development / optimization of the new high-efficiency nano-catalyst immobilization technology for...
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Development / Optimization of the new High-Efficiency Nano-Catalyst
Immobilization Technology for ex-situ treatment of
contaminated waters
K. Cross, Cross Consulting Engineers, Cardiff, CA and
Charles Schaefer, Ph. D., Shaw Environmental, Inc., Lawrenceville, NJ
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Overall Introduction and Outline•Section 1: Overview of treatment w micro/nano-particles
•Section 2: HENCI Technology Overview•HENCI TOP•Phase 1 tests of late ’04
•Section 3: Phase 2 Testing•Objectives and key issues•Scope of Experiments•HENCI Reactor sub-optimization and sizing
•Section 4: Phase 3 Pilot Test•Objectives•Approach•Potential Sites•HENCI System Process PID’s•Cost Evaluations
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Section 1
Micro / Nano-Catalyzed Remediation Overview
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Micro/Nano-Catalysis Highlights
NanoTech now has ~2000 Application Categories - all sectors http://azonano.com/Applications.asp
CNST / CBEN at Rice University: “We developed high-performance nano-scale catalysts for treating particularly challenging contaminants in water that must be removed to a very low level.”
In-Situ Success with Pd/Fe on TCE by Zhang, Schrick, et. al. Rapid, Complete, Inexpensive Breakdown of ~50 (so far)
ubiquitous recalcitrant carcinogenics at sub-ppb levels Cl’d Olefinics, Cl’d Aromatics, THMs, Pesticides, PCHs,
PCBs, Dyes, NDMA, TNT, Cr2O2,AsO3, NO, Hg, Ni,
City Redlands, CA Env. Council: “TCE and PCPs contamin-ating about half the wells in Midwest and Western U.S. Many in Redlands have been closed due to the high levels of TCE”
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Ex Situ Treatment of Waters Containing Organic Contaminants
• Groundwater
• Drinking water
• Leachate
• Wash Down
Bio-reactors
Activated Carbon
UV-oxidation
Thermal CATOX
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Zero Valent Metal Particles for Treatment of Organic
Contaminants
Metal Diameter(µm)
Surface Area (m2/g)
Composition
ZVI filings 1,000 1.0 Fe0
MZVI 80 2.0 Fe0
NZVI 0.01 25 Fe0
Metal Catalysts 1.0 190 60% Pd or Ni on alumina support
Bimetallic MZVI/NZVI
0.01 25 Fe0 doped with 0.1% Pd or Ni
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Zero Valent Metal Particles
Zero Valent metals have been show to treat a wide range of compounds:
•Chlorinated solvents•Explosives (e.g., TNT, RDX)•NDMA•Nitrate•Perchlorate (?)
Limited use in ex situ treatment systems due to:
• Longevity• Matrix Effects • Particle Retention
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Conceptual Model
RX
RH + X- + Fe2+
Fe
H+
Un-catalyzed ZVI
Catalyzed ZVI
RX
Fe2+ + H2
Fe
H+
Catalyst RH + X-
H2OH+
e-
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Reactor Data
0.0
1.0
2.0
3.0
4.0
0 5 10 15 20
R e a c to r Vo lu m e s
In f lu e n t E ff lu e n t
• 3 hour residence time
• 10g Ni catalyst
• TCE converted to ethane
• No sulfate reduction
• No nickel in effluent
• Influent DO = 8 mg/L
Influent = artificial groundwater containing TCE, sulfate, nitrate, carbonate, and manganese
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Reactor Data
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0 5 10 15 20 25 30 35
R e a c to r Vo lu m e s
T C E In flu e n t ND M A In flu e n t T C E E ff lu e n t ND M A E ff lu e n t
• 3 hour residence time
• 10g Ni catalyst
• No sulfate reduction
• Influent DO = 8 mg/L
• Nitrate reduction
Influent = artificial groundwater containing sulfate, nitrate, carbonate, and manganese
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0.0
0.2
0.4
0.6
0.8
1.0
0 20 40 60 80 100 120 140 160
Reactor Volumes
Re
mo
va
l E
ffic
ien
cy
Catalyst regeneration using dilute acid
Reactor Data
Influent = artificial groundwater containing sulfate, nitrate, carbonate, and manganese
Influent TCE 1 ppm
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Geochemical Effects on observed PCE Degradation Rate Constants
Soil Slurry pH Fluoride Bromide Chloride Sulfate Nitrate Nitrite CarbonateSoil A 7.5 <0.1 <0.1 20 22 <0.1 <0.1 0.03Soil B 9.7 0.14 0.17 308 51 0.17 0.4 35.1
0.44 ± 0.060 0.22 ± 0.048 0.16 ± 0.0410.048 ± 0.007 0.20 ± 0.057 0.23 ± 0.062
Soil A Soil B Soil B (buffered)Ni
NZVI
pH7.2
Rate Constants normalized to catalyst surface area (day-m2 cat)-1
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Batch Data - Mixtures
• Timescale of weeks
• NDMA inhibits PCE decay
•1st-order decay
• Negligible sorption
0
0.2
0.4
0.6
0.8
1
1.2
0 5 10 15 20
Time (days)
Rel
ativ
e P
CE
Aq
. C
on
cen
trat
ion
Soil A Soil A+NDMA Expon. (Soil A)
NZVI Treatment
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Section 2
HENCI Overview
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•As Previously noted, due to their size (and also structure / morphology), micro/nano-particles rapidly degrade many dissolved contaminants
•However, due to their small size, there has been no way to cost-effectively immobilize large
quantities of MNPs in a flow-through reactor
•HENCI cost-effectively immobilizes most nano- & micro-catalysts in a new and novel way, free of the main technical and financial drawbacks inherent to today’s less viable technologies:
•Homogeneous, Dense Dispersion – no channeling•Insignificant Del-P even at high flows = Low Cost• Often NO NEW CONTACT MATERIALS exposed to stream
HENCI High-Efficiency Nano-Catalyst Immobilization
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What HENCI Means to the Process Engineer
All advantages of a Continuous Packed-Bed ReactorNo moving partsNanoparticle agglomeration can be tuned outHENCI can immobilize any new macro-structured nanocatalysts which have high-µ or paramagnetic components
Multiple Standardized HENCI units can be Manifolded Valved in series, parallel or any combination ‘on-line’ Process any combination of Inlet stream flow rate and concentration
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Phase 1 Results (late 2004)
• Prototype Rxrs Immobilized ¼ g of BNPC’s per cm3 @ ~2gpm
•Video Clip shows release of particles upon unit power-down•Greater loading capacities very likely achievable
• HENCI Immobilization force more than adequate for all app’s
• Negligible Pressure Drops: allows High Flows, Long Reactors
• HENCI Prototypes operated with TCE - polluted inlet stream
•Preliminary Trial Report Circulated to NWRI Early ’05
•TCE Run data yield fast Pseudo First-Order Rate Constants
•No effect on efficacy of catalyst by HENCI observed
Verification of results is one task of phase 2
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Section 3: Phase II Development
1: NMCR Database Gather data from Treatability Studies and literature Compile into ever-growing NMCR Database
2: Treatability Studies / RXR Development Build several bench-scale rxrs, install in Shaw’s Lab verify degradation of target contaminants in site groundwater determine the most appropriate metallic particles determine degradation kinetics reactor residence time estimate extent of particle “change-out” or regeneration Use data and experience to incorporate improvements to reactors
Locations:Shaw Environmental, Inc.Lawrenceville, NJCross ConsultingCardiff, CA
Objectives
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1. Batch Screening Tests
Phase II Testing
• site groundwater• degradation end products• kinetics
2. Bench scale Reactor Testing• reactant loading in HENCI reactor • degradation rates• daughter product generation• reaction longevity• hydraulic properties
3. Data Evaluation & Conceptual Design• calculate rate constants• reactor sizing and optimization
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Reactor Sizing and Optimization
1st-order degradation rate constant
for ZVI/Pd, area ≥ 7130 m2/L
2mh
L01.0k
2mh
L001.0
to
Key parameter: area = m2/L of catalyst in reactor
Basic Design Equation
k´= k • area
x1
1
k
1
area
ln
For 99.9% conversion, = 12 minutes For 1 gpm flow, Reactor volume = 12 Gal
Process Optimization Parameters
RXR Eff = (% Conversion/ (Tresx MassBNMC) )
Fluid Dyn. Eff = SABET / (PSID / GPM / Axs)
= SABET / (PSID / v)
dEff / dPD goes thru max for each material
Scale-Up Using Optimal RXR tres
Reactor / system configuration det’d from Tresmin and Inlet stream flowrate
Total DelP then allows pump sizing, system design, add controls
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Section 4: Phase III - Pilot Demonstration
ObjectivesDemonstrate HENCI particle retention system at the field scale
Remediate in-field: Verify treatment effectiveness of target contaminants
Evaluate long-term operation
Identify potential design improvements and modifications
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Potential SitesPicatinny Arsenal, Dover, NJ• Existing P&T system operated by Shaw• TCE1000 µg/L• Low ppb levels CT, DCE, VC
Former Naval Surface Warfare Ctr, White Oak, MD
• former waste water discharge area• TCE, TNT, RDX
19th St. GAC PlantCity of San Bernardino
• ~7ppb TCE, ~ 5ppb NDMA
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Approach
• Construct and install HENCI System with selected nano/micro particles, controls, redundancies
• Treat and monitor for 3 to 4 months (1 gpm flow)
• Perform O&M activities as needed
• Evaluate results with respect to overall treatment effectiveness and costs
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Typical HENCI Process PID
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SummaryRapid and cost-effective ex-situ treatment of a variety of contaminants
HENCI technology applicable to wide range of nano/micro particles
Significant Potential to revolutinize CHC Site remediation – Point-of-Distribution Systems: Pump/Treat, and USE!
Reactor-based nanocatalysis will merit applications in other Environmental sub-sectors as Rural P.O.D., portable/Field unit, and other non-Groundwater applications arise
Potential to Usher in new era in water remediation globally