 115, 16831690.

49 10 gpm unit

10 gpm unit

Photo provided by Steward Environmental Solutions

50 Run this through ERICA

Run this through ERICA

We will make an at large request for a test site for soils clean up using SAMMS Bring touchy-feelies (SAMMS, extrudates, PECO filter cartridge, also bring slides with pictures of SES test-bed apparatus) Bring presentation on thumb-drive (can also email it ahead to Maria) Audience will be very concerned with end of life issues and life-cycle issues (disposal)

Removing Heavy Metals from Water: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)
http://900igr.net/prezentacija/anglijskij-jazyk/removing-heavy-metals-from-water-self-assembled-monolayers-on-mesoporous-supports-samms-145417.html
c

661

29
900igr.net > > > Removing Heavy Metals from Water: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)