SYNTH

ESIS OF K‐ZEOLITES FROM FLY ASH

 FO

R TH

E AM

MONIUM AND PHOSPHAT

E UPTAK

E FROM URB

AN W

ASTE

 WAT

ER 

TREATM

ENT PLAN

TS

Worldof CoalA

shCo

nferen

ceWOCA

 Nasville, TE, 2015

Font

O1 , Moren

o N1 , Que

rolX

1 , HermassM

.2,3 , Co

rtina JL

2 . 

1 Institu

te of E

nviro

nmen

tal A

ssessm

ent a

nd W

ater Research (ID

ÆA‐CSIC), JordiG

irona

18‐26, E‐08034

‐Ba

rcelon

a, Spain/

2 Chemical Eng

ineerin

g De

partment. Universita

tPolitè

cnicade

 Catalun

ya‐Barcelona

 TECH (Spa

in)

3 Departm

ent o

f Biological and

 Chemical Eng

ineerin

g, Nationa

l Institute of App

lied Sciences and

 Techno

logy (INSAT), U

niversity

 of C

arthag

e (Tun

isia)

2015

Wo

rld

of

Co

al A

sh (

WO

CA

) C

on

fere

nce

in N

asvh

ille,

TN

- M

ay 5

-7, 2

015

htt

p:/

/ww

w.f

lyas

h.in

fo/

I.INTR

ODU

CTION AND OBJEC

TIVE

S

Zeolite

 prope

rties

Zeolite

 synthe

sis from

 Fly ash

Zeolite

 aolications

Overall concep

t and

 objectives of the

 research

2. RESULTS

3 CO

NCLUSIONS

Synthe

sis of K

 zeolite

s from PCC

 fly ash for a

mmon

ium uotake

4. ONGOING AND FU

RTHE

R RE

SEAR

CH

OUTLINE

Synthe

sisof Na‐Ca

 zeolite

s from

flyashandP sorptio

ncapacity

A ze

olite

4.1 Å

X-Y

zeol

ita

7.3 Å

soda

lite

2.3 Å

PORO

US S

IZE

(Å)

CO, C

H 4

1234567810

A

X

NH3

H 20Cl

2N 2

, SO 2

H 2Isobu

tane

MOLE

CULA

R DI

AMET

ER (Å

)

CCl 4

(C4H

9) 3N

(C2F

5) 2NC

3F7

9

INTR

ODU

CTION ZEO

LITE PRO

PERT

IES

Unb

alancedcharge

allowingcatio

nexchange

(Ca

2+, Sr2

+ , Ba

2+ , Zn

2+, Pb2

+ ,Cd2

+ , Cu

2+)

Specificpo

rous

sizes

allowingselectivegas a

dsorption

Hölle

r& W

irsch

ing(1

985)

..orig

inal

Quer

olet

al. (1

997)

.......m

icrow

ave

Park

et al.

(20

00)..

.dry c

onve

rsion

2. Di

rect

conv

ersio

n

NaOH

, KOH

ZEOL

ITIC

MAT

ERIA

L

1. Hi

gh pu

rity ze

olite

synth

esis

Hollm

anet

al. (1

998)

More

no et

al. (

2005

)Na

OH, K

OHSi

O 2Al

2O3

PURE

ZEO

LITE

3. Al

kalin

e fus

ionSh

igemo

toet

al. (1

992)

Aging

& cry

stalliz

ation

ZEOL

ITIC

MAT

ERIA

LFU

SED

MATE

RIALNa

OHKO

H

INTR

ODU

CTION: SYN

THESIS M

ETHO

D FROM FLY ASH

Theo

reticalCEC K‐zeolite

s and

someK‐silicates

Theo

reticalCEC Na‐Ca

‐zeo

lites

CEC

meq

/gCa

 clin

optilolite(Ca3) (Al8Si40)O96

*24H

2O1,8

Clinop

tilolite

(Na3K3

) (Al6Si30)O72

*24H

2O2,2

Morde

rnite

Na8)(A

l8Si40

O96

) * 24H

202,3

A zeolite

(Na12(Al12

 Si12 O48

) * 27H

2O5,5

X zeolite

(Na86)(Al86Si106

O38

4) * 264

H20

4,7

Y zeol

(Na56)(Al56Si136

O38

4) * 250

H2O

3,2

Laum

onite

(Ca4)(A

l8Si16

O48

) * 16H

2O4,3

NaP

1(Na6Al6Si10O

32*12H

2O4,6

Erionite

(Na4Ca

2K4)(Al4Si14

O36

) * 15H

2O7,2

Erionite

(Na3Ca

3K2)(Al9Si27

O72

) * 27H

2O3,8

INTR

ODU

CTION: C

EC OF ZEOLITES

CEC

CEC

meq

/gmeq

/gW zeo

lite

K10.32

(Si21.7A

l10.3O

64)(H

2O)24.32

3,7Natrolite

K2Al2Si3O10

*2H2

O4,8

W zeo

lite

K42(Si76

 Al42 O23

6) 10*7H

2O4,0Willhe

ndersonite

KCaA

l3Si3O

12*5H2

O5,7

K‐H W

 type

K2Al2Si4O12

∙*H2

O3,8F

K11A

l11Si11O

44*16H

2O5,4

Lind

e L or perlialite

K2NaA

l3Si9O

24∙7H2

O3,2Q

7 K2

O∙7 Al2O3∙14

 SiO2*21

.7 H2O

5,4

Lind

e L or perlialite

K9(AlO2)9 (SiO2)27

*22H

203,1H

7 K2

O∙ 7Al2O

3∙14

 SiO2*28

 H2O

5,2

Merlin

oite

K5Ca

2(Al9Si23O

64)∙2

4H2O

3,4To

berm

orite

Ca2.25

 (Si3O7.5 (OH)1.5) (H

2O)

Parana

trolite

Na2K0

.25(Al,Si)5

O10

*3H2

O4,1Ch

abazite

 K or G

K2[Al2Si4O

12*6.5H2

O3,6

Merlinoite

A_zeolite

NaP1_zeolite

Doña

naslu

rry s

pill

rem

edia

tion

For w

ater and

 soil remed

iatio

n (app

lied at field scale test) 

Befo

re

Afte

r

Ferti

lizer

s (p

lant

gro

wth

in s

oil r

ecla

mat

ion

area

s)

RFCS

Eur

opea

n Pr

ojec

t SIL

EX; P

hD th

esis

Nata

lia M

oren

o (2

002)

PhD

thes

is Jin

g Li

(201

2)

Aplications

of ze

olite

s synthetise

dfrom

flyash(ID

AEA combu

stionresearch

grou

p) 

As slow

 release fertilisers

(app

lied at lysim

iterscale)

INTR

ODU

CTION: A

PLICATIONS OF ZEOLITES

Mostof

theNa‐zeolite

sha

veahigher

CICthan

K‐zeolite

s:mostof

thestud

iesan

dfie

ldap

plications

repo

rted

intheliteratureha

vebe

enpe

rformed

with

Na‐zeolite

s.

Th

eslow

releaseof

Kfrom

thezeolite

compa

redwith

that

ofothe

rfertilizers,allows

redu

cing

leaching

losses

Th

epo

rous

structure

ofzeolite

spe

rmits

the

retention

ofothe

rnu

trients(m

ainlyN)

increasing

theup

take

byplan

ts.,increasing

theab

sorptio

nof

essentialn

utrie

ntsin

plan

tsan

dcrop

yields

By

them

selves

K‐zeolite

sare

espe

ciallyrelevant

inK‐po

orsoils

Th

eap

plicationof

thesezeolite

smay

bebe

neficialtoredu

ceap

plicationratesof

chem

ical

fertilizers,thereb

yim

provingthesustaina

bilityof

restorationactiv

ities

andagric

ultural

system

s.

INTR

ODU

CTION : ZEOLITE APLICATION AS FERT

ILIZER

 

ADVA

NTATG

ES

ENVIRO

NMEN

TAL ISSU

ESHigh

contents of P

 (euthrop

ication) 

andNH4

+ (HighDB

O dem

and)

UWWTP

SYNTH

ESIS OF K‐Mg ZEOLITES

Res

tora

tion

of c

oal m

ines

an

d C

CR

land

fills

Cemen

t ind

ustry 

Land

filling

Low add

ed value

  & unp

rodu

ctive uses 

Nutrie

nt loaded

NH4

+‐P‐(K,Na, Ca)  

ZEOLITES

Slow

release fertilizers

Sorptio

nNH4

+ andP 

Coal extractive activ

ities 

Coal com

bustion for 

power gen

eration 

Fly ashe

s and

 CCR

s

COAL

 UTILITZATION  

ENVIRO

NMEN

TAL ISSU

ESRe

storation

Emissions & wastes

Valorisation

INTR

ODU

CTION : OVE

RALL CONCE

PT OF TH

E RE

SEAR

CH

OBJECTIVE

S

Synthe

thise

K‐zeolite

s and

Ca‐zeo

lites from

flyash

suita

blefor the

uptake

of NH4

+ andP from

WWTP

 andits

subseq

uent

reuseas

asowreleasefertilizers

SYNTH

ESIS OF K ZEOLITES FROM FLY ASH

SAMPLES

TELB

Amorph

ous

7774

Qz

SiO2

618

Mullite

Al6Si2O13

147

Hematite

Fe2O

31.6

0.5

Maghe

mite

Fe2O

31.4

0.5

8‐16

‐24 h

1‐3‐5 M

2‐4L/kg

150‐200o

C

Conventio

nal 

hydrothe

rmal activation:

tKO

HKO

H/FA

 ratio

T

Analysis: 

Zeoliticprod

ucts:    

XRD,   CEC (IS

RIC metho

d: NH4

Cl bacht, selective HN

4+ electrode

)

Experim

ental con

ditio

ns

Fly ash (FA) sa

mples

125 mL

PARR

 4744

%TE

LBAl

14,9

11,1

Ca3,0

1,6

Fe13,2

5,1

K1,2

2,0

Mg

0,7

1,4

Na

0,1

0,9

P<0,1

<0,1

S_0,3

0,2

Mineralogy

Chem

istry

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13

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168

24

11

13

33

55

5

XRD intensity XRD intensity

1500C

1500C

2000C

2000C

KOH/FA=2L/kg

KOH/FA=4L/kg

t(h)

KOH M)

t(h)

KOH M)

LB FA

SYNTH

ESIS OF K ZEOLITES FROM FLY ASH

WMerlinoite

LF

Megakalsilite

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33

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5

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120

816

248

1624

816

24

11

13

33

55

5

1500C

2000C

KOH/FA=2L/kg

TE FA XRD intensity XRD intensity

t(h)

KOH M)

t(h)

KOH M)

1500C

2000C

KOH/FA=4L/kg

SYNTH

ESIS OF K ZEOLITES FROM FLY ASH

WMerlinoite

LF

Megakalsilite

K‐H

Natrolite

KOH (M

)ratio

 L/S

Tªt

WMerlionite

LMegakalisilite

K‐H

ZSM‐5

CEC

LB4

52

150

895

3,3

LB5

32

150

842

141,5

LB16

52

150

2475

2,8

LB23

32

200

1538

363,3

LB24

12

200

1570

272,6

LB28

52

200

2436

506

3,8

LB29

32

200

2444

332,1

LB34

52

200

89

582,7

LB35

32

200

86

412,1

LB40

54

150

853

318

2,3

LB46

54

150

1659

316

2,0

LB47

34

150

1676

2,5

LB48

14

150

1656

3,1

LB52

54

150

2474

320

1,7

LB53

34

150

2483

2,0

LB54

14

150

2474

2,6

LB58

54

200

812

5033

0,8

LB59

34

200

887

5,3

LB60

14

200

854

4,2

LB58

'5

420

016

4254

3,7

LB59

'3

420

016

874,6

LB60

'1

420

016

783,7

LB64

54

200

2482

2,8

LB65

34

200

2490

3,4

LB66

14

200

2483

3,1

High

CEC (>3 meq

/g) o

btaine

dby

synthe

thisn

ghigh

prop

ortio

nsof W

, L, m

erlinoite, and

K‐H, 

or m

ixtures o

f tho

se

SYNTH

ESIS OF K ZEOLITES FROM FLY ASH

CEC by

NH4

+ exchange

Optim

alsynthe

siscond

ition

sfor NH4

+ up

take

:Mixtures o

f W, K

‐H. L and

or M

erlinoite

Optim

alsynthe

siscond

ition

sfor NH4

+ andP up

take:

Merlinoite

(K‐Ca zeolite

)      

WMerlionite

LNatrolite

Erionite

Chavazite

K‐H

F Megakalisilite

CEC exp

KOH M

KOH/FA

  rTemp. (o

Ctim

e (h)

15

215

024

2330

203,8

23

215

024

393,3

75

215

016

3011

233,8

203

220

016

532,6

211

220

016

18

1065

1,9

263

220

024

3324

3,4

315

220

08

130

413,6

323

220

08

322,6

375

415

08

3319

3,8

435

415

016

3727

2,8

495

415

024

5727

3,2

503

415

024

502,3

563

420

08

583,1

56'

34

200

1640

2,2

57'

14

200

896

2,9

571

420

016

543,2

623

420

024

5050

2,5

631

420

024

654,5

Optim

alsynthe

siscond

ition

sfor NH4

+ up

take

:Mixtures o

f W, K

‐H. L and

or M

erlinoite

TE FA

EXPERIMEN

TAL CEC k‐zeolite

s

High

CEC (aroun

d3 meq

/g) a

reob

tained

bythesynthe

sisof W

, F, L, natrolite,

andmixtures o

f tho

se

SYNTH

ESIS OF K ZEOLITES FROM FLY ASH

Optim

alsynthe

siscond

ition

sfor NH4

+ andP up

take:

Merlinoite

(K‐Ca zeolite

)      

P sorptio

ncapacityby

NaPa1

 and

CaP1

‐NA zeolite

sSYNTH

ESIS NA‐CA

 ZEO

LITES

NaP

1‐NA 

Na+‐zeo

lite (NaP1‐NA) was sy

nthe

sized from

 Spanish coal fly ash (3M

 NaO

H, 125°C fo

r 8h and NaO

H/FA

 =2L/kg) b

y direct con

version

Ca

P1‐NA from

 NaP

1‐NA

Calcium ze

olite

 (Ca2

+ ‐zeolite

 CaP1‐NA) was prepared by a cationexchange process.  A sample of  250

 g of N

aP1‐

NA was im

mersed in 1000 mL of a 0.5 m

ol/L CaCl2 chloride for 1

h at ro

om te

mpe

rature and

 then

 filte

red with

 a 

0.2 µm

 mem

brane filter a

nd rinsed

 with

 distilled

 water to

 remove the calcium chloride solutio

n[16]. 

PHOSPHAT

ERE

MOVA

LEQ

UILIBRIUM

EXPE

RIMEN

TS

Ba

chte

xperim

entsmixingsynthe

ticsolutio

nsof

P(12mL,ob

tained

from

Na 2HP

O4.2

H 2O)w

ithZeolite

s(0.2g)

atroom

tempe

rature

(21±1ºC)for2

4h(toachieveeq

uilibriu

m)

Pconcentrations

=100

–160

00mg/

L

pH

influ

ence

:add

ing0.1mol/L

HClorN

aOHsolutio

nto

adjusttheinitialpH

.After

phaseseparatio

n,with

a0.2

µmsyrin

gefilter,theeq

uilibriu

mpH

was

measuredusingapH

electrod

eandtotalpho

sphate

concen

trationwas

measuredby

ionchromatograph

y.

TheP(V)e

quilibrium

sorptio

ncapacity

determ

ined

accordinglyto

equatio

n:

(1)

whe

reC 0

(mg/L)andCe

(mg/L)represen

tstheinitialandeq

uilibriu

mtotalP

(V)con

centratio

ns,respe

ctively;v(L)is

theaque

oussolutio

nvolumeandm

s(g)isthe

masso

fzeo

lite.

7

7,58

8,59

9,510

030

6090

120

150

180

pHequilibrium

Initial Con

centartio

n of PO43‐

(mmol/L)

NaP

1‐NA

CaP1

‐NA

050100

150

200

250

030

6090

120

150

180

qe (mg/g)

Initial Con

centartio

n of PO43‐

(mmol/L)

NaP

1‐NA

CaP1

‐NA

Equilibriu

m pH with

 initial P pH=

8

P up

take

P sorptio

ncapacityby

NaPa1

 and

CaP1

‐NA

zeolite

s

Eq. pH for C

aP1 

(P>25 mmol/L)

203 mg P (PO43

‐)/g, 

90% P uptakeyied

1. For high P concentrations (5

0‐200 mmol/L): 

Form

ationof

Ca‐pho

sphate

minerals(m

ainlyBrusite

,CaH

PO4∙2H

2O):

1.1)

With

Ca(II)p

resent

onthezeoliticmaterialasC

aO(s):

HPO4‐ /H

PO42‐+C

aO(s)=

Ca‐pho

sphates(CaHP

O4(s)or

Ca5(OH)(PO4)3(s))

1.2.With

Ca(II)ion

sintheionexchange

grou

psof

thezeoliticstructure

(ZO

‐ ) 2Ca

2++H

2PO4‐ +

2Na+

2(ZO

‐ Na+)+

CaHP

O4(s)+H

+

5(ZO

‐ ) 2Ca

2++3H 2PO

4‐ +10

Na+

10(ZO

‐ Na+)+

Ca5(OH)(PO4)3(s))+

7H+

whe

reZO

‐=zeolite

’sanionicgrou

ps

P  (H

2PO4‐and HP

O42‐

)  rem

ovalmechanism

s

2. For low P con

centratio

ns  (<50 mmol/L):

Surface complexationwith

 the A

lOHand FeO

Hfunctio

nal group

s of zeo

lites th

rough tw

o main reactio

ns:

2.1) Labile com

plexes with

 MOH2+surface grou

ps

MOH2+ +

H 2PO

4‐ /HPO

42‐

MOH2+ H

2PO4‐ /H

PO42‐

2.2) Inne

r‐sphe

re com

plexes with

 MOH surface group

sM

OH+

H 2PO

4‐ /HPO

42‐

MH 2PO

4‐ /HPO

42‐+O

H‐

whe

re M

 = Al or F

e.

Precipita

tionof highe

rsolub

le brushite

(logK

so=6.59) insteadHy

droxiapatite

(logK

so=116

.8) m

ayen

hancetheuseof th

esezeoliticprod

uctsas fertilizers

P sorptio

ncapacityby

NaPa1

 and

CaP1

‐NA zeolite

s

CONCLUSIONS

High

CEC  (com

mon

ly3‐4 me/g) K‐zeo

lites (m

ainlyW, K

‐H, M

erlionite

andlinde

F, L) re

aching

up to

 90 % ze

olite

purity(XRD

 ) can be

 synthe

tised

from

spanish

TE and

LB flyash

High

 P uptakeby

CaP1

 (up to

203 mg P/g, 90%

 P uptakeyied

) mainlyby

precipita

tionof 

Brushite

(CaH

PO4∙2H

2O)

Precipita

tionof highe

rsolub

le brushite

(Kps

‐6,6) instead

Hydroxiapatite(1.0 x 10‐36) 

may

enhancetheuseof ze

oliticprod

uctsas fertilizers

TheK‐zeoliticprod

uctsaresuita

blefor the

NH4

+ up

take

for W

WT at

thefollowingcond

ition

s:

Cond

ition

sLB:   KO

H/FA= 2L/kg, 5M KOH, 150oC

, 8h or KOH/FA= 4L/kg, 1‐3M KOH, 200oC

, 8h

Cond

ition

sTE:   KO

H/FA= 2L/kg, %M KOH, 150oC

, 16h

Thesynthe

sisof re

lativelyhigh

CEC merliniotizeolitc

prod

uctsmay

be of insterestfor the

simultane

ousu

ptakeof NH4

+ andP Merlionite

from

WWTP

Cond

ition

sLB: KO

H/FA= 2L/kg, 1‐5M KOH, 200oC

, 16‐24h 

Cond

ition

sTE:   KOH/FA= 4L/kg, 1M KOH,  200oC

, 8‐16h

          

ONGOING AND FU

RTHE

R RE

SEAR

CH

Co

mpleteresearch

on sy

nthe

sisof K‐zeo

lites from

FA , (le

aching

tests, ....)

Testingsuita

bilityof K‐zeo

liticprod

uctsfor the

ammon

ium

andP up

take

from

actual W

WTP

Testingsuita

bilityof Ca‐(Na) ‐zeo

liticprod

uctsfor the

P up

take

from

actual 

WWTP

Testingre‐use

of nutrie

nt loaded

zeoliticprod

ucts(after

NH4

+ andP up

take) 

as slow

release fertilisersfor tests fo

r plants g

rowth

atlysim

eter

scale

MAN

Y TH

ANK’S FO

R YO

UR ATTENTION!!!!!!!