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Electron Beam Technology: Environmental Applications. William J. Cooper Director and Professor Urban Water Research Center Department of Civil and Environmental Engineering University of California, Irvine Irvine, CA 92697 wcooper@uci.edu. Overview of Water.
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Electron Beam Technology:Environmental Applications William J. Cooper Director and Professor Urban Water Research Center Department of Civil and Environmental Engineering University of California, Irvine Irvine, CA 92697 wcooper@uci.edu
Overview of Water • Water availability/sustainability • Water reuse • Water treatment through the CO2 lens • Considerations • Pharmaceuticals and other emerging chemicals of concern • Biosolids/sludge treatment • RO Retentate Treatment • Engineered nanoparticles in water • Agricultural Production – food and water • Economic models for assessing options in water • Salinity and agricultural practices • Infrastructure • Smart Water Systems • Reinvestigation of innovative water treatment processes
Historical Perspective • 1988 – received funds from the NSF to refurbish and operate the Electron Beam Research Facility, Miami, FL (1988 – 2001) • 1989 – incorporated High Voltage Environmental Applications (1989 – 2011) • Conducted large scale and pilot scale studies on over 150 compounds. • To my surprise – published 59 papers and 22 chapters in books • On the team that had B. anthraces data before the letters were received
Operating Electron Beam • Accelerator = 1.5 MeV; 75 kWScanned to penetrate water or vapor • 100 – 150 gallons per minute
EBRF – Miami, FL • Located at a wastewater treatment plant • Had four input lines (up to 150 gpm) • Drinking water • Secondary treated wastewater • Digested sludge (now referred to as biosolids) • Tanker/2500 gallon tank in yard to receive any sample that was shipped to the facility • Separate electrical line to measure energy consumption • Problem – we called it a research facility
Mobile Electron BeamSavannah River Site – EPA Demonstration – 1994 Sept – Nov.
Research Approach Chemistry Laboratory Experiments Large Scale Studies “Real World” Kinetic Information Product Identification Removal Information Contaminant Removal Understanding/AOP Application
Initial Studies • Chloroform • TCE • PCE • Benzene • Toluene • Phenol • Carbon Tetrachloride
Conditions • Three influent concentrations • Three pH’s – to test effect of carbonate • 5 or less • 7 • 9 • With and without solids (3 % kaolin) • 4 doses (including a zero dose)
Conclusions • Carbonate/bicarbonate effects treatment • used pH to study this • has different effects on different compounds • Solids (3 % clay) did not effect treatment • Each compound is different in it removal pattern
Advantages of E-Beam • The most efficient process for generating hydroxyl radicals, •OH, the defining reactive species for Advanced Oxidation Processes (AOPs) • Measured 72 % efficiency from wall power to chemistry • No need of additives – only the electrons • Solids do not interfere with the process
Advantages of E-Beam • Simultaneously generates oxidizing (•OH) and reducing (e-, •H) radicals • Based on aqueous radiation chemistry H2O \/\/\/\/\/ 2.7 •OH + 0.6 •H + 2.6 e- + 0.45 H2 + 0.7 H2O2 + 2.6 H+
Advantages of E-Beam • Equipment is reliable – with Insulated Core Transformers (ICTs) having 98 – 99 % uptime • Mobile trailer machine built in 1963 • No residuals – e.g. sludge's etc.
Early Approach • We obtained a lot of phenomenological data on contaminant removal • Effect of pH – really the impact of the carbonate/bicarbonate system on pollutant removal • Dose destruction curves – all first order (conc. vs dose) • Effect of solids
Early Approach • Mid-1990’s we started to model the system using AECL’s MAKISIMA CHEMIST • PC’s back then were slow – 2 hours a run (now 5 – 10 seconds on lap tops) • Modeling showed that pulsed beams (with Los Alamos) were not as efficient as continuous beams • Had to do with recombination of radicals at high doses of pulsed systems
Large Scale Studies - Example: Thioanisole Removal pH 5 pH 9
Laboratory Conditions - Kinetic Information Rate Constant Results For Each Initial Radical Reacting WithThioanisole (TA): kIIobs = 1.1 x 1010 M-1s-1 kIIobs = 3.1 x 108 M-1s-1 kIIobs = 1.2 x 109 M-1s-1
Removal Simulation - Comparison of Simulation and Large Scale Results pH 5 pH 9 Red = Simulation Black = Exp. Values
Early Approach • Then measuring new reaction rate constants at NDRL – opened more detailed modeling • More recently have started to deal with by-products of reactions using gamma – photons as the source (NDRL, INL, and UCI)
Early Approach • More recently – due to lack of a pilot facility we have turned to gamma sources (NDRL, INL, and UCI) to work on mechanism • Also requires extensive mass spec capability • From a chemical point of view – we have explored the efficiency of the actual reactions
e-aq rate constant (1.61 ± 0.03) × 109 105% Portion of OH and e-aq reaction with diclofenac and function group OH rate constant (6.97 0.24) x 109 75%
Gemfibrozil (a) slope= -1.87 x 10-4 M kGy-1 Clofibric acid (b) slope= -3.47 x 10-4 M kGy-1 Bezafibrate (c) Slope= -4.85 x 10-4 M kGy-1
Efficiency reaction of both •OH and e-aq with clofibrates: 98 % with bezafibrate 95 % with clofibric acid 62 % with gemfibrozil
Applications • Have ‘played’ in the chemical and biological warfare arena
MEAN DOSE REQUIRED (kGy) AGENT 1 log kill 4 log kill Bacillus subtillis var globigii (BG) spores 1.34 6.00 Bacillus anthracis sterne spores 3.27 10.40 Influenza virus 5.65 22 (approximately) Serratia marcescens 0.043 0.174 Biological Summary
Markets • Environmental market is enormous and will remain that way • Environmental markets are very fragmented • Environmental markets are VERY risk adverse • PROBLEM – no one wants to be first to install a full scale plant
VERY risk adverse – opportunities for out of the box thinking • There are no installed E-Beams for environmental applications in the US? • The industry will NOT take a chance – at all – and that in part stems from the regulatory oversight • Whenever you are talking environmental remediation – it is always a “red” on the bottom line • The remediation market is totally regulatory driven
Water – Food = A Market? • World food production will have to increase 70 % by 2050 • A very large market exists in food irradiation for pest control – in the import and export markets • Just visited a fruit pacing facility in the CA central valley not totally sure this is a target BUT there are possibilities – water and food
E-Beam TechnologyWhat are the Markets? • Wastewater treatment – biosolids • Working with Arlington WWTP to show that process can eliminate endocrine disruptors • Then they have agreed to put in a full scale demonstration plant • Water Reuse – RO retentates or reject water • Food Irradiation • Agricultural – pest management
Commercialization • Only one company has made it through the valley of death – EB Tech of Korea – Dr. Bumsoo Han • Major area is that he has reduced the capital cost of equipment tremendously • We paid for e-beam (75 kW system in 1980) - $1.5 million • EB Tech has a 400 kW system for around $2 M
Commercialization • Radiation Dynamics – Dynamitron - now a member of IBA is around (Long Island) • Jacob Applebaum – in central Florida is very interested – was involved in food irradiation • Biggest problem with many E “beamers” is that always want to build a new system
Thoughts • We have never quite figured out how to REALLY assist ‘start-up’ companies commercialize new processes • There needs to have thought given to a location for testing and validation (third party) • Nobody wants to be first in the environmental field – especially where capital costs are high • E Beam – no clients could get over the initial cost – even though O & M was minimal • Need to develop a system where biological treatment is last step and tested
