technical advisory group meeting-minutes2labees.civil.fau.edu/technical advisory group...

Technical Advisory Group Meeting “Investigation of Energized Options for Leachate Management”

By D.E. Meeroff, C.T. Tsai, F. Gasnier, and T. Martin (Florida Atlantic University) Funded by the Florida Center for Solid and Hazardous Waste Management (FCSHWM)

DATE: Friday, October 27, 2006 TIME: 11:00 am WHERE: Solid Waste Authority 7501 N. Jog Road, West Palm Beach, FL 33412

Sign-In Sheet

Name: Joe Lurix Title: DEP Waste Program Administ. Address: 400 N. congress Avenue WPB, FL Email: [email protected] Phone: 561‐681‐6672 Name: Fred Bloetscher Title: Assistant Professor, FAU Address: 777 Glades Road Boca Raton, FL 33431 Email: [email protected] Phone: 561‐297‐0744 Name: Marc Bruner Title: Dir.Env.Programs/SWA Address: 7501 N. Jog Road West Palm Beach, FL 33412 Email: [email protected] Phone: 561‐640‐4000 Name: Shaowei Chen Title: Assistant Research Professor Address: 250 S. Ocean Blvd. Boca Raton, FL 33401 Email: [email protected] Phone: 561‐368‐0128 Name: Matt Zuccaro Title: Project Engineer CDM Address: 1601 Belvedere Road, Ste. 211 S West Palm Beach, FL Email: [email protected] Phone: 561‐689‐3336

Name: Richard Meyers Title: Project Manager III Address: 1 N. University Drive, Ste. 400 Plantation, FL 33324 Email: [email protected] Phone: 954‐474‐1848 Name: Manuel Hernandez Title: Project Engineer CDM Address: 1601 Belvedere Road, Ste. 211 S West Palm Beach, FL Email: [email protected] Phone: 561‐689‐3336 Name: Ray Schauer Title: Director Engineering, SWA Address: 7501 N. Jog Road West Palm Beach, FL 33412 Email: [email protected] Phone: 561‐640‐4000x4603 Name: John Booth Title: Executive Director, SWA Address: 7501 N. Jog Road West Palm Beach, FL 33412 Email: [email protected] Phone: 561‐640‐4000 Name: C.T. Tsai Title: Professor, FAU Address: 777 Glades Road Boca Raton, FL 33431 Email: [email protected] Phone: 561‐297‐2824

Minutes 1. Opening Address (11:15 PM) by Dr. Meeroff followed by introduction of the group members

and participants 2. Introduction of Landfill Leachate Project by Dr. Meeroff

- Objectives - Overview

3. Discussion of Study Methodology by François Gasnier - Literature review - Landfill surveys - Evaluation of leachate quality data - Evaluation of management strategies - Discussion of Photochemical Iron‐Mediated Aeration (PIMA) laboratory experiments

4. Discussion of Photocatalytic Nanoparticles by Dr. Shaowei Chen 5. Discussion of Future Work by Dr. Meeroff

- Summary of Energized Processes (in lay terms) - Management Model - Broader Impacts - Project Website - Acknowledgements

6. Discussion of TAG Input Needs (Open Forum)

‐ Previous Experiences ‐ General Discussion ‐ Dr. Bloetscher commented about upcoming reuse standards for permitting new deep

well injection systems ‐ Marc Bruner commented about residuals generated in the process and the possibility of

needed a TCLP analysis to determine if the residuals generated can be landfilled. ‐ John Booth asked for several clarifications about the potential applications of these new

technologies. ‐ Joe Lurix volunteered to provide additional information concerning leachate volumes

discharged as well as information concerning management technologies and contacts for solid waste management personnel not represented at this TAG meeting (i.e. Okeechobee, Medley, St. Lucie, Martin County)

7. Adjourn (12:35 PM), thank you for participating

1

Daniel E. Meeroff, Ph.D. Daniel E. Meeroff, Ph.D. ▪▪ FCSHWM Technical Advisory Group Meeting, West Palm Beach, FL FCSHWM Technical Advisory Group Meeting, West Palm Beach, FL ▪▪ Oct. 27, 2006Oct. 27, 2006

““Investigation of Energized Options Investigation of Energized Options For For LeachateLeachate ManagementManagement””

D.E. MEEROFF, Ph.D., E.I.Assistant Professor, Department of Civil Engineering, Florida Atlantic University

Director, Laboratories for Engineered Environmental SolutionsC.T. Tsai, Ph.D., S. Chen, Ph.D.

Professor, Department of Mechanical Engineering, Florida Atlantic UniversityF. Gasnier

MSCE, Florida Atlantic University

Presentation to the FCSHWM Technical Advisory GroupSolid Waste Authority of Palm Beach County, West Palm Beach, FL, October 27, 2006


AgendaAgenda

1. Introductions/Opening Remarks1. Introductions/Opening Remarks

2. Preliminary Results2. Preliminary Results

3. Photocatalytic Nanoparticles3. Photocatalytic Nanoparticles

4. Future Work/Open Forum4. Future Work/Open Forum

Dr. Meeroff

F. Gasnier

Dr. Chen

Everyone

2


Leachate IssuesLeachate Issues

• Leachate quality is highly variableType of solid waste (MSW, Ash monofill, C&D)Maturity of landfill

Color

Elevated TDS, BOD, NH3, VOCs

High COD/BOD

ratio

pH toxicity

Heavy metalsPb, As, Cd, Hg

PathogensOdor


RationaleRationale• All-inclusive solutions are not currently

available for leachate management• Need for sustainable options to safely

discharge to the environment• Futuristic energized processes developed

for detoxification of groundwater and soils may be the answer:

Photochemical Iron-Mediated Aeration (PIMA)TiO2-magnetite

3


Objectives of the ResearchObjectives of the Research

DevelopManagement Tool

DevelopManagement Tool

Evaluate EPs

Evaluate EPs

Evaluate AlternativesEvaluate

Alternatives

Objective 1Objective 1 Objective 2Objective 2 Objective 3Objective 3

• Review & collect leachate quality data

• Identify trends• Rank alternatives

(performance, risk, environmental and economic factors)

• Technical data (with the goal of achieving sewer discharge limits )

• PIMA• TiO2-Magnetite

• Preliminary cost analysis

• Preliminary risk assessment

• Web-based BMP guide

• Interactive and goal-based

Year 2Year 1


““Investigation of Energized Options Investigation of Energized Options For For LeachateLeachate ManagementManagement””


Director, Laboratories for Engineered Environmental SolutionsC.T. Tsai, Ph.D., S. Chen, Ph.D.


MSCE, Florida Atlantic University

Presentation to the FCSHWM Technical Advisory GroupSolid Waste Authority of Palm Beach County, West Palm Beach, FL, October 27, 2006

4


Future WorkFuture Work1. Design TiO2-magnetite reactor2. Complete scoping tests on Pb, TDS,

conductivity, ammonia, and COD3. Begin performance testing with

mixtures & actual leachate from SWA4. Develop cost analyses and risk

assessments for BMP guide5. Develop management tool


Management ToolManagement ToolUser

InterfaceProfileModule

User Input Profile

UserID

ContactInfo

LandfillType

LandfillAge

WasteGenRate

CurrentTechnology

TrtCapacity

ClimateData

BMPModule

ReportModule

InteractiveGoal-based

5


Benefits to the UniversityBenefits to the University• Stimulate progress

in technologies for reducing toxics

• Strengthen the cooperative relationship between FAU and SWA

• Hands-on student training in solid waste management


Additional SupportAdditional Support• FAU College of Engineering and Computer Science

Generous equipment donationNew ME/CE Nanoparticle Applications Laboratory

• Lanny and Kay Hickman Internship Program with the Solid Waste Authority of Palm Beach County

• USF Center for Biological Defense project• Leverage related work in technology development

for water quality restorationIn-situ remediation of hazardous waste sitesEDCs, DBPs, and membrane concentrate treatment

6


LabLab‐‐EES EES


NanoparticleNanoparticle Applications LabApplications Lab

Nanoparticle ApplicationsLaboratory

7


Web SiteWeb Site

www.civil.fau.edu/~daniel/labees/html/index.html


AcknowledgmentsAcknowledgments

1

Investigation Of Energized Options For Leachate

ManagementPresentation to the Technical Advisory Group

MeetingOctober 27, 2006, Solid Waste Authority of Palm Beach County,

West Palm Beach, FL


Director, Laboratories for Engineered Environmental SolutionsC.T. Tsai, Ph.D.


MSCE, Florida Atlantic UniversityDr. Shaowei Chen

Post-Doctoral Researcher

Outline Part 1

• Literature reviewLandfill surveysEvaluation of leachate quality dataEvaluation of management strategies

2

Literature Review (1/12)

• Goals:Collect leachate quality dataIdentify management alternatives with emphasis on energized options for leachate treatmentRank these alternatives according to:

Environmental sustainabilityEfficiencyRisksEconomic factorsPerformance experience (TAG member input)


• Methodology, tools usedFAU S.E. Wimberley Library services:

Electronic databases (FirstSearch)WorldCatElectronic journals

Internet:Reliable sources such as government or schools web sites (www.epa.gov, www.dep.state.fl.us)

Record Review at the FDEP of Palm Beach

3


• Landfill survey in Florida:25 million tons of MSW were generated across the State in 2000 (FDEP 2002)58% is landfilled in

60 Class I landfills34 Class III landfills11 ash monofill landfills


• ResultsLeachate quality data worldwide and more precisely in Florida

Florida leachate characteristics Worldwide leachate characteristics

Parameters Range Average

Lead in mg/L

pH

Conductivity in μS/cm

TDS in mg/L

Ammonia in mg/L as N

COD in mg/L as O2

BOD5 in mg/L

TSS in mg/L

Concentrations

BDL - 0.1 0.03

1,000 - 95,000 11,600

n/a n/a

900 - 88,000 9,300

BDL - 1,350 500

55 - 14,000 3,000

BDL - 445 150

2.0 - 11.3 7.5

Parameters Range Average

BOD5 in mg/L

pH

0.11

5.2 - 95,000 13,000

0 - 88,000 11,000

Lead in mg/L

Conductivity in μS/cm

TDS in mg/L

BDL - 5.0

Ammonia in mg/L as N

COD in mg/L

Concentrations

TSS in mg/L n/a n/a

0.1 - 8,750 850

2.0 - 11.3 7.5

0.4 - 152,000 10,600

BDL - 80,800 4,100

4


• Results, continuedCompilation of several sources across the world and FloridaLarge range of concentrations for all constituentsFlorida leachate is lower strength than the worldwide average: one explanation is the dilution due to climate impactsCan one technology handle this special type of wastewater?

• Evaluating existing alternatives


• Existing alternatives1. MUNICIPAL SEWER DISCHARGE:

A common optionDoes not address bio-toxicsA flow > 5% will disrupt WWTP’s due to high COD and ammonia, (Boyle and Ham 1974, Chain and DeWalle 1977)

2. NATURAL ATTENUATIONDeep well injection (monitoring problems)Evaporation ponds (does not work in Florida due to the climate)

5


• Existing alternatives, continued3. HAULING OFF-SITE

Does not address the problem, just displaces itHigh transportation risk and cost: $110 per 1,000 gal (Polk County)

4. LEACHATE RECIRCULATIONUnder study by the Florida Center, showed great reduction capacities (Morris et al. 2003)Mass balance issue: the leachate cannot be recirculated endlessly


• Existing alternatives, continued5. ON-SITE TREATMENT:

Biological processes› Equivalent to discharge to a WWTP› Does not address bio-toxics

Physical and chemical processes (air stripping, precipitation, ion exchange, filtration, etc.)

› Transfer pollutants to another media› Issue with concentrates and residuals

6


• Comparative statement of the onsite treatment alternatives

Technology % COD removal Source

Acclimated sludge

Coagulation and flocculation

Coagulation and flocculation

93 Anagiotou et al. (1993)

Silva et al. (2003)

Wu et al. (2004)

Slater et al. (1983)

23

60

68Reverse osmosis


• Advanced Oxidation Processes (AOP’s) or Energized Processes (EP’s) can be the solution

AOP = near ambient temperature and pressure water treatment processes which involve the generation of hydroxyl radicals in sufficient quantity to effect water purification, Glaze et al. (1987)

H2O2, Fenton (H2O2/Fe2+) , O3, IMAEP = AOP + UV energy

UV, UV/ H2O2, Photo-Fenton, PIMA, TiO2-magnetite

7


• Comparative statement of the AOP’s and EP’s% COD removal Source

PIMA ?

Technology

H2O2

H2O2

Fenton

16

60

35

Fenton

Ozone

Loizidou et al. (1993)

Shu et al. (2006)


Englehardt et al. (2005)

UV / H2O2 65 Shu et al. (2006)EP

Photo-Fenton 70 Soo-M. Kim et al. (1997)

IMA 56 Englehardt et al. (2005)

UV / O3 / H2O2 89 Ince (1998)

AOP

UV / H2O2 59 Ince (1998)

UV / O3 54 Ince (1998)

61

35 Imai et al. (1998)


• Several treatment options available• All show pros and cons• None seems totally efficient, but EP’s show

the best results

Developing other technologies such as the PIMA process could offer a future alternative.

8

Outline Part 2

Photochemical Iron Mediated Aeration Process (PIMA)

PrincipleLaboratory scale reactorMethodologyPreliminary results

PIMA principle

• Reaction mechanism not completely known, but evidence suggests:

The oxidation of Fe to Fe2+

The creation of hydroxyl radical HO• by 2 paths:Photo-Fenton reaction Interaction of UV energy with water

The removal action of HO•

9

PIMA reactor (1/3)

PIMA reactor (2/3)

10

PIMA reactor (3/3)

Humidifier Test tubes and lamp

Methodology (1/2)

• Pilot reactor used to develop preliminary testing conditions with simulated leachate:

Air requirementsMass of catalyst/reactantUV intensityReaction times: sampling after 0, 2, 6, 16 and 24 hours of treatmentpH monitored (~6), but not adjusted

11

Methodology (2/2)

• Pilot reactor used to generate performance data that are currently not available for the PIMA process on these five constituents:

AmmoniaCODBOD5

Conductivity and TDSLead

Preliminary Results (1/6)

• Scoping tests on simulated leachateEvaluation, adjustments, validation of the reactorMethod development for the monitoring of the pollutantsValidation of expected results with simulated leachate prior to using real leachate samples

12

Preliminary Results: COD (2/6)• 3 Scoping tests conducted on low (1,500 mg/L),

medium (3,300 mg/L) and high (11,000 mg/L) levels

• Best overall removal efficiency of 44% after 24 hrs on COD with the PIMA process and 54% on the low level

C / C0 versus Time

0.00

0.20

0.40

0.60

0.80

1.00

0 5 10 15 20 25

Time in hrs

C /

C0

UV, x = 10.2 cm IMA, x = 10.2 cm PIMA, x = 6.3 cm PIMA, x = 10.2 cm PIMA, x = 15.2 cm

Preliminary Results: Ammonia (3/6)• 3 Scoping tests conducted on low (110 mg/L),

medium (550 mg/L) and high (925 mg/L) levels

• Despite the air stripping, a low removal of ammonia has been observed

C / C0 versus Time

0.00

0.20

0.40

0.60

0.80

1.00

1.20

0 5 10 15 20 25

Time in hrs

C /

C0


13

Preliminary Results: BOD5 (4/6)• 3 Scoping tests conducted on low (55 mg/L),

medium (125 mg/L) and high (425 mg/L) levels

• Best removal efficiency of 56% after 16 hrs on BOD5 with the PIMA process

C / C 0 v e r s u s T im e

0 .0 0

0 .2 0

0 .4 0

0 .6 0

0 .8 0

1 .0 0

1 .2 0

0 2 4 6 8 1 0 1 2 1 4 1 6 1 8

T im e in h rs

C /

C 0

IM A , x = 1 0 .2 c m PIM A , x = 1 0 .2 c m

Preliminary Results: TDS (5/6)• 2 Scoping tests conducted on medium (8,125

mg/L) and high (40,000 mg/L) levels

• No removal observed. Increase probably due to dissolving iron.

C / C0 versus Time

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

0 5 10 15 20 25

Time in hrs

C /

C0


14

Preliminary Results: Conductivity (6/6)• 2 Scoping tests conducted on medium (16,250

µS/cm) and high (81,600 mg/L) levels

• Same conclusion than for TDS

C / C0 versus Time

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

0 5 10 15 20 25

Time in hrs

C /

C0


Conclusion

• Literature review almost complete• PIMA reactor fully operational• Reactor parameters are being measured and

will be checked regularly.• Monitoring program of experiments established• 2 more scoping tests to be performed followed

by simulated mixtures and then real leachate.

15

Conclusion

• Comparative statement of the AOP’s and EP’s, including the PIMA process

Low level experiment reduced COD concen-tration below the Boca Raton sewer discharge limit.

% COD removal Source

PIMA 54 Present work

Technology

H2O2

H2O2

Fenton

16

60

35

Fenton

Ozone


Shu et al. (2006)


Englehardt et al. (2005)

UV / H2O2 65 Shu et al. (2006)EP

Photo-Fenton 70 Soo-M. Kim et al. (1997)

IMA 56 Englehardt et al. (2005)

UV / O3 / H2O2 89 Ince (1998)

AOP

UV / H2O2 59 Ince (1998)

UV / O3 54 Ince (1998)

61

35 Imai et al. (1998)

Next Steps

• 1 scoping test on Pb, and 1 on TDS and conductivity

• Scoping tests on simulated mixture (BOD5 & COD, ammonia & TDS)

• Collect real leachate samples from the Solid Waste Authority of Palm Beach County (FL) and evaluate the PIMA process

• Rank the available alternatives including the new PIMA process (TAG input)

16

Investigation Of Energized Options For Leachate

ManagementPresentation to the Technical Advisory Group Meeting

October 27, 2006, Solid Waste Authority of Palm Beach County, West Palm Beach, FL


Director, Laboratories for Engineered Environmental SolutionsC.T. Tsai, Ph.D.


MSCE, Florida Atlantic UniversityDr. Shaowei Chen

Post-Doctoral Researcher

Discussion

• Questions without answer, yet!Statistics and process performance data concerning the treatment methods used in Florida:

Leachate quantitiesCurrent management practicesLeachate quality data (influent and effluent)

Rank the viable alternatives (the alternatives table is being constructed)

• Previous experiences/issues• General discussion

17

Goals: Sewer limits

• City of Boca Raton Sewer Use Policy Limits Regulated Pollutants:

Iron: 21.0 mg/LLead: 0.37 mg/LTotal Dissolved Solids: 2000.0 mg/LCOD: 800.0 mg/LBOD5: 400.0 mg/LpH: 6.0 – 8.5(Maximum allowable value over any 24 hrs period)

1

Photocatalyst TiO2 Coated Magnetic Composite Nanoparticle

And Potential Application in Leachate Treatment

Dr. Shaowei Chen and Dr. C.T. TsaiFlorida Atlantic University

October 27, 2006

Background

– Magnetic TiO2 nanoparticles• Larger surface area in unit volume (~100-400 sqm/g)• Higher efficiency in treating environmental

contamination• TiO2 is extractable and reusable.• TiO2 is currently the most popular and effective

photocatalyst for a number of applicationsOxidation of organic pollutantsRemoval of inorganic pollutants in waterPhotoreduction of N2 or CO2 Photodestruction of cancer cells, bacteria and virus

2

Possible Application In Landfill Leachates Treatment

• photocatalytic oxidation (PCO) to break down and destroy many types of organic pollutants.

• It has been used to purify drinking water• destroy bacteria and viruses• remove metals from waste streams, and • breakdown organics into simpler components of

water and CO2. • The treatment of non-biodegradable organics • The photocatalytic process (UV/TiO2) has

proved to be effective for the decolourisation as well as mineralization of humic acids solution

Process - Results1. The process occurs under ambient

conditions2. The formation of photocyclized intermediate

products3. Oxidation of the substrates to CO2 is

complete 4. TiO2 can be supported on suitable reactor

substrates 5. The process offers great potential as an

industrial technology to detoxify wastewaters

3

Photocatalytic Principle• Irradiated with UV light (sun light or near λ< 400 nm)

semiconductor TiO2 produces electron-hole pairs that can initiative reductive & oxidative reactions on the surface

• The injection of these electrons and holes into fluid region surrounding the TiO2 particles causes electrochemical modification of substance within the region

• Redox reaction – produce hydroxyl radicals that can oxidize most organic pollutants or microbial agents

• The pollutant could be dissolved (organic/inorganic)

Problems• If TiO2 is in solution then some sort

of recovery system is necessary in order to reuse the catalyst

• TiO2 particles are electrical insulator

• Difficult to extract and recycle

4

Synthesis of Titania Coated Magnetic Nanoparticle

• Methods– Sol-Gel technique

• The core particles (Fe3O4) are produced by a chemical process and then dispersed in the coating solution

• Hydrolysis of titanium butoxide (Ti4O2) in the presence of seeds particle (4-10 nm) – deposition

• Size hard to control (>300nm) – in bulk solution• Clustered magnetite • TiO2 porosity – incomplete encapsulation of

magnetite core surface

General procedure of sol-gel technique

• Alkoxides dissolved an alcoholic solution to form the corresponding hydroxide

• Condensation of the hydroxide molecules by elimination of water leads to formation of a network of metal hydroxide. When all hydroxide species are linked in one networklike structure, gelation is achived

• The gel is a polymer of 3-dimensional skeleton surrounding interconnected pores

• Removal of the solvents and appropriate drying of the gel results in an ultrafine powder the metal hydroxide.

• Further heat treatment the hydroxide leads to the corresponding nanosize metal oxide

5

Sol-Gel MethodsFe3O4 seed EtOH

(half)(half)

H2O HClTBOT

Alcoholic solutionof TBOT & Fe3O4

Hydrolysis &condensation

Gel at 295K

Dry at 338k

Thermal treatment at 723 K

TiO2-Fe3O4

– Proposed Novel Microemusion Process • W/O emulsion to create “Microreactor” or

“Water pool”, reactionTiCl4 + H2O → TiOCl2 + 2HCl

control heating and ageing Time, Temperature, pH, pool compositions

• Controlling the size and shape of the assemblies – Mixing, Surfactant

• Effectively control the resulting nanoparticlesize by control the dimension of “Microreactor”

6

Organic Solvent

Surfactant

FeCl2 aqueous solution

Microemultion

NH4OH

Organic phaseWater phase

Surfactant

Fe3O4 nanoparticle

Formation of Fe3O4 nanoparticlesin microemulsion

Aging at 50∼100 °C

TiOCl2 aqueous solution

TiO2

Formation of TiO2 coating on nano Fe3O4

TiO2 Fe3O4

Nanoparticles composed of a Fe3O4 core and a TiO2 shell

Heat treating

Centrifuging, washing and drying

Schematic showing the w/o microemulsion process for synthesizing TiO2 coated Fe3O4 nanoparticles.

Advantages of Microemulsionmethod

• uniform size – Limited within the “microreactor”

• spherical shape • Homogeneous precipitation of TiO2

• Heterogeneously onto the magnetic (Fe3O4) nanoparticles

• complete encapsulation of Fe3O4

magnetite by TiO2

• no aggregation

7

Control of particle size and agglomeration

• No work has been found on synthesizing TiO2 coated Fe3O4 composite nanoparticles

• Related reports – SiO2/Fe3O4 (see Fig.)

Particles by Sol-Gelmethod

Fig2 TEM morphology of the sample (d)

Sample ( d) is the hydrolysis of Titanium Butoxide in absolute alcohol medium

(d)

280nm

Fig1 TEM morphology of the sample (c)

Sample (c) is prepared by hydrolysis

of Titanium Butoxide in 95% alcohol acidic medium

200nm

(c)

8

TEM photographs of SiO2 coated Fe3O4 nanoparticles

prepared using a w/o microemulsion method

Conclusion• TiO2/Fe3O4 core-shell structure magnetic nanoparticle

can:– Apply magnetic stir to increase photocatalyst efficiency and – Low-cost inorganic metal salt will be used rather than commonly

used expensive metal-alkoxides– Subject to be reuse (recycle) to lower cost

• Collection by megnetic field• Calcination to remove contaminants

• The non-hazardous, reusable catalyst (TiO2), solar energy (UV) and atmospheric oxygen

• The photocatalytic process can occur in ambient condition make it feasible to construct an efficient landfill leachate treatment system

technical advisory group meeting-minutes2labees.civil.fau.edu/technical advisory group...

Documents