Overall research trends in nano-based water treatment ... · Nano-based Water Treatment Technologies ... This year marks the 41st anniversary of the MEST as well as the 42nd anniversary

Overall research trends in nano-based water treatment technologies in South Korea

2009. 7. 16.

Young H. Lee, Ph.D.

Senior Research ScientistCenter for Environment Technology Research

Korea Institute of Science and Technology (KIST)

Nano-based Water Treatment Technologies

Introduction of KIST and Center for Environment Technology Research

Current Researches in Nano-based Water Treatment Technologies • Phosphate Removal by Zirconium Mesostructures • Photocatalytic Oxidation of Dioxane by using Gold

Nanoparticles supported on Titania• Reduction of Nitrate by Resin-supported Nanoscale

Zero-valent Iron• Membrane-coupled Water Treatment Technologies

This year marks the 41st anniversary of the MEST as well as the 42nd anniversary of the KIST. Throughout these years KIST has been the incubator of national S&T development, spearheading the achievements which have enabled Korea to become one of the world’s top 10

economic powers.

Personnel

R&D Budget~160 million$

Korea Institute of Science and Technology

Total: 1808Location : Seoul, South Korea

Gangneung Institute

Established in 1966Multidisciplinary research institute of science and technology in SeoulLand area: 271,527m2

11 research buildings

Seoul Headquarters

KIST Europe(Germany)

Seoul Headquarters

Chonbuk Institute

Development Path of KIST

Adoption & modification ofimported advanced

technologies

Key industrial technologies,public & welfare technologies

Frontier & fundamentaltechnologies

Fast industrialization byimporting technologies

and materials

Developing major industrialtechnologies and

Advancing quality of life

Ensuring the core competencyfor The 21st century

knowledge - based economy

KIST established

1966 70s 80s 90s 21C

SCI research articlesOther

Total number

1,000 9781,026 1,038

500

0

612

366

654

372

706

332332366366

654

372372

706

332332332366366

800

Application Registration

450

300

401

320

405423

200

250

350

400

439442423

401401

320

405

320320

Research Articles Patent

Annual contract income

Total number

20

2123 24

2

Unit : $ Million

1.8

2.72.2

3

1

2.72.2

1.8

Technology Transfer

Moscow OfficeSiberia Office

Russia

FranceKIST- CNRS LIA

ItalyKIST-SSSA Lab

Korea-Mongolia CenterMongolia

MIT Lab CMU Lab

U.S.A.

GermanyKIST Europe

CAS (China), CEA, CNRS LIA (France), IISc (India), WUT (Poland),MSU (Russia), BNL, Purdue University (U.S.A), AIT(Thailand),Korea-Germany Nanophotonics Workshop, Korea-Mongolia Joint Workshop,Korea-South Africa Joint Workshop

Annual Joint Symposium

5 Main Research Fields

Center for Environmental Technology Research

20 Ph.D. researchers(Total 103)

Funding: 10~12 million $/yr

10

Core Technology Sustainable Society

FutureFusionTech.

Advanced Water& WW Treatment

Technology(MBR, AOPs, etc)

Fusion Technology(Nano-ET, Bio-ET, etc)

Monitoring(Biosensor, Test Kits)

RenewableEnergy Production(Biogas, Biofuel

Production)Phytoremediation

Major Research Areas in Water Environment

Phosphate Removal by Zirconium Mesostructures

Entrapped in Calcium Alginate

Dr. Sang-hyup Lee

Introduction : Research Background

Limited resources of phosphate Exhaustion within 100 years

Deposit

Increase Rate

year

Phos

phat

e m

iner

al (b

illio

n To

n)

Fundamental Deposit

Demand of highly effective technology for phosphate recovery from various wastewaters

Life of phosphate ores (USGS, 2002)

Zr-mesostructure as the promising adsorbent for phosphate recovery

Reject water as the potential resource for phosphate recovery


1. Eutrophication control2. Zirconium Mesoporous structure (ZM) for

removing the phosphorus3. Powder-form ZM

1. packing difficulty of the bed2. decreasing free flow with the operation3. high operating pressure caused by

suspended solids accumulated in the bed.

The reusability of ZM powder► ZM entrapped in calcium alginate (Ca-Alg)

for practical application

Synthesis of Entrapped Zirconium Mesostructure

Drying for 24 hrs at room temperature

Sodium Alginate 10 % w/v ZM powder 30 ~70 % w/v

Crosslinker : Calcium chloride 1 % w/v + Hardener: polyethylenimine 5 % w/v

Mixing for 3 hrs at room temperature

30 % Zr(SO4)2CTABr & 10 % Alginate





Cs=bQmaxCe/(1+bCe)Cs : sorption amount, Ce: equilibrium conc.,

b : Langmuir constant, Qmax: max. sorption amount

Langmuir sorption isotherm model

dqt / dt = k(qe-qt)2

qe : sorption amount at equilibrium, qt: sorption amount at t., t :time, k : reaction rate constant

Pseudo-second order kinetic model

Effects of the ZM Contents in Calcium Alginate on the Removal of Phosphate (1)

Condition: initial phosphate concentration = 1000 ppm; equilibriumtime = 24 hours; ZM content = 30 ~ 60 % w/v; sodium alginate = 10 %w/v; ZM_Ca-Alg dosage = 0.30 ~ 1.0 g; and at 20 ℃.

Equilibrium Conc. of solution [mg/L]

0 200 400 600 800 1000

Mas

s of

phs

phat

e so

rbed

to

uni

t wei

ght o

f sor

bent

[mg/

g]

0

10

20

30

40

50

60

30 % Zr-alginate particle40 % Zr-alginate particle50 % Zr-alginate particle60 % Zr-alginate particle

sample Qmax [mg/g] b [L/kg] r2

30% ZM_Ca-Alg 26.95 0.006 0.98

40% ZM_Ca-Alg 31.31 0.012 0.99

50% ZM_Ca-Alg 38.44 0.021 0.99

60% ZM_Ca-Alg51.74

(1.63meq/g)0.058 0.98

Langmuir constants

Cs=bQmaxCe/(1+bCe)Cs : sorption amount, Ce: equilibrium conc.,

b : Langmuir constant, Qmax: max. sorption amount

Langmuir isotherm

30 % w/v ZM = 66.7 % of total mass40 % w/v ZM = 73.0 % of total mass50 % w/v ZM = 76.9 % of total mass60 % w/v ZM = 80.0 % of total mass

The max. sorption capacity increases as the ZM content increases


Condition: initial phosphate concentration = 1000 ppm; equilibriumtime = 24 hours; ZM content = 30 ~ 60 % w/v; sodium alginate = 10 %w/v; ZM_Ca-Alg dosage = 0.30 ~ 1.0 g; and at 20 ℃.

Time elapsed [min.]

0 200 400 600 800 1000 1200 1400 1600

Mas

s of

pho

phat

e so

rbed

to u

nit g

ram

of s

orbe

nt [m

g/g]

0

5

10

15

20

25

30 % Zr-alginate particle40 % Zr-alginate particle50 % Zr-alginate particle60 % Zr-alginate particle

k [g/mg min] qe[mg/g] r2

30% ZM_Ca-Alg 1.17 * 10-4 23.81 0.88

40% ZM_Ca-Alg 0.65 * 10-4 28.18 0.96

50% ZM_Ca-Alg 0.30 * 10-4 35.29 0.97

60% ZM_Ca-Alg 0.23 * 10-4 39.84 0.95




Kinetic constants

The overall reaction rate decreases as the ZM content increases


60 % w/v ZM (80% of total mass) in Ca-Alg. bead

30 % w/v ZM (66.7% of total mass) in Ca-Alg. bead

Overall reaction rate= f (1/Zr mesostructure content)

Ca-AlginateZr mesostructure

Entrapmentsize of pore opening < immobilized catalyst

Sorption Kinetics

Effects of the Bead Size on the Removal of Phosphate

Condition: initial phosphate concentration = 1000 ppm; equilibriumtime = 24 hours; ZM content = 60 % w/v; sodium alginate = 10 % w/v;ZM_Ca-Alg dosage = 0.30 ~ 1.0 g; bead size, mean diameter = 10.17,30.15, 70.12 mm; and at 20 ℃.

k [g/mg min] qe[mg/g] r2

1mm ZM_Ca-Alg 1.00 * 10-4 62.89 0.99

3mm ZM_Ca-Alg 0.41 * 10-4 59.33 0.99

7mm ZM_Ca-Alg 0.23 * 10-4 40.28 0.99




Kinetic constants

Time elapsed (min)

0 200 400 600 800 1000 1200 1400 1600

Phos

phat

e so

rptio

n am

ount

(mg/

g)

0

10

20

30

40

50

60

70

7mm size 3 mm size 1 mm size

Smaller beads have the higher frequency to react with phosphate ions

Comparison of zirconium mesostructure with Ion-exchange resin (IRA 402 Cl)

qe[mg/g] k [g/mg min] Equivalent [meq/g]Zirconium mesostructure(powder)

163.40 9.0 * 10-4 5.17

Zirconium mesostructure(powder) after surfactant template removal

378.71 9.0 * 10-4 11.98

Anion exchange resin (IRA 402Cl)

80.47 3.0 * 10-4 2.54

Adsorption constants

5

11 times

30% 40%

50% 60%

ZM powders (white color)are entrapped by calciumalginate (dark graycolor)

ZM powders (white color)

calcium alginate(dark gray color)

Regeneration of Zr-Alg Beads (1)

Phosphate removal process

Feed solution containing phosphate

adsorption

Desorption regeneration

processPhosphate adsorbed zirconium

mesostructures

RegenerationChemicalregeneration(NaOH, NaCl, Na2SO4)

Electroregeneration

FlushingDistilled water

Regenerated mesostructures

Phosphate recovery process

Exhausted desorption

solution

desorption solution

Supply of NaOH

addition of CaCl2

Calcium phosphate

ElectroregenerationAEM: anion exchange membrane

ELECTROREGENERATION-Power consumption (@ 1.0 mA/cm2) 1.06 Wh/L

- Power 1.07 W- regeneration efficiency 96%

Regeneration solution k [g/mg min] qe[mg/g] r2

Zr-Alg before saturation 9.07 * 10-4 49.65 0.99

NaOH

0.3N 11.04 * 10-4 46.38 0.990.5N 10.52 * 10-4 46.70 0.990.7N 10.01 * 10-4 46.94 0.991.0N 9.75 * 10-4 46.70 0.99

NaCl

0.3N 9.56 * 10-4 47.07 0.990.5N 9.34 * 10-4 48.16 0.990.7N 8.79 * 10-4 49.42 0.991.0N 8.65 * 10-4 49.56 0.99

Na2SO4

0.3N 9.48 * 10-4 47.34 0.990.5N 9.42 * 10-4 47.57 0.990.7N 9.35 * 10-4 47.45 0.991.0N 9.28 * 10-4 47.74 0.99

Electrochemical regeneration 9.97 * 10-4 47.85 0.99

Adsorption constants Regeneration efficiency 93 ~ 99%

Time elapsed (min)

0 200 400 600 800 1000 1200 1400 1600

Mas

s of

pho

spha

te s

orbe

d to

uni

t gra

m o

f sor

bent

(mg/

g)

01045

46

47

48

49

50

Zr-Alg before saturationNaOH-0.3 NNaOH-0.5 NNaOH-0.7 NNaOH-1.0 NNaCl-0.3 NNaCl-0.5 NNaCl-0.7 NNaCl-1.0 NNa2SO4-0.3 NNa2SO4-0.5 NNa2SO4-0.7 NNa2SO4-1.0 NElectroregeneration

Regeneration of Zr-Alg Beads (2)

Summary

The powder of zirconium mesostructure (ZM), which was prepared with the

template of surfactant, was successfully entrapped in calcium alginate for

practical application.

This study showed that the zirconium mesostructure bead could be used as a

promising adsorbent material for the treatment of phosphate ion.

Prior to field application, the problem of high cost for preparing ZM powder

should be addressed. It is speculated that the high cost for ZM powder might be

compensated by • increasing the sorption capacity of ZM beads through the removal of

surfactant template which occupies the potential sorption sites in ZM, • regenerating the ZM bead for reuse by chemical treatment or by

electrochemical treatment.• These possibilities are now under estimation, and the results will be

reported minutely in near future.

Tuning of the Photocatalytic Oxidation with Surface

Plasmon Resonance of Gold Nanoparticles on Titania

Drs. Byoung K. Min and Young H. Lee

Time (min)

Dye

Con

cent

ratio

n (m

g/L)

0

10

20

30

40

50

60TiO2 0.05g/L TiO2 0.10g/L TiO2 0.25g/L TiO2 0.50g/L TiO2 1.00g/L

604020 120100800Time (min)

0 10 20 30 40 50 60

Dye

Con

cent

ratio

n (m

g/L)

0

10

20

30

40

50

60

6 W18 W24 W30 W36 W

UV Lamp: 36 W(no O2 purging)

TiO2: 1.0 g/L(O2 purging at 100 mL/min)

0 10 20 30 40 50 60 90 120 min

Introduction : Photocatalytic Oxidation

- TiO2 (Degussa P-25)- UV-C lamp 6 W X 6 (max =

254 nm, Philips TUV)


Gold nanoparticles have been highlighted to promote the photocatalyticactivity of TiO2 by acting as a role of

The field enhanced light absorption

The assistant for charge separation

The sensitizer for visible light

Surface plasmon resonance originating from the collective oscillations of the electrons on the surface of the gold nanoparticles has been suggested as the essential factor

Visible light can be absorbed by gold nanoparticles due to the surface plasmon resonance which leads to the photoexcited state of the gold nanoparticles followed by the transfer of the electrons into the TiO2

1,4-dioxane which has been widely used as an industrial solvent and as a stabilizer for chlorinated solvent, and is also known as a toxic hazard and is suspected to be a potential carcinogen for humans

Preparation of Modified Au-TiO2 (P25) Samples

400 500 600 700 800

0.0

0.2

0.4

Abs

orba

nce

(a.u

.)

Wavelength (nm)

- Leaching procedure- Gold nanoparticles supported TiO2

generates light absorption in the range of visible light (400–800 nm) due to the surface plasmon resonance

- Absorbance spectra in the range of visible light for a TiO2 (P25) (gray dash)- An as-prepared (commercial) Au–TiO2 (gray solid), a leached Au–TiO2 for 15 sec (black dots) - A leached Au–TiO2 for 30 sec (black solid), a leached Au–TiO2 for 1 min (black dash)- A leached Au–TiO2 for 10 min (black short dash), a leached Au–TiO2 for 30 min (black dash-

dot), A leached Au–TiO2 for 13 hr (black dash-dot–dot).

Preparation of Modified Au-TiO2 (P25) Samples

200

400

600

800

0

4

8

12

1.2 0.8 0.4 0.00

4

8

12

Total Amount of Gold (wt%)

Size

(nm

)

Num

ber D

ensi

ty (1

09 cm-2)

d- TEM images of (a) an as-

prepared Au–TiO2, (b) a leached Au–TiO2 for 30 sec, and (c) a leached Au–TiO2 for 10 min.

- (d) The plots of number density (empty squares) and size (filled squares) of gold nanoparticles on TiO2 with respect to the total amount of gold.

Photocatalytic Degradation of Dioxane (1)

0 1 2 3 4

0.4

0.6

0.8

1.0

C/C

o

Time (hr)

● as-prepared Au-TiO2□ 30 sec leaching Au-TiO2■ 10 min leaching Au-TiO2○ 1 hr leaching Au-TiO2

• The efficiency of the 1,4-dioxane photodegradation was enhanced by the sample prepared by the leaching procedure.

• In the case of the 30 sec leaching Au–TiO2, 59% of the 1,4-dioxane was decomposed in 4 h reaction.

• Notably, the sample prepared by the 1 h leaching was basically in the same state as the TiO2 itself since no gold moiety was detected.

- Reactor (10 cm Ý 5 cm Ý 10cm) with a quartz window

- TiO2 and/or Au–TiO2powders (0.5 g/l)

- IR filter was installed in front of a light source.

- An Xe-lamp (2 kW) was used as a light source, and its irradiation intensity was calibrated to 100 mW/cm2

with a standard reference solar cell

Photocatalytic Degradation of Dioxane (2)

0

20

40

60

80

0 200 400 600 800

20

40

60

Rea

ctiv

ity [1

-C/C

o] (%

)

SPA

Inte

nsity

(a.u

.)

Leaching Time (min)

TiO2(P25)

0 5 1040

50

60

70

0 5 1020

40

60

• The reactivity of 1,4-dioxane photodegradation more clearly revealed their strong relationship with the overall intensity of the surface plasmon absorption

Summary

The promoting effect of gold was found to be strongly correlated

with its surface plasmon resonance of which the magnitude is

sensitive to the density and size of gold nanoparticles.

The surface plasmon resonance of gold nanoparticles may assist

to separate the charges created in TiO2, which resulted in

enhancing the catalytic activity of TiO2 for 1,4-dioxane

photodegradation.

Enhanced Reduction of Nitrate by Resin-supported Nanoscale Zero-valent Iron

Drs. Sang-hyup Lee and Young H. Lee


• Contamination status by Nitrate– A wide range of contamination– Groundwater contamination of farm circumstance

– Effective removal techniques for Nitrate in groundwater is needed

bacteria

bacillus

pH

chloride ion

Nitrate

Contamination Ratio of Contaminatants

0

10

20

30

40

50

60

70

80

'02 '03 '04 '05 '06

Contamination Status ofNitrate Contamination in Ground Water

Permeable Reactive Barrier (PRB) System

Nanoscale Zero-Valent Iron (n-ZVI)

Contaminants

• Chlorinated VOCs

• Nitrates

• Metals (e.g. Cr, As)

•Chlorinated Pesticides

10 – 600 nm

e-Fe2+

Fe0

RClnRHn + nCl-

NO3-

NH4+ or N2

To increase the reactivity, nanosizedZVI has been introduced. Its surface area is 30 times larger than

the regular ZVI & 1 to 1000 times higher reactivity has been reported.

Alternative for Nano-Scale ZVI demerits

Problem

Reduction of Nitrates Using nZVI having high reactivity

High reactivity decreases its stabilityApplication is limited due to its fine

powdery characteristicAmmonium can be released

Solution

Use a supporter that can adsorb ammonium

NO3- + 4Fe + 10H+ → 4Fe 2+ + NH4

+ + 3H2OHuang et al. (1998)

NO3- + 8Fe + 10H+ → 8Fe 3+ + NH4

+ + 3H2OHuang and Zhang (2004)

NO3- + 4Fe + 7H2O → 4Fe 2+ + NH4

+ + 10OH-

Till et al. (1998)

6NO3- + 10Fe + 3H2O → 5Fe2O3 + 3N2 + 6OH-

Flis (1991)

2NO3- + 5Fe + 6H2O → 5Fe 2+ + N2 + 12OH-

Chew and Zhang (1998)

Resin-supported nZVI

Fe-coating on anion exchange resin (Amberlyst 15 wet)

Material packing

Fe(II) loading with FeCl2 solution

Fe(II) reduction to Fe(0) with NaBH4

Drying with N2 gas

Preparation of resin-supported nZVI The properties of the supported nZVI

Fe adsortion(m g Fe/g)

BETSurface area

(m 2/g)

A verage size(m m )

Perm eability Coefficient

Com pression Strength(kg/cm 2)

6.86 35.00 0.72 2.0 ×10-2 1.122

BETsurface area

(m 2/g)

m edian pore w idth(nm )

m icropore volum e (cm 3/g)

m esopore volum e (cm 3/g)

cum ulative pore volum e (cm 3/g)

originalresin

78.41 37.95 0 0.973 1.00

Fe-loadedresin

56.00 31.48 0 0.375 0.51

The changes of surface area and pore distributionZero Valent Iron

Resin

Nitrate Reduction by the Supported nZVI

• In an early stage, high reaction rate constant was observed

• Its reactivity was lost as the reaction proceeded.

• Mass transfer limitation

3

3 NOkdt

NOr obsPseudo first order kinetic model

Resin-supported nZVI for Field Test

Fe(+ 2) ion adsorption Create Fe(0+ )

Resin-Supported nZV I

Tank for R eactive m aterial

Colum n for ZV I A dsorption

Tank for m aterial synthesized

Field Test Result of PRB System

0

1

4

6

8

10

12

14

16

18

20

22

24

26

28

30Results of soil sample analyses

- NO3--N : 0~38.46mg/kg (78%)

- TN : 33~626mg/kg (24%)

- TP : 143.08~2,918.88mg/kg

- pH : 5.01~8.8 NO3--N Contamination range

Groundwater Analysis

- 10 groundwater monitoring wells

- Installation depth : 5m

(Casing 1m, Screen 4m)

PRB

PRB

Location : Chungchungnam-Do, Chunbuk-Myun

Summary

The surface area of the resin-supported nZVI was increased.

Its reaction rate was high in 0.4255 h-1 , and then decreased to

0.0436 h-1 due to the limitation of mass transfer.

Reduction of Nitrate without ammonium release was achieved.

Nano-based Technology for Membrane-coupled Wastewater

Treatment System

Drs. Young H. Lee, Jinwoo Cho, Sang-hyup Lee, and Seokheon Lee

Background

World market prediction

45% of current desalination plant (38,000,000 m3/d) is SWRO.

IDA prediction: 31,000,000 m3/d will be constructed within 10 years.

Fast growing market (yearly 17%)

Demands large scale (over 50,000 m3/d)

Characteristics of SWRO market

Desalination process using SWRO

http://www.awa.asn.au

Intake

Pretreatment

RO Process

Post treatment

Treated waterStorage

PretreatmentPretreatmentPretreatmentPretreatment

Development of Optimal Pretreatment Process Tailored by Raw Seawater Quality

Fouled membrane from SWRO plant

RO membrane autopsy

CLSMDisinfectant

CLSM analysis

CDC reactorsystem

CYTO9 (Live, green), PI (Dead, red)

E-SEM analysis of fouled RO membrane

Biofoulants

DNA extraction

PCR amplification

Cloning

Sequence analysis

Phylogeneticanalysis

Probe design

FISH (fluoresncein-situ hybridization)

Full-cycle rDNA analysis

Lab scale RO Bio-fouling analysis

Lab scale RO unit:2 train, 3 stage RO module

Chlorination-UV sequential disinfection

Disinfection using ClO2

Development of Biofouling/ScalePrevention Technology

90nm

Fluorescent Nano particlesFluorescent Nano particles?

?

Finding out the holes, cracks, damaged parts on membrane surface

Membrane Surface Integrity Detection UsingFluorescent Nano-particles (1)

Functional relationship establishment using dimensional analysis


Dimensional analysis (Buckingham’s Pi theory)

Assuming : m = fn (c, a, J, μ)

= mass of particles through holes [M]= concentration of particles [ML-3]= flux [LT-1]= viscosity [ML-1T-1]= hole area [L2]

mcJμa

Set J, c, μ as independent control factors, then

1 3 1 1 0 0 01

1 3 1 1 2 0 0 02

( ) ( ) ( ) ( )

( ) ( ) ( ) ( )

x y z x y z

x y z x y z

J c m LT ML ML T M L M TJ c a LT ML ML T L L M T

To solve the simultaneous equations of , 21

2 3Jc Jc ma fn

c

Membrane surface (with one 2mm hole) after filtration (P=2psi)

Collected permeate

5 ppm 25 ppm 50 ppm 75 ppm 100 ppm

Nano-particles addition

Permeatecollection

Mass of Nanoparticles [g]

0 1 2 3 4 5 6

Avera

ge in

tesity

of R

GB im

age [

CData

/ pixe

l]

0

20

40

60

80

Intensity dataRegression(Exponential rise to max)

(1 )bxf a e

Estimation of m by image analysis

2 3Jc Jc ma fn

c


(J c / )3 (m / c)

0 2e-12 4e-12 6e-12 8e-12 1e-11

(J c

/

)2 a

0.0

2.0e-9

4.0e-9

6.0e-9

8.0e-9

1.0e-8

1.2e-8

1.4e-8

1.6e-8

50 ppm

y = 1090.3xR2=0.85

(J c / )3 (m / c)

0 1e-11 2e-11 3e-11 4e-11 5e-11 6e-11

(J c

/

)2 a

0

1e-8

2e-8

3e-8

4e-8

75 ppm

y = 680.49xR2=0.76

(J c / )3 (m / c)

0.0 2.0e-11 4.0e-11 6.0e-11 8.0e-11 1.0e-10 1.2e-10 1.4e-10 1.6e-10

(J c

/

)2 a

0

2e-8

4e-8

6e-8

8e-8

100 ppm

y = 439.7xR2=0.86

(J c / )3 (m / c)

0.0 2.0e-15 4.0e-15 6.0e-15 8.0e-15 1.0e-14 1.2e-14

(J c

/

)2 a

0.0

2.0e-11

4.0e-11

6.0e-11

8.0e-11

1.0e-10

1.2e-10

5 ppm

y = 10740xR2=0.71

(J c / )3 (m / c)

0 1e-13 2e-13 3e-13 4e-13 5e-13 6e-13

(J c

/

)2 a

0

5e-10

1e-9

2e-9

2e-9

3e-9

3e-9

25 ppm

y = 4952.4xR2=0.86

(J c / )3 (m / c)

0.0 2.0e-11 4.0e-11 6.0e-11 8.0e-11 1.0e-10 1.2e-10 1.4e-10 1.6e-10

(J c

/

)2 a

0

2e-8

4e-8

6e-8

8e-8

1e-7

5ppm25ppm50ppm75ppm100ppm

Total

(J c

/

0

2e-8

4e-8

(J c / )3 (m / c)

1e-11 2e-11 3e-11 4e-11

Linear regression

Empirical equation2 3

Jc Jc ma fnc

Jma k

( )k fn c∴ and let

0.039688.7406 12995.5552 c Jma e

∴

Biological Decolorization and Subsequent Reuse of Textile Reactive Dyes (1)

• Reactive anthraquinone dyes are extensively used due to the increased use of cotton– More than 80% of cotton fibers dyed using reactive dyes

(Reactive dyes share 20-30% of the total dye market)– Anthraquinone dyes are the second most common class of

textile reactive dyes after azo dyes– Under typical reactive dyeing conditions (pH 10,

temperature 60C, salt 60 to 100 g/L), up to 50% of the dye remains in the spent dyebath

• Challenges:– Color (up to 1.0 g/L dye) and salt (up to 100 g/L NaCl)– Highly water soluble (very poorly adsorbed onto the biomass)

NH2O

O NH NH

SO3H

SO3H

N

N

N

Cl

Cl

Reactive Blue 4 (RB4)(Anthraquinone Dichlorotriazinyl)

NH2O

O NH

SO3Na

SO2CH2CH2OSO3Na

Reactive Blue 19 (RB19)(Anthraquinone Vinyl Sulfonyl)

Dyeing Process- Dyebath

NaCl > 100 g/LpH > 11

Temp. > 80oC

Anaerobic Bioreactor

(Color removal)

Aerobic Bioreactor

(Carbon removal)

Renovated Process Water (Reuse of Water and Salt)

Fresh Process Water+ Salt + Dye

Waste

Dyeing Process- Dyebath

NaCl > 100 g/LpH > 11

Temp. > 80oC

Anaerobic Bioreactor

(Color removal)

Aerobic Bioreactor

(Carbon removal)

Renovated Process Water (Reuse of Water and Salt)

Fresh Process Water+ Salt + Dye

Waste


NF Membrane(Particle removal)

WAVELENGTH (nm)

400 450 500 550 600 650 700

REF

LEC

TAN

CE

(%)

0

20

40

60

80

100

REF

LEC

TAN

CE

(%)

0

20

40

60

80

100Low strength RB4 dyebath

Standard

1 2 3 4 5

Redyeing Cycle #:

High strength RB4 dyebath

Standard

1 2 3 4 5

Redyeing Cycle #:Standard

1 2 3 4 5

Redyeing Cycle #:

Reduction Mechanism of Anthraquinone Dyes by LC/ESI-MS and MALDI-MS

Decolorization by microbial reduction

Anthraquinone

R1

R2

R3O

O R1

R3

R2

OH

OH

Dihydroxy-Anthracene

2H+ + 2e-

Repetitive dyeing of spent RB4 dyebaths after the FBR and NF processes

Visual Fabric Color


Dr. Young Haeng LeeE-mail) [email protected]

Tel) +82-2-958-5841

Hoping to have great relationship and co-working opportunity among OECD countries’ researchers

Thanks for your attention !!!

Overall research trends in nano-based water treatment ... · Nano-based Water Treatment Technologies ... This year marks the 41st anniversary of the MEST as well as the 42nd anniversary

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