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Energy Procedia 114 (2017) 2537 – 2544

13th International Conference on Greenhouse Gas Control Technologies, GHGT-13, 14-18

November 2016, Lausanne, Switzerland

Waste is a misplayed resource:

Synthesis of zeolites from fly ash for CO2 capture
Zhonghua Zhang, Yongfeng Xiao, Baodong Wang*, Qi Sun†, Huidong Liu
National Institute of Clean-and-Low-Carbon Energy, Shenhua P.O.001Future Science &Technology City, Beijing, CHINA

Abstract

Fly ash is a kind of industrial waste and large amount of fly ash is produced by power plants throughout the world every year. It
is a worldwide concern for disposal of fly ash and converse them into useful products instead of burying them to landfills. Zeolite
13X, a benchmark adsorbent for CO2 capture has been successfully synthesized from solid waste fly ash by a hydrothermal
treatment without adding any extra silica or alumina sources. Actually, CO2 is believed to be the primary cause to the greenhouse
effect, and a large portion of the CO2 in the atmosphere is from the burning of fossil fuels. CO2 capture from flue gases has been
considered as a key measure to reduce this effect in the short term. The prepared zeolite 13X was characterized by X-ray powder
diffraction, N2-adsorption-desorption measurements, X-ray fluorescence and scanning electron microscopy. The CO2 adsorption
performance of the zeolite 13X was examined by using thermogravimetric analysis. The zeolite 13X showed a high BET surface
area of 643 m2/g with a microspore volume of 0.35 cm3/g, and gave high CO2 adsorption capacity (223 mg/g) at 25 Ԩ and
normal atmosphere. Meanwhile, the prepared zeolite 13X showed stable CO2 adsorption/desorption regenerability. The results
indicate that the zeolite 13X synthesized by this environmentally friendly and cost effective method has potential application for
low temperature CO2 capture in terms of its outstanding features such as high capture capacity, fast sorption/desorption rate,
infinite regenerability and cost-effective.
© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2017 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-reviewunder
Peer-review under responsibility
responsibility of organizing
of the the organizing committee
committee of GHGT-13.
of GHGT-13.

Keywords: Fly Ash; CO2 Capture; Zeolites; CO2 Sorbent

* Baodong Wang. Tel.: 86-10-5733-9633. E-mail address: wangbaodong@nicenergy.com

* Qi Sun. Tel.: 86-10-5733-9628. E-mail address: sunqi@nicenergy.com

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
doi:10.1016/j.egypro.2017.08.036
2538 Zhonghua Zhang et al. / Energy Procedia 114 (2017) 2537 – 2544

1. Introduction

Fly ash is a kind of industrial by-product, which is produced by coal based power plant. It is piled up cause to
environmental pollution and cultivated land wasting since it is the most complex and abundant anthropogenic
materials [1-5]. Some fly ash is rich in alumina, and it can be used as a substitute for bauxite. Recovering alumina
from fly ash has attracted extensive attentions in China, because the bauxite resources are limited [6]. The Shenhua
Group CO., Ltd. Initiated recovering alumina from fly ash by acid leach method in 2004. A pilot-scale plant has
been running successfully recovering 4000 tons of alumina with a “one-step acid leaching method”. The schematic
diagram of this technology is displayed in solid line part of Fig 1. In this plant, 0.43 ton production Al2O3 can be
recovered from 1 ton fly ash, but there are still 0.57 ton solid wastes which are called white slag to be dissolved. The
white slags are rich in silica since the alumina is almost extracted from fly ash. In our research program, these white
slags can synthesize to glass, ceramic and other high silica building materials. The efficient way is still studying to
use white slags to develop new product with high additional value.
It is widely accepted that the amount of CO 2 has raisin in the atmosphere from fossil fuels burning, and these
more and more CO2 in the atmosphere contributes to climate change. CO 2 capture and separation from flue gases
have been considered as a key opportunity to reduce the greenhouse gases emissions from the power plant in the
short term [7]. Zeolites are the most widely reported physical adsorbents for CO 2 capture in the literatures [8-10].
The alumina and silica are the in process-product and by-product of “one-step acid leaching method” product line,
and they can be used as the raw material of zeolite synthesis (as in dash line part of Fig 1).

Fly ash

Leaching

White slag Filtering

Alkali

Si-rich solution Leachate Extracting Ga

Hydrothermal
Crystallizing
reaction

Al-rich
Filtering Product

Drying Calcining

Zeolite Al2O3

Fig. 1. Schematic diagram of one step acid leach process

 Zhonghua Zhang et al. / Energy Procedia 114 (2017) 2537 – 2544 2539

The objective of this work is to develop a new route to increase the utilizing rate of fly ash and convert white
slags into zeolites with the high CO2 adsorption performance without adding any extra silica or alumina source. The
prepared low-cost zeolite 13X was characterized and tested for CO2 adsorption performance, and the commercial
zeolite 13X was also tested for comparison.

2. Experimental Section

2.1. Synthesis of zeolite from fly ash

Si-rich residue (white slag) and Al-rich products were obtained from Zhungeer pilot-scale plant, Erdos city,
China. A supernatant solution of silicate species was extracted from white slag by alkali fusion. The weight ratio of
the reaction mixture was 1 white slag: 0.45 NaOH: 2.55 H 2O stirring at 95 °C for 30 min. After filtration, the Si-rich
solution was obtained which contained massive silicate. The gel used for prepared of zeolite was obtained by mixing
Si-rich solution, Al-rich products, NaOH and water under vigorous stirring. The molar composition of the gel was x
Na2O: 1 Al2O3: y SiO2: z H2O (molar ratio). The gel was hydrothermally treated at 95 Ԩ for 6~16h h. The solid
product obtained was filtered, washed with distilled water, and dried overnight at 120 Ԩ.

2.2. Characterization

X-ray powder diffraction (XRD) patterns were recorded on Rigaku RINT-2000 using Cu Kα radiation at a scan
rate of 2 °/min. The scanning electron microscopy (SEM) images were obtained on a Sirion 200 scanning electron
microscope operating at 5 kv. N2 adsorption isotherms were measured in an ASAP-2020 instrument at 77 k. The
surface area of fly ash and samples were calculated by BET method.

2.3. CO2 sorption/desorption performance measurement

The CO2 adsorption performance of the zeolite was evaluated by using TGA (NETZSCH). A typical analysis is
described as below: About 50 mg of the zeolite was placed at the TGA sample pan. The sample was first heated
from room temperature to 550 °C at a rate of 10 °C/min under a pore N2 flow with a flow rate of 100 ml/min, and
was kept at 550 °C for 60 min to remove the the sorbed CO2 and moisture from the sample. The sample was cooled
down to the 25 °C and kept at this temperature for 30 min. The sorption was stated by switching the flow as from N 2
to CO2 at the same flow rate and hold at the adsorption temperature for 30 min for CO2 adsorption. After the
adsorption, the flow gas was switched back to the pore N2 and the temperature was increased to 550 °C for
desorption. The sorption capacity of the sample was calculated according to the mass change during sorption.

3. Results and discussion

3.1. Silica source and alumina source

The composition of fly ash, white slags and residues from white slags desiliconized are shown in Table 1. The fly
ash content more than 50% Al2O3, and this kind of fly ash is a potential substitute for bauxite. After acid leaching,
the white slags have silica content almost 80%, and their XRD results (shown in Fig 2) indicates that phase of SiO2
are the amorphism. Thus, it is assumed that SiO2 in white slags can react with alkali solution easily.

Table 1. Chemical composition of fly ash, white slags and residues

SiO2 Al2O3 CaO TiO2 Fe2O3 Cl C & others
Fly Ash 35.0 54.4 3.77 2.43 1.99 - 2.41
White Slags 78.7 13.4 0.37 5.20 0.45 0.83 1.05
DeSi-WS 23.2 56.7 0.95 11.7 1.71 0.64 5.1
2540 Zhonghua Zhang et al. / Energy Procedia 114 (2017) 2537 – 2544

Choosing sodium hydroxide as alkali source has a benefit that it is raw material for synthesizing zeolite. The Si-
rich solution (recorded as LSi) was prepared from white slag by alkali fusion. Effect of reaction time on SiO 2
concentration of solution was examined, and the result was shown as Fig 3. The SiO2 concentration of LSi was
increased rapidly and then smoothly with reaction time increasing. It indicated SiO 2 supplied by white slag is highly
reactive, and it confirm the assumption above. The maximum SiO2 concentration of LSi was about 120 g/L which
was achieved within 30 min.

TiO2, Anatase
TiO2, Rutile
Carbon

10 30 50 70 90
2θ (o)

Fig. 2. XRD patterns of white slags(i=Anatase –JCPDS 21-1272, '= Rutile – JCPDS 21-1276, ●=Carbon – JCPDS 26-1077)

The alumina source for zeolite synthesizing is picked up before the calcining process and it also shows the
amorphism phase. It can react with alkali solution easily.

150
SiO2 Con., g/L

100

50

0
0 30 60 90 120 150
Time, min

Fig.3. Effect of reaction time on SiO2 Con. of LSi

3.2. Effect of SiO2/Al2O3 mole ratios and alkalinity

SiO2/Al2O3 mole ratio of the starting gels prior to hydrothermal reaction is important aspect to phase of zeolites.
As shown in Fig 3, zeolite 13X was synthesized at the ratio range from 3.0 to 5.0. At the ratio range from 2.0 to 2.5,
 Zhonghua Zhang et al. / Energy Procedia 114 (2017) 2537 – 2544 2541

zeolite 4A phase was obtained. These finding shows that SiO2/ Al2O3 mole ratio is a key factor for the preparation of
different types of zeolites.

0.06

A X

0.04
Na2O/H2O

0.02

0
1 2 4 8 16
SiO2/Al2O3

Fig 3 Effect of SiO2/Al2O3 mole ratio on the zeolite type

Sodalite
13X
4A
3.75

2.50

1.25

0 30 60
2θ (o)

Fig. 4. Effect of alkalinity on the zeolite type

2542 Zhonghua Zhang et al. / Energy Procedia 114 (2017) 2537 – 2544

Alkalinity is another important factor for the preparation the different types of zeolites, because crystallization of
zeolites occurs through nucleation and crystal growth. When SiO 2/Al2O3 mole ratio of the starting gels was 3.0, the
effect of alkalinity of the starting gels was examined by XRD and the results were shown in Fig 4. At the alkalinity
of 1.25, the zeolite is 4A type. Increasing the alkalinity to 2.50, the zeolite 13X was obtained. Further increase the
alkalinity to 3.75, the product was the sodalite.

3.3. Characterization of zeolite 13X

Fig 5 shows the XRD pattern of the prepared zeolite 13X. The result was almost identical to that of the standard
sample, indicating the successful preparation of zeolites 13X using in process-product of Al extraction from fly ash
as the raw material. As shown in Fig 6, zeolite 13X was made of uniform particles (about 3 μm), which were regular
octahedron structure.

0 30 60
2θ (o)

Fig. 5. XRD patterns of prepared zeolite 13X

Fig. 6. SEM images of prepared zeolite 13X

Furthermore, XRF results were shown in Table 1 that the preparad zeolite 13X consists of TiO 2, Fe2O3 and others
with a total weight of 0.9%. It indicated that zeolite 13X was formed with very little impurities. The N2 adsorption
 Zhonghua Zhang et al. / Energy Procedia 114 (2017) 2537 – 2544 2543

isotherm at 77K of prepared zeolite 13X is shown in Fig 7. BET surface area of prepared zeolite 13X was 643 m 2/g,
which is higher than that of the commercial one (595 m2/g).

Table 1. Chemical composition of prepared zeolite 13X

SiO2 Al2O3 Na2O TiO2 K2O Fe2O3 SO3 Cl

49.9 30.9 18.3 0.051 0.129 0.124 0.082 0.514

200
Quantity Adsorbed, cm3/g STP

100

0
0 0.2 0.4 0.6 0.8 1
Relative pressure, P/P0

Fig. 7. N2 adsorption-desorption isotherms of prepared zeolite 13X

CO2 sorption capacity, mg/g

200

100 Prepared 13X

Commercial 13X

0
0 20 40 60
Time, min

Fig. 8. N2 adsorption-desorption isotherms of prepared zeolite 13X

The CO2 adsorption performance of prepared and commercial zeolite 13X was investigated by TGA. As shown
in Fig 8, both of them gave fast CO 2 adsorption kinetics with practical CO2 adsorption equilibrium achieved with in
2544 Zhonghua Zhang et al. / Energy Procedia 114 (2017) 2537 – 2544

15 min. Compared with the commercial zeolite 13X, the prepared one gave a higher CO 2 adsorption capacity, 225
mg-CO2/g-zeolite.

4. Conclusions

Zeolite 13X has been successfully synthesized using in process-product of Al extraction from fly ash as the raw
material by hydrothermal treatment, without adding any extra silica or alumina source. The prepared zeolite 13X
showed a highly crystalline structure and uniform octahedral particles. BET surface area of prepared zeolite 13X
was 643 m2/g. The prepared zeolite 13X gave a high CO 2 capture capacity (225 mg-CO2/g-zeolite) and exhibited
fast adsorption kinetics. This study may bring a new and alternative approach for recycling of fly ash for making
valuable zeolite 13X that are highly in demand for adsorption base carbon capture processes in the future.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21407005) and the National
High Technology Research and Development Program of China (863 program-2012AA06A115).

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