Upload
ashlynn-bell
View
221
Download
0
Tags:
Embed Size (px)
Citation preview
Electron Beam Technology:Electron Beam Technology:Environmental ApplicationsEnvironmental Applications
William J. CooperWilliam J. Cooper
Director and ProfessorDirector and ProfessorUrban Water Research CenterUrban Water Research Center
Department of Civil and Environmental EngineeringDepartment of Civil and Environmental EngineeringUniversity of California, IrvineUniversity of California, Irvine
Irvine, CA 92697Irvine, CA 92697
Overview of WaterOverview of Water Water availability/sustainabilityWater availability/sustainability
Water reuseWater reuse
Water treatment through the COWater treatment through the CO22 lens lens
ConsiderationsConsiderations Pharmaceuticals and other emerging chemicals of concernPharmaceuticals and other emerging chemicals of concern Biosolids/sludge treatmentBiosolids/sludge treatment RO Retentate TreatmentRO Retentate Treatment Engineered nanoparticles in waterEngineered nanoparticles in water Agricultural Production – food and waterAgricultural Production – food and water Economic models for assessing options in waterEconomic models for assessing options in water Salinity and agricultural practicesSalinity and agricultural practices InfrastructureInfrastructure Smart Water SystemsSmart Water Systems Reinvestigation of innovative water treatment processesReinvestigation of innovative water treatment processes
Historical PerspectiveHistorical Perspective 1988 – received funds from the NSF to refurbish 1988 – received funds from the NSF to refurbish
and operate the Electron Beam Research and operate the Electron Beam Research Facility, Miami, FL (1988 – 2001)Facility, Miami, FL (1988 – 2001)
1989 – incorporated High Voltage Environmental 1989 – incorporated High Voltage Environmental Applications (1989 – 2011)Applications (1989 – 2011)
Conducted large scale and pilot scale studies on Conducted large scale and pilot scale studies on over 150 compounds.over 150 compounds.
To my surprise – published 59 papers and 22 To my surprise – published 59 papers and 22 chapters in bookschapters in books
On the team that had On the team that had B. anthraces B. anthraces data before data before the letters were receivedthe letters were received
Electron Beam Research Electron Beam Research Facility – Miami, FLFacility – Miami, FL
Large Scale Studies
Large Scale Studies - Electron Beam Research Facility
Large Scale Studies - Electron Beam Research Facility
Large Scale Studies - Electron Beam Research Facility
Operating Electron BeamOperating Electron BeamAccelerator = 1.5 MeV; 75 kW
Scanned to penetrate water or vapor 100 – 150 gallons per minute
EBRF – Miami, FLEBRF – Miami, FL Located at a wastewater treatment plantLocated at a wastewater treatment plant Had four input lines (up to 150 gpm)Had four input lines (up to 150 gpm)
Drinking waterDrinking water Secondary treated wastewaterSecondary treated wastewater Digested sludge (now referred to as biosolids)Digested sludge (now referred to as biosolids) Tanker/2500 gallon tank in yard to receive any sample Tanker/2500 gallon tank in yard to receive any sample
that was shipped to the facilitythat was shipped to the facility
Separate electrical line to measure energy Separate electrical line to measure energy consumptionconsumption
Problem – we called it a research facilityProblem – we called it a research facility
Mobile Electron BeamMobile Electron BeamSavannah River Site – EPA Savannah River Site – EPA
Demonstration – 1994 Sept – Nov.Demonstration – 1994 Sept – Nov.
Cross Section thru Mobile UnitCross Section thru Mobile Unit
Research ApproachChemistry
Laboratory Experiments Large Scale Studies “Real World”
Kinetic Information Product Identification Removal Information
Contaminant Removal Understanding/AOP Application
Initial StudiesInitial Studies
ChloroformTCEPCEBenzeneToluenePhenolCarbon Tetrachloride
ConditionsConditions
Three influent concentrationsThree pH’s – to test effect of carbonate
– 5 or less– 7– 9
With and without solids (3 % kaolin)4 doses (including a zero dose)
ConclusionsConclusionsCarbonate/bicarbonate effects
treatment– used pH to study this– has different effects on different
compoundsSolids (3 % clay) did not effect
treatmentEach compound is different in it removal
pattern
Organic Compound Removal using Organic Compound Removal using the the
E-Beam ProcessE-Beam Process
0
10
20
30
40
50
60
70
80
90
100
Experiment A
MTBE
TCE
PCE
Benzene
Toluene
E-Benzene
o-Xylene
CHCL3
EDB
NDMA
Atrazine
Simazine
Advantages of E-BeamAdvantages of E-Beam
The most efficient process for generating The most efficient process for generating hydroxyl radicals, •OH, the defining hydroxyl radicals, •OH, the defining reactive species for Advanced Oxidation reactive species for Advanced Oxidation Processes (AOPs)Processes (AOPs)Measured 72 % efficiency from wall power to Measured 72 % efficiency from wall power to
chemistrychemistryNo need of additives – only the electronsNo need of additives – only the electronsSolids do not interfere with the processSolids do not interfere with the process
Advantages of E-BeamAdvantages 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-BeamAdvantages of E-Beam
Dose(kGy)
Concentration(mM)
•OH e-aq H• H2O2
1 0.28 0.27 0.06 0.07
5 1.4 1.4 0.3 0.4
10 2.8 2.7 0.7 0.7
Advantages of E-BeamAdvantages of E-Beam
Equipment is reliable – with Insulated Equipment is reliable – with Insulated Core Transformers (ICTs) having 98 – 99 Core Transformers (ICTs) having 98 – 99 % uptime% uptimeMobile trailer machine built in 1963Mobile trailer machine built in 1963
No residuals – e.g. sludge's etc.No residuals – e.g. sludge's etc.
Advantages of E-Beam;Advantages of E-Beam;Design ConsiderationDesign Consideration
Early ApproachEarly Approach
We obtained a lot of phenomenological We obtained a lot of phenomenological data on contaminant removaldata on contaminant removalEffect of pH – really the impact of the Effect of pH – really the impact of the
carbonate/bicarbonate system on pollutant carbonate/bicarbonate system on pollutant removalremoval
Dose destruction curves – all first order (conc. Dose destruction curves – all first order (conc. vsvs dose) dose)
Effect of solidsEffect of solids
Early ApproachEarly Approach
Mid-1990’s we started to model the system Mid-1990’s we started to model the system using AECL’s MAKISIMA CHEMISTusing AECL’s MAKISIMA CHEMISTPC’s back then were slow – 2 hours a run PC’s back then were slow – 2 hours a run
(now 5 – 10 seconds on lap tops)(now 5 – 10 seconds on lap tops)
Modeling showed that pulsed beams (with Los Modeling showed that pulsed beams (with Los Alamos) were not as efficient as continuous Alamos) were not as efficient as continuous beamsbeamsHad to do with recombination of radicals at Had to do with recombination of radicals at
high doses of pulsed systemshigh 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 = 1.2 x 109 M-1s-1
kIIobs = 3.1 x 108 M-1s-1
kIIobs = 1.1 x 1010 M-1s-1
Removal Simulation - Comparison of Simulation and Large Scale Results
pH 5 pH 9
Red = SimulationBlack = Exp. Values
Early ApproachEarly Approach
Then measuring new reaction rate constants at Then measuring new reaction rate constants at NDRL – opened more detailed modelingNDRL – opened more detailed modeling
More recently have started to deal with by-More recently have started to deal with by-products of reactions using gamma – photons as products of reactions using gamma – photons as the source (NDRL, INL, and UCI)the source (NDRL, INL, and UCI)
Pharmaceutical and Personal Care Products have been studied
Pharmaceutical Pharmaceutical and Personal and Personal
Care Products Care Products CompoundCompound
Reaction RatesReaction Rates
ReferencesReferences••OHOH (M(M-1-1 s s-1-1)) ee--aqaq (M(M-1-1 s s-1-1))
Lipid RegulatorsLipid Regulators
Clofibric AcidClofibric Acid (6.98(6.980.12) × 100.12) × 1099 (6.59(6.590.43) ×100.43) ×1088 B. Razavi, W. Song, B. Razavi, W. Song, William J. Cooper et alWilliam J. Cooper et al J. J. Phys. Chem. A.Phys. Chem. A. 2009, 2009, 113113, 1287 , 1287
BenzafibrateBenzafibrate (8.00(8.000.22) × 100.22) × 1099 (1.12(1.120.03) × 100.03) × 101010
GemfibrozilGemfibrozil (10.0(10.00.60) × 100.60) × 1099 (6.26(6.260.58) × 100.58) × 1088
Insect repellentInsect repellent DEETDEET (4.95±0.18) × 10(4.95±0.18) × 1099 ((1.34±0.04) × 101.34±0.04) × 1099W. Song, W. Cooper et. W. Song, W. Cooper et. al.al. Water Research.Water Research. 2009, 2009, 4343, 635, 635
Beta-blockerBeta-blockerAtenololAtenolol (7.05(7.050.27) × 100.27) × 1099 (5.91(5.910.21) ×100.21) ×1088 W. Song W. Cooper et. W. Song W. Cooper et.
al. al. Environ. Sci. Technol.Environ. Sci. Technol. 20082008, , 4242, 1256, 1256
MetoprololMetoprolol (8.39(8.390.06) × 100.06) × 1099 (1.73(1.730.03) ×100.03) ×1088
PropranololPropranolol (1.07(1.070.02) × 100.02) × 101010 (1.26(1.260.02) ×100.02) ×101010
Beta-lactamBeta-lactam(Antibio(Antibiotics)tics)
Penicillin GPenicillin G (7.97(7.970.11) ×100.11) ×1099 (3.92(3.920.10) ×100.10) ×1099 W. SongW. Song,, W. Cooper et. al. W. Cooper et. al. J. Phys. Chem. A.J. Phys. Chem. A. 2008 2008, , 112112 ,7411 ,7411
Penicillin VPenicillin V (8.76(8.760.28) ×100.28) ×1099 (5.76(5.760.24) ×100.24) ×1099
AmoxicillinAmoxicillin (6.94(6.940.44) ×100.44) ×1099 (3.47(3.470.07) ×100.07) ×1099
FluoroquinolonesFluoroquinolones
DanofloxacinDanofloxacin (6.15(6.150.11) ×100.11) ×1099 (1.68(1.680.02) ×100.02) ×101010
H. Santoke, W. Song, W. H. Santoke, W. Song, W. Cooper et al.Cooper et al. J. Phys. J. Phys. Chem. AChem. A. . 20092009 113113, 7846 , 7846
OrbifloxacinOrbifloxacin (6.94(6.940.08) ×100.08) ×1099 (2.25(2.250.02) ×100.02) ×101010
MarbofloxacinMarbofloxacin (9.03(9.030.39) ×100.39) ×1099 (2.41(2.410.02) ×100.02) ×101010
EnrofloxacinEnrofloxacin (7.95(7.950.23) ×100.23) ×1099 (1.89(1.890.02) ×100.02) ×101010
FlumequineFlumequine (8.26(8.260.28) ×100.28) ×1099 (1.83(1.830.01) ×100.01) ×101010
Pharmaceutical Pharmaceutical and Personal and Personal
Care Products Care Products CompoundCompound
Reaction RatesReaction Rates
ReferencesReferences••OHOH
(M(M-1-1 s s-1-1))ee--
aqaq
(M(M-1-1 s s-1-1))
AntibioticsAntibiotics
TetracyclineTetracycline (6.34(6.340.11) × 100.11) × 1099 (2.16(2.160.08) × 100.08) × 101010J. Jeong, W. SongJ. Jeong, W. Song W. J. Cooper, et al W. J. Cooper, et al Chemosphere 2010, Chemosphere 2010, 78, 53378, 533
ChlortetracyclineChlortetracycline (5.20(5.200.23) × 100.23) × 1099 (1.32(1.320.18) × 100.18) × 101010
OxytetracyclineOxytetracycline (5.63(5.630.03) × 100.03) × 1099 (2.32(2.320.05) × 100.05) × 101010
DoxycyclineDoxycycline (7.58(7.580.12) × 100.12) × 1099 (2.52(2.520.02) × 100.02) × 101010
Non-Steroidal Non-Steroidal anti-anti-
inflammatoryinflammatory
DiclofenacDiclofenac (9.29 ± 0.11) × 10(9.29 ± 0.11) × 1099 (1.53 ± 0.03) × 10(1.53 ± 0.03) × 1099
Manuscripts in Manuscripts in Prepare Prepare IbuprofenIbuprofen (5.97 ± 0.22) × 10(5.97 ± 0.22) × 1099 (4.76 ± 0.18) × 10(4.76 ± 0.18) × 1088
NaproxenNaproxen (7.53 ± 0.26) × 10(7.53 ± 0.26) × 1099 (2.43 ± 0.13) × 10(2.43 ± 0.13) × 1099
X-ray contrast X-ray contrast agentsagents
DiatrizoateDiatrizoate (9.58 (9.58 0.23) × 10 0.23) × 1088 (2.13 (2.13 0.03) × 10 0.03) × 101010
J. Jeong, W. SongJ. Jeong, W. Song **, , W. J. Cooper, et al W. J. Cooper, et al Water ResearchWater Research
IohexolIohexol (3.21 (3.21 0.13) × 10 0.13) × 1099 (3.35 (3.35 0.03) × 10 0.03) × 101010
IopromideIopromide (3.34 (3.34 0.14) × 10 0.14) × 1099 (3.25 (3.25 0.05) × 10 0.05) × 101010
IomeprolIomeprol (2.03 (2.03 0.13) × 10 0.13) × 1099 (3.47 (3.47 0.02) × 10 0.02) × 101010
IopamidolIopamidol (3.42 (3.42 0.28) × 10 0.28) × 1099 (3.37 (3.37 0.05) × 10 0.05) × 101010
AntibioticAntibiotic TrimethoprimTrimethoprim (8.34 (8.34 0.47) × 10 0.47) × 1099 (1.36 (1.36 0.01) × 10 0.01) × 101010 Luo et al., Luo et al., Wat. ResWat. Res. . 2012, 46, 1327 2012, 46, 1327
On going projects related with PPCPs
Early ApproachEarly Approach
More More recently – due to lack of a pilot facility recently – due to lack of a pilot facility we have turned to gamma sources (NDRL, we have turned to gamma sources (NDRL, INL, and UCI) to work on INL, and UCI) to work on mechanismmechanismAlso requires extensive mass spec capabilityAlso requires extensive mass spec capability
From a chemical point of view – we have From a chemical point of view – we have explored the efficiency of the actual explored the efficiency of the actual reactionsreactions
300 350 400 450 5000.000
0.005
0.010
0.015
0.020
0.025
Ab
sorb
an
ce
Wavelength (nm)
1 s 5 s 50 s 100 s 250 s
HN
Cl
O
ONaCl
300 350 400 450 500
0.000
0.005
0.010
0.015
0.020
0.025
Ab
sorb
an
ce
Wavelength (nm)
1 s 5 s 50 s 100 s 250 s
NH2
Cl
Cl
Compare transit Spectra of diclofenac with model Compare transit Spectra of diclofenac with model compoundcompound
HN
Cl
ONa
O
Cl
OH rate constant(6.97 0.24) x 109
75%
ee--aqaq rate constant rate constant
(1.61 ± 0.03) × 10(1.61 ± 0.03) × 1099
105% 105%
Portion of OH and ePortion of OH and e--aqaq reaction with diclofenac and function group reaction with diclofenac and function group
HN
OH
O
Cl
Cl
Diclofenac
HN
OH
O
Cl OH
Cl HN
OH
O
ClHO
Cl
HN
OH
O
O
Cl
N
Cl
Cl
O
OH
O
HN
OH
O
Cl
Cl
HO
HN
OH
O
Cl
OH
MW 311 MW 311MW 311
MW 275MW 309
MW 277
Degradation Mechanism of OH radical oxidation of Diclofenac
NH
OH
O
Cl
Cl
NH
OH
O
Cl
NH
OH
O
Cl
NHOH
O
Cl
NHOH
O
Diclofenac
MW 261MW 261 MW 259
MW 225
Degradation Mechanism of e-aq Reduction of diclofenac
0 2 4 6 80.0
0.1
0.2
0.3
0.4
0.5
0.6
a
Co
nce
ntr
atio
n o
f G
em
fib
rozil
(mM
)
Irradiation dose (kGy) 0 1 2 3 4 5 6 7 8
0.0
0.1
0.2
0.3
0.4
0.5
0.6
b
Co
nce
ntr
atio
n o
f C
lofib
ric A
cid
(m
M)
Irradiation dose (kGy)
0 1 2 3 4 5 6 7 8
0.0
0.1
0.2
0.3
0.4
0.5
0.6
c
Co
nce
ntr
atio
n o
f B
eza
fib
rate
(m
M)
Irradiation dose (kGy)
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 Efficiency reaction of both ••OH OH and eand e--
aqaq with clofibrates: with clofibrates:
98 % with bezafibrate98 % with bezafibrate
95 % with clofibric acid 95 % with clofibric acid
62 % with gemfibrozil62 % with gemfibrozil
ApplicationsApplications
Have ‘played’ in the chemical and Have ‘played’ in the chemical and biological warfare arenabiological warfare arena
ChemicalsChemicals
Chemical DestructionChemical Destruction
Biological DestructionBiological Destruction
Biological SummaryBiological Summary
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
MarketsMarkets
Environmental market is enormous and will Environmental market is enormous and will remain that wayremain that way
Environmental markets are very fragmentedEnvironmental markets are very fragmented
Environmental markets are VERY risk adverseEnvironmental markets are VERY risk adverse
PROBLEM – no one wants to be first to PROBLEM – no one wants to be first to install a full scale plantinstall a full scale plant
VERY risk adverse – opportunities for VERY risk adverse – opportunities for out of the box thinkingout of the box thinking
There are no installed E-Beams for environmental There are no installed E-Beams for environmental applications in the US?applications in the US?
The industry will NOT take a chance – at all – and that in The industry will NOT take a chance – at all – and that in part stems from the regulatory oversightpart stems from the regulatory oversight
Whenever you are talking environmental remediation – it Whenever you are talking environmental remediation – it is always a “red” on the bottom lineis always a “red” on the bottom line
The remediation market is totally regulatory drivenThe remediation market is totally regulatory driven
Water – Food = A Market?Water – Food = A Market?
World food production will have to increase 70 % World food production will have to increase 70 % by 2050by 2050
A very large market exists in food irradiation for A very large market exists in food irradiation for pest control – in the import and export marketspest control – in the import and export marketsJust visited a fruit pacing facility in the CA Just visited a fruit pacing facility in the CA
central valley not totally sure this is a target central valley not totally sure this is a target BUT there are possibilities – water and food BUT there are possibilities – water and food
E-Beam TechnologyE-Beam TechnologyWhat are the Markets?What are the Markets?
Wastewater treatment – Wastewater treatment – biosolidsbiosolids Working with Arlington WWTP to show that process Working with Arlington WWTP to show that process
can eliminate endocrine disruptorscan eliminate endocrine disruptors Then they have agreed to put in a full scale Then they have agreed to put in a full scale
demonstration plantdemonstration plant
Water Reuse – Water Reuse – RO retentates or reject waterRO retentates or reject water
Food IrradiationFood Irradiation
Agricultural – Agricultural – pest managementpest management
CommercializationCommercializationOnly one company has made it through the Only one company has made it through the
valley of death – EB Tech of Korea – Dr. valley of death – EB Tech of Korea – Dr. Bumsoo HanBumsoo HanMajor area is that he has reduced the capital Major area is that he has reduced the capital
cost of equipment tremendouslycost of equipment tremendouslyWe paid for e-beam (75 kW system in 1980) - We paid for e-beam (75 kW system in 1980) -
$1.5 million$1.5 millionEB Tech has a 400 kW system for around $2 EB Tech has a 400 kW system for around $2
M M
CommercializationCommercialization
Radiation Dynamics – Dynamitron - now a Radiation Dynamics – Dynamitron - now a member of IBA is around (Long Island)member of IBA is around (Long Island)
Jacob Applebaum – in central Florida is Jacob Applebaum – in central Florida is very interested – was involved in food very interested – was involved in food irradiationirradiation
Biggest problem with many E “beamers” is Biggest problem with many E “beamers” is that always want to build a new systemthat always want to build a new system
ThoughtsThoughts We have never quite figured out how to REALLY We have never quite figured out how to REALLY
assist ‘start-up’ companies commercialize new assist ‘start-up’ companies commercialize new processesprocesses
There needs to have thought given to a location There needs to have thought given to a location for testing and validation (third party)for testing and validation (third party)
Nobody wants to be first in the environmental Nobody wants to be first in the environmental field – especially where capital costs are high field – especially where capital costs are high
E Beam – no clients could get over the initial E Beam – no clients could get over the initial cost – even though O & M was minimalcost – even though O & M was minimal
Need to develop a system where biological Need to develop a system where biological treatment is last step and testedtreatment is last step and tested