SYNTHESIS OF K‐ZEOLITES FROM FLY ASH 

FOR THE AMMONIUM AND PHOSPHATE 
UPTAKE FROM URBAN WASTE WATER 
TREATMENT PLANTS
Font O1, Moreno N1, Querol X1, Hermass M.2,3, Cortina JL2. 
1Institute of Environmental Assessment and Water Research (IDÆA‐CSIC), Jordi Girona 18‐26, E‐08034‐
Barcelona, Spain/
2Chemical Engineering Department. Universitat Politècnica de Catalunya‐Barcelona TECH (Spain)
3Department of Biological and Chemical Engineering, National Institute of Applied Sciences and 

Technology (INSAT), University of Carthage (Tunisia)

World of Coal Ash Conference

WOCA Nasville, TE, 2015
OUTLINE
I. INTRODUCTION AND OBJECTIVES

Zeolite properties
Zeolite synthesis from Fly ash
Zeolite aolications
Overall concept and objectives of the research

2. RESULTS
Synthesis of K zeolites from PCC fly ash for ammonium uotake
Synthesis of Na‐Ca zeolites from fly ash and P sorption capacity

3 CONCLUSIONS

4. ONGOING AND FURTHER RESEARCH
 INTRODUCTION ZEOLITE PROPERTIES

Unbalanced charge
allowing cation exchange
( Ca 2+, Sr2+, Ba2+ , Zn2+, Pb2+,Cd2+, Cu2+)

10
Specific porous sizes
9
allowing selective gas adsorption (C4H9)3N
X 8
(C2F5)2NC3F7
7

6 CCl4
5 Isobutane
A
4 CO, CH4
N2, SO2
3 H2 Cl2
H20
NH3
2
A zeolite X-Y zeolita sodalite
1
4.1 Å 7.3 Å 2.3 Å
POROUS SIZE (Å) MOLECULAR DIAMETER (Å)
 INTRODUCTION: SYNTHESIS METHOD FROM FLY ASH
1. High purity zeolite synthesis 2. Direct conversion
Hollman et al. (1998) Höller & Wirsching (1985)..original
Moreno et al. (2005) Querol et al. (1997).......microwave
NaOH, KOH Park et al. (2000)...dry conversion
SiO2
Al2O3 NaOH, KOH

PURE ZEOLITE NaOH ZEOLITIC MATERIAL

KOH

3. Alkaline fusion Aging

Shigemoto et al. (1992) &
crystallization

FUSED MATERIAL ZEOLITIC MATERIAL

 INTRODUCTION: CEC OF ZEOLITES
Theoretical CEC K‐zeolites and some K‐silicates
CEC CEC
meq/g meq/g
W zeolite K10.32(Si21.7Al10.3O64)(H2O)24.32 3,7 Natrolite K2Al2Si3O10*2H2O 4,8
W zeolite K42(Si76 Al42 O236) 10*7H2O 4,0 Willhendersonite KCaAl3Si3O12*5H2O 5,7
K‐H W type K2Al2Si4O12∙*H2O 3,8 F K11Al11Si11O44*16H2O 5,4
Linde L or perlialite K2NaAl3Si9O24∙7H2O 3,2 Q 7 K2O∙7 Al2O3∙14 SiO2*21.7 H2O 5,4
Linde L or perlialite K9(AlO2)9 (SiO2)27*22H20 3,1 H 7 K2O∙ 7Al2O3∙14 SiO2*28 H2O 5,2
Merlinoite K5Ca2(Al9Si23O64)∙24H2O 3,4 Tobermorite Ca2.25 (Si3O7.5 (OH)1.5) (H2O)
Paranatrolite Na2K0.25(Al,Si)5O10*3H2O 4,1 Chabazite K or G K2[Al2Si4O12*6.5H2O 3,6

Theoretical CEC Na‐Ca‐zeolites
CEC
meq/g
Ca clinoptilolite(Ca3) (Al8Si40)O96*24H2O 1,8
Clinoptilolite (Na3K3) (Al6Si30)O72*24H2O 2,2
Mordernite Na8)(Al8Si40O96) * 24H20 2,3
A zeolite (Na12(Al12 Si12 O48) * 27H2O 5,5
X zeolite (Na86)(Al86Si106O384) * 264H20 4,7
Y zeol (Na56)(Al56Si136O384) * 250H2O 3,2
Laumonite (Ca4)(Al8Si16O48) * 16H2O 4,3
NaP1 (Na6Al6Si10O32*12H2O 4,6
Erionite (Na4Ca2K4)(Al4Si14O36) * 15H2O 7,2
Erionite (Na3Ca3K2)(Al9Si27O72) * 27H2O 3,8
 INTRODUCTION: APLICATIONS OF ZEOLITES
Aplications of zeolites synthetised from fly ash (IDAEA combustion research group) 

For water and soil remediation  As slow release fertilisers
(applied at field scale test)  (applied at lysimiter scale)

A_zeolite NaP1_zeolite Merlinoite

Doñana slurry spill remediation Fertilizers (plant growth in soil reclamation areas)

Before After

RFCS European Project SILEX; PhD thesis Natalia Moreno (2002) PhD thesis Jing Li (2012)
INTRODUCTION : ZEOLITE APLICATION AS FERTILIZER 
Most of the Na‐zeolites have a higher CIC than K‐zeolites : most of the studies and field applications
reported in the literature have been performed with Na‐zeolites.

ADVANTATGES

 The slow release of K from the zeolite compared with that of other fertilizers, allows
reducing leaching losses

 The porous structure of zeolites permits the retention of other nutrients (mainly N)
increasing the uptake by plants., increasing the absorption of essential nutrients in plants
and crop yields

 By themselves K‐zeolites are especially relevant in K‐poor soils

 The application of these zeolites may be beneficial to reduce application rates of chemical
fertilizers, thereby improving the sustainability of restoration activities and agricultural
systems.
 INTRODUCTION : OVERALL CONCEPT OF THE RESEARCH
COAL UTILITZATION  
Coal combustion for 
Coal extractive activities  Fly ashes and CCRs Low added value  
power generation 
& unproductive uses 

Cement industry  Landfilling

Restoration Emissions & wastes Valorisation

ENVIRONMENTAL ISSUES

Restoration of coal mines SYNTHESIS OF K‐Mg ZEOLITES

and CCR landfills
UWWTP

Sorption
NH4+ and P 
Nutrient loaded
NH4+‐P‐(K,Na, Ca)   ENVIRONMENTAL ISSUES
ZEOLITES High contents of P (euthropication ) 
Slow release fertilizers and NH4+ (High DBO demand)
 OBJECTIVES

Synthethise K‐zeolites and Ca‐zeolites from fly ash

suitable for the uptake of NH4+ and P from WWTP 
and its subsequent reuse as a sow release fertilizers
 SYNTHESIS OF K ZEOLITES FROM FLY ASH
Fly ash (FA) samples
Mineralogy Chemistry
TE LB % TE LB
Amorphous SAMPLES 77 74 Al 14,9 11,1
Qz SiO2 6 18
Ca 3,0 1,6
Fe 13,2 5,1
Mullite Al6Si2O13 14 7
K 1,2 2,0
Hematite Fe2O3 1.6 0.5 Mg 0,7 1,4
Maghemite Fe2O3 1.4 0.5 Na 0,1 0,9
P <0,1 <0,1
S_ 0,3 0,2

Experimental conditions 125 mL
PARR 4744
Conventional  T KOH/FA ratio KOH t
hydrothermal activation:

150‐200oC 2‐4L/kg 1‐3‐5 M 8‐16‐24 h

Analysis: 
Zeolitic products:     XRD,   CEC (ISRIC method: NH4Cl bacht, selective HN4+ electrode)
 SYNTHESIS OF K ZEOLITES FROM FLY ASH
W Merlinoite L Megakalsilite F
KOH/FA=2L/kg
LB FA 1500C 2000C
100 120
90
100
80
70 80
60
50 60
40
40
30
20 20
10

XRD intensity
0 0
8 16 24 8 16 24 16 8 24 8 16 24 8 16 24 16 8 24
t(h)
KOH M) 1 1 1 3 3 3 5 5 5 1 1 1 3 3 3 5 5 5

KOH/FA=4L/kg
1500C 2000C
120 120

100 100

80 80

60 60

40 40

XRD intensity
20 20

0 0
8 16 24 8 16 24 16 8 24 8 16 24 8 16 24 16 8 24
t(h)
1 1 1 3 3 3 5 5 5
KOH M) 1 1 1 3 3 3 5 5 5
 SYNTHESIS OF K ZEOLITES FROM FLY ASH
W Merlinoite L Megakalsilite F K‐H Natrolite

TE FA KOH/FA=2L/kg
1500C 2000C
80 100

70 90
80
60
70
50 60
40 50

30 40
30
20
20
10 10

XRD intensity
0 0
8 16 24 8 16 24 8 16 24 8 16 24 8 16 24 8 16 24
t(h)
KOH M) 1 1 1 3 3 3 5 5 5 1 1 1 3 3 3 5 5 5

1500C KOH/FA=4L/kg 2000C

90 120
80
100
70
60 80
50
60
40
30 40

XRD intensity
20
20
10
0 0
8 16 24 8 16 24 8 16 24 8 16 24 8 16 24 8 16 24
t(h)
KOH M) 1 1 1 3 3 3 5 5 5 1 1 1 3 3 3 5 5 5
 SYNTHESIS OF K ZEOLITES FROM FLY ASH
CEC by NH4+ exchange

KOH (M) ratio L/S Tª t W Merlionite L Megakalisilite K‐H ZSM‐5 CEC

LB4 5 2 150 8 95 3,3
LB5 3 2 150 8 42 14 1,5
LB16 5 2 150 24 75 2,8
LB23 3 2 200 15 38 36 3,3
LB24 1 2 200 15 70 27 2,6
LB28 5 2 200 24 36 50 6 3,8
LB29 3 2 200 24 44 33 2,1
LB34 5 2 200 8 9 58 2,7
LB35 3Optimal 200
2 synthesis 8
conditions for NH4+ and 6 P uptake: 41 2,1
LB40 5 4 150 8 53 3 18 2,3
LB46 5 Optimal
4
Merlinoite
synthesis
150
(K‐Ca zeolite)      
16 conditions
59 for NH4+ uptake
3 16: 2,0
LB47 3 150 16 76
4Mixtures of W, K‐H. L and or Merlinoite 2,5
LB48 1 4 150 16 56 3,1
LB52 5 4 150 24 74 3 20 1,7
LB53 3 4 150 24 83 2,0
LB54 1 4 150 24 74 2,6
LB58 5 4 200 8 12 50 33 0,8
LB59 3 4 200 8 87 5,3
LB60 1 4 200 8 54 4,2
LB58' 5 4 200 16 42 54 3,7
LB59' 3 4 200 16 87 4,6
LB60' 1 4 200 16 78 3,7
LB64 5 4 200 24 82 2,8
LB65 3 4 200 24 90 3,4
LB66 1 4 200 24 83 3,1

High CEC (>3 meq/g) obtained by synthethisng high proportions of W, L, merlinoite, and K‐H, 

or mixtures of those
 SYNTHESIS OF K ZEOLITES FROM FLY ASH
EXPERIMENTAL CEC k‐zeolites
TE FA
W Merlionite L Natrolite Erionite Chavazite K‐H F  Megakalisilite CEC exp
KOH M KOH/FA r Temp. (oCtime (h)
1 5 2 150 24 23 30 20 3,8
2 3 2 150 24 39 3,3
7 5 2 150 16 30 11 23 3,8
20 3 2 200 16 53 2,6
21 1 2 200Optimal synthesis conditions
16 1 for NH4+ uptake
8 10 : 65 1,9
26 3 2 200 2433 24
Mixtures of W, K‐H. L and or Merlinoite 3,4
31 5 2 200 8 1 30 41 3,6
32 3 2 200 8 32 2,6
37 5 4 150 8 33 19 3,8
43 5 4 150 16 37 27 2,8
49 5 4 150 24 27
Optimal 57synthesis conditions for NH4+ and P uptake: 3,2
50 3 4 150 24 50 2,3
56 3 4 200 8 Merlinoite (K‐Ca zeolite)       58 3,1
56' 3 4 200 16 40 2,2
57' 1 4 200 8 96 2,9
57 1 4 200 16 54 3,2
62 3 4 200 24 50 50 2,5
63 1 4 200 24 65 4,5

High CEC (around 3 meq/g) are obtained by the synthesis of W, F, L, natrolite,

and mixtures of those
 P sorption capacity by NaPa1 and CaP1‐NA zeolites
SYNTHESIS NA‐CA ZEOLITES

 NaP1‐NA 
Na+‐zeolite (NaP1‐NA) was synthesized from Spanish coal fly ash  (3M NaOH , 125°C for 8h and NaOH/FA 
=2L/kg) by direct conversion

 CaP1‐NA from NaP1‐NA
Calcium zeolite (Ca2+‐zeolite CaP1‐NA) was prepared by a cation exchange process.  A sample of  250 g of NaP1‐
NA was immersed in 1000 mL of a 0.5 mol/L CaCl2 chloride for 1h at room temperature and then filtered with a 
0.2 µm membrane filter and rinsed with distilled water to remove the calcium chloride solution[16]. 

PHOSPHATE REMOVAL EQUILIBRIUM EXPERIMENTS

 Bacht experiments mixing synthetic solutions of P (12 mL, obtained from Na2HPO4.2H2O) with Zeolites (0.2 g) at
room temperature (21±1 ºC) for 24h ( to achieve equilibrium)

 P concentrations =100–16000 mg/ L

 pH influence : adding 0.1 mol/L HCl or NaOH solution to adjust the initial pH. After phase separation, with a 0.2
µm syringe filter, the equilibrium pH was measured using a pH electrode and total phosphate concentration was
measured by ion chromatography.

 The P (V) equilibrium sorption capacity determined accordingly to equation:

௩
‫ݍ‬௘ ൌ ሺ‫ܥ‬଴ െ ‫ܥ‬௘ ሻ
௠ೞ
(1)
where C0 (mg/L) and Ce (mg/L) represents the initial and equilibrium total P (V) concentrations, respectively; v (L) is
the aqueous solution volume and ms (g) is the mass of zeolite.
P sorption capacity by NaPa1 and CaP1‐NA
zeolites
10
Equilibrium pH with  NaP1‐NA
9,5 initial P pH=8 CaP1‐NA
9

8,5

8 Eq. pH for CaP1 

pHequilibrium
(P>25 mmol/L)
7,5

7
0 30 60 90 120 150 180
Initial Concentartion of PO4 3‐ (mmol/L)

250
NaP1‐NA
P uptake
CaP1‐NA 203 mg P (PO43‐)/g, 
200
90% P uptake yied
150

100

qe (mg/g)
50

0
0 30 60 90 120 150 180
Initial Concentartion of PO4 3‐ (mmol/L)
 P sorption capacity by NaPa1 and CaP1‐NA zeolites
P  (H2PO4‐ and HPO42‐) removal mechanisms

1. For high P concentrations (50‐200 mmol/L): 

Formation of Ca‐phosphate minerals (mainly Brusite , CaHPO4∙2H2O):

1.1) With Ca(II) present on the zeolitic material as CaO(s):

HPO4‐/HPO42‐+CaO(s) = Ca‐phosphates (CaHPO4(s) or Ca5(OH)(PO4)3 (s))

1.2. With Ca(II) ions in the ion exchange groups of the zeolitic structure

(ZO‐)2Ca2++H2PO4‐+2Na+ 2(ZO‐Na+) +CaHPO4(s) +H+

Precipitation of higher soluble brushite (logKso=6.59) instead Hydroxiapatite
5(ZO‐)2Ca2++3H2PO4‐+10Na+ 10(ZO‐Na+) + Ca5(OH)(PO4)3 (s))+7H+
where ZO‐ =(logK =116.8) may
zeolite’ssoanionic groups enhance the use of these zeolitic products as fertilizers

2. For low P concentrations  (<50 mmol/L):

Surface complexation with the AlOH and FeOH functional groups of zeolites through two main reactions:

2.1) Labile complexes with MOH2+ surface groups

MOH2++H2PO4‐/HPO42‐ MOH2+H2PO4‐/HPO42‐

2.2) Inner‐sphere complexes with MOH surface groups
MOH+H2PO4‐/HPO42‐ MH2PO4‐/HPO42‐+OH‐
where M = Al or Fe.
 CONCLUSIONS

 High CEC  (commonly 3‐4 me/g) K‐zeolites (mainly W, K‐H, Merlionite and linde F, L) reaching

up to 90 % zeolite purity (XRD ) can be synthetised from spanish TE and LB fly ash

 The K‐zeolitic products are suitable for the NH4+ uptake for WWT  at the following conditions:

Conditions LB:   KOH/FA= 2L/kg, 5M KOH, 150oC, 8h or KOH/FA= 4L/kg, 1‐3M KOH, 200oC, 8h
Conditions TE:   KOH/FA= 2L/kg, %M KOH, 150oC, 16h

 The synthesis of relatively high CEC merlinioti zeolitc products may be of insterest for the
simultaneous uptake of NH4+ and P Merlionite from WWTP

Conditions LB:  KOH/FA= 2L/kg, 1‐5M KOH, 200oC, 16‐24h 

Conditions TE:   KOH/FA= 4L/kg, 1M KOH, 200oC, 8‐16h          

 High P uptake by CaP1 (up to 203 mg P/g, 90% P uptake yied) mainly by precipitation of 

Brushite (CaHPO4∙2H2O)

 Precipitation of higher soluble brushite (Kps ‐6,6) instead Hydroxiapatite (1.0 x 10‐36) 

may enhance the use of zeolitic products as fertilizers
 ONGOING AND FURTHER RESEARCH

 Complete research on synthesis of K‐zeolites from FA , (leaching tests, ....)

 Testing suitability of K‐zeolitic products for the ammonium and P uptake from

actual WWTP

 Testing suitability of Ca‐(Na) ‐zeolitic products for the P uptake from actual 

WWTP

 Testing re‐use of nutrient loaded zeolitic products (after NH4+ and P uptake) 

as slow release fertilisers for tests for plants growth at lysimeter scale
MANY THANK’S FOR YOUR ATTENTION!!!!!!!