7th AUN/SEED-Net Regional Conference on Chemical Engineering

Synthesis of Zeolite Form Lake Sludge

using Microwave Heating
Wenjing Wang1, Chris Salim2, Winarto Kurniawan1 and
Hirofumi Hinode1
1 Tokyo Institute of Technology, Department of International
Development Engineering
2 Surya University, Department of Environmental
Engineering

The Kasumigaura Lake is located in the extent from

Southeast Ibaraki to Northeast Chiba.

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Back ground
Closed
Closedwater
watersystem
systemof
oflakes
lakes Human
Humanactivities
activities
Increasing
Increasingof
ofnutrient
nutrientsalts
saltsand
andcontaminants
contaminants
Lake
Lakesludge
sludgeisisdredged
dredgedto
to
alleviate
alleviateeutrophication
eutrophication
Conventional disposal method
Utilization
Utilizationas
asaazeolite
zeolite Conventional disposal method
Recycle
Landfilldisposal
disposal
Recycleofofunused
unusedresources
resources Landfill
Large
Largescale
scaleofofdisposal
disposalland
land
Soft
Softground
ground

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Material
Sludge from Kasumigaura lake (Si,Al,O,C etc.)
Mineralizer: NaOH
Table the chemical component of lake sludge from Kasumigaura
Element

Si

Al

Fe

Cl

Content
32.6 25.7 11.4 8.13 3.01 1.30 0.78 0.48 0.31 0.29
[wt%]

Others

16

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Introduction Zeolite

Definition : porous crystalline aluminosilicate

Components : silica and alumina

xM2OyAl2O3zSiO2nH2O
(structural formula)

(Crystal structure)

Characteristics catalytic activity, adsorption ability,

ion exchange ability etc.

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Research objectives
Synthesis of zeolite from lake sludge using
hydrothermal reaction in alkali solution
Investigation of microwave irradiation effects on
synthesis of zeolites
Investigation of the effect of ultrasonic mixing

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Methodology - Synthesis procedure of zeolite

drying of sludge (105) (from kasumigaura)
crushing and sieving (<106m)
impregnating with alkali solution (1 - 8M
NaOH ),
adjusting Si/Al molar ratio (Si/Al=1.5 - 3.0)
and liquid to solid ratio (2 8 ml/g),
stirring (24 h, 150 rpm)
heating 3 30 h, 90 - 150
filtrating, washing (several times),
drying (room temperature )

zeolite product
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Experimental
Microwave heating Method
teflon container
thermal insulator
Drying of sludge stirrer
Crushing and sieving
(<150m)
Treatment with alkali solution(1,2,3M NaOH)
Magnetic mixing (24h) or
Ultrasonic mixing (3h)
Microwave treatment (90, 120, 150, 6h)
Filtrating, washing, drying
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microwave heating set

Results Effect of L / S ratio

(24h, Si/Al=1.9, 120, 2M NaOH)

10m
10kv2000

2 -150

10m
10kv2000

2 -120

Q : Quartz - SiO2
P : Na-P1(Na6Al6Si10O32 12H2O)

10m
10kv2000

2 -90

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The influence of heating method

Conventional heating method : mixing time 24h, heating time 24h
Microwave heating method : mixing time 24h, heating time 6h
Synthesis condition : Si/AL = 1.9, CNaOH = 2M, heating temperature = 120
Q : Quartz SiO2

P1: Zeolite P1(Na) Na6Al6Si10O32!12H2O

U : Unnamed zeolite Na6[AlSiO4]6!4H2O A : Analcime-C Na(Si2Al)O6!H2O

P1
P1
UAP1

U Q
P1
A

Microwave heating
P
1

U P1

P1

Conventional heating
P1

P1
P1

P1
Q
P1

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GIS

Na-P1
Gismondine

11/16

Analcime-C

structure

8-ring in respect chan

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The influence of ultrasonic mixing

Mixing time : 3h Microwave heating time = 3h , NaOH = 2M

Synthesis condition : Si/AL = 1.9, heating temperature = 120

Q : Quartz SiO2
U : Unnamed zeolite
Na6[AlSiO4]6!4H2O
P1: Zeolite P1(Na)
Na6Al6Si10O32!12H2O

P1
P1
U

P1

P1

P
1

P1

US 3h
US 1h

US 30min
Mixing 1day

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The influence of ultrasonic mixing

Microwave heating method : mixing time 24h, heating time 6h

Ultrasonic assisted microwave heating method : mixing time 3h, heating time 6h
Synthesis condition : Si/AL = 1.9, CNaOH = 2M, heating temperature = 120
Q : Quartz SiO2

P1: Zeolite P1(Na) Na6Al6Si10O32!12H2O

U : Unnamed zeolite Na6[AlSiO4]6!4H2O A : Analcime-C Na(Si2Al)O6!H2O

P1
A
Q

P1

A
P1
P1
U
U

A P
1

Ultrasonic assisted
Microwave heating
U

P1

P1

P1
P1
UA

Q
P1U
A

Microwave heating

P
A
1 U

P1

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Conclusion
Zeolites are synthesized successfully from lake sludge by
using microwave heating method.
Microwave heating requires shorter synthesis time.
Output control is easy and fast.
(10min is needed to ramp to target temperature while 20min for
drying oven. Cooling down is done automatically after heating )
In order to improve the synthesis of zeolites, the advantages

of using ultrasonic mixing is studied.

The XRD result shows that ultrasonic mixing is more effective than
stirrer mixing.
Mixing time is shortened from 24h to 3h.
By calculating the energy 0.57kWh is needed for US mixing while
magnetic mixing is 1.9kWh for 4 samples. Ultrasonic mixing required
lesser energy.
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Thank you for listening

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Results Adsorption of Cu2+ ion (30, 24 h)

X[mg/g]

Si/Al=2.5, 120, L/S=5ml/g,

2M NaOH
NaP1, Species-P
Si/Al=1.5, 90, L/S=5ml/g,
2M NaOH
NaP1
Si/Al=1.5, 150, L/S=5ml/g,
2M NaOH
Analcime-C
C[ppm]

Langmuir adsorption isotherm of the Cu2+ ion

Results Adsorption of Pb2+ ion (30, 24 h)

X[mg/g]

Si/Al=2.5, 120, L/S=5ml/g,

2M NaOH
NaP1, Species-P
Si/Al=1.5, 90, L/S=5ml/g,
2M NaOH
NaP1
Si/Al=1.5, 150, L/S=5ml/g,
2M NaOH
Analcime-C
C[ppm]

Langmuir adsorption isotherm of the Pb2+ ion

Results Adsorption of Cd2+ ion (30, 24 h)

X[mg/g]

Si/Al=2.5, 120, L/S=5ml/g,

2M NaOH
NaP1, Species-P
Si/Al=1.5, 90, L/S=5ml/g,
2M NaOH
NaP1
Si/Al=1.5, 150, L/S=5ml/g,
2M NaOH
Analcime-C
C[ppm]

Langmuir adsorption isotherm of the Cd2+ ion

Results Heavy metal adsorption

Major
phase

Synthesis
condition

Xm(mg/g) Xm(mg/g) Xm(mg/g)

for
for
for
(meq/100g)
Cu2+
Pb2+
Cd2+
CEC

NaP1,
Si/Al=2.5, 120,
Species-P L/S=5ml/g, 2M NaOH

362

53.1

55.3

40.9

NaP1

Si/Al=1.5, 90,
L/S=5ml/g, 2M NaOH

313

31.7

41.1

35.2

Analcime-C

Si/Al=1.5, 150,
L/S=5ml/g, 2M NaOH

158

19.6

37.3

24.0

(Xm : calculated by Langmuir adsorption isotherm equation)

Conclusions
From lake sludge, several types of zeolites were successfully
synthesized by hydrothermal reaction in alkali solution.
Zeolite Na-P1 and Zeolite Species-P that were formed at Si/Al
ratio of 2.5 and reaction temperature of 120 showed the highest
value of CEC (362meq/100g).
The L/S ratio showed no effect on the type of zeolite formed.
The zeolite product showed adsorption ability for Cu2+
(Xm=53.1mg/g), Pb2+ (Xm=55.3mg/g) and Cd2+ (Xm=40.9mg/g).
These values were higher than those reported on previous study.
(Activated carbon Xm(Pb2+)=35.7mg/g and artificial zeolite
Xm(Cd2+)=38.55mg/g).

The artificial zeolite applied in various fields such as

agriculture, fisheries, stockbreeding, civil engineering,
architecture and environment improvement.
The example of utilizing the ability of cation exchange
Soil improvement, water purification, water processing
/ sewage treatment
The example of utilizing the ability of adsorption
Deodorization, moisture absorption, humidity
regulation; the adsorption of the poisonous gas;
waste oil processing; adsorption separation; the
adsorption decomposition of the dioxin

The mechanism of microwave heating

Microwave heating belongs to dielectric heating an internal heating method.

The object to be heated is the heating element during heating. When it is put in the
electric field of the microwave, molecules (permanent dipole) are subject to the radio
forces. Molecules in electrical neutral state are displaced and polarized, they will
vibrate violently according to the frequency of microwave. (In the case of 2450MHz,
2.45 billion times/sec.)
Ionic
polarization

Electronic
Polarization

Orientation
polarization

Interface
polarization
Dielectric polarization types by microwave heating
Reference : Microwave Engineering homepage
http://www.microwave.ne.jp/06/001.html

The mechanism of ultrasonic

Ultrasonic belongs to longitudinal wave that is transmitted through a medium.

When sound source vibrates, the medium (water) around it is pushed or pulled
resulting in periodical density change.

pressure reduction
The reduced pressure cause bubbles which didnt dissolve in water completely.
Cavitation occurs when bubbles burst and water molecules accelerated by
ultrasonic are considered to result in a good mix of the sludge - NaOH mixture in a
shorter time.