Water Absorption and Retention of Porous
Ceramics Cosintered from Waste Diatomite and
Catalyst
Kae-Long Lin,a* Tzen-Chin Lee,b Jen-Chieh Chang,a and Ju-Ying Lana
a
Department of Environmental Engineering, National Ilan University, Ilan City, 26047, Taiwan, Republic of China;
kllin@niu.edu.tw (for correspondence)
b
Department of Civil and Disaster Prevention Engineering, National United University, Miao-Li 36003, Taiwan, Republic of China
Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.11675
This study examines potential waste diatomite and cata-
lyst reuse to prepare water absorption and retain porous
ceramics. The operating conditions are constant pressure (5
MPa), sintering temperature (1000–12708C), sintering time
(2 h), waste diatomite containing waste catalyst at different
proportions (0–20%), respectively. The porous ceramic sam-
ples containing waste catalyst show low thermal conductivity
properties (0.278–0.349 W/mK), probably owing to the more
pores than those in the concrete (1.458 W/mK). Water release
(t1/2 value) by the porous ceramic samples is decelerated by
porous ceramic samples containing waste catalyst, due to the
synergy effect of high water absorption by the waste catalyst
and better than in the foamed glass material (4 h). Porous
ceramic samples containing waste catalyst is highly promis-
ing for use in water absorption and retention applications. Ó
2012 American Institute of Chemical Engineers Environ Prog, 00:
000–000, 2012
Keywords: diatomite, catalyst, porous ceramics, compressive
strength, humidity
INTRODUCTION
At present, around 1.8 million tonnes of diatomaceous
earth are mined worldwide annually [1]. Diatomaceous earth
is an attractive and suitable material for fabricating porous
ceramics because of its low cost, well-defined porosity, low
density, and high thermal stability [2]. The chemical composi-
tion and physical structure of diatomite give it great commer-
cial value for a wide range of applications, including beer fil-
ter aids, the removal of textile dyes from waste water [3, 4]
and the sorption of heavy metal ions [5, 6]. Small diatomite
particles with high porosity can be used in the fabrication of
highly permeable microporous membrane filters [7]. Clearly,
low-grade materials require purification but whether that pu-
rification is sufficient as diatomite obtained with a high spe-
cific surface area and impurities have an inferior porous
microstructure after sintering. Macroporous ceramics combine
high permeability with favorable mechanical, thermal, and
chemical stability, and are therefore attractive for a wide
range of industrial applications [1, 8]. On the other hand, the
annual production of waste catalyst by the petroleum refin-
ing industry in Taiwan is 13,419 tonnes. When the activity of
Ó 2012 American Institute of Chemical Engineers
Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
a catalyst falls below an acceptable level, it is generally
regenerated and reused. However, regeneration is not always
possible [9] and the catalyst activity may decline to very low
levels and further regeneration may not be economically fea-
sible. Such spent catalysts are discarded as solid wastes [10,
11]. Sanitary landfills are commonly used to dispose of waste
catalyst, but rapid urbanization has made locating suitable
landfill sites increasingly difficult. Increasing demand for nat-
ural resources and a scarcity of environmentally acceptable
solid waste disposal sites are motivating numerous munici-
palities in Taiwan to consider resource recovery as an
alternative.
Porous ceramics with well-defined macroscopic shapes
and high mechanical stability can be fabricated using novel
processing route, while retaining the intrinsic porosity of the
porous powder from which they are manufactured [12, 13].
Sintering is a thermal process that transforms a compact
powder into a bulk material, and is used in mass-producing
complex-shaped components. Sintering is a complex process
of microstructural evolution, which involves bond formation,
neck growth, pore channel closure, pore shrinkage, densifi-
cation, coarsening, and grain growth. The force that acts
between particles, the sintering force, comprises both surface
tension and grain boundary tension. The shrinkage is
approximately proportional to the sintering force [14, 15].
The features and properties of the porous ceramic material,
for example, porosity, pore size distribution, pore morphol-
ogy, and pore connectivity (commonly identified as the rela-
tionship between open and closed porosity), depend
strongly on the composition and processing method.
Rising temperatures in large cities poses an increasing
environmental threat, especially during the summer in Tai-
wan. This predicament arises from the increasing amount of
heat generated by human activity (e.g., vehicles and air con-
ditioners) and the increasing amount of surface areas covered
by artificial materials with a high solar absorption capacity.
This global warming phenomenon is referred to as the ‘‘heat
island effect’’ [16]. Water absorption and retention of porous
ceramics as building materials are characterized by their per-
manence, heat insulation [17] and water retention. This study
demonstrates the feasibility of producing water absorption
and retention of porous ceramic monoliths from diatomite
and waste catalyst. The ability to use diatomite and waste
catalyst produced as water absorption and retention of po-
rous ceramic is also examined by studying their water reten-
Month 2012 1
tion and thermal conductivity properties. Their mineral com-
position and crystalline phase of porous ceramic monoliths
are determined using Fourier transform infrared spectroscopy
(FTIR) and X-ray diffraction (XRD). Finally, the microstruc-
ture of porous ceramic monoliths is determined using scan-
ning electron microscopy (SEM).
MATERIALS AND METHODS
Materials
The waste diatomite and waste catalyst used were col-
lected from the food-processing industry and refinery plants
located in Taipei County, Taiwan. In total, 500 kg of waste
diatomite and waste catalyst were obtained from the food-
processing industry and refinery plants, respectively. The
waste diatomite and catalyst were pulverized using a ball
mill until they could pass through a 100 mesh (0.149 mm)
sieve. The resultant pulverized waste diatomite and catalyst
were then stored in a desiccator until testing.
Preparation of Compacted Sintered Porous Ceramics
Samples
The waste diatomite and the catalyst samples were oven-
dried at 105oC for 24 h and ground in a ball mill to form fine
powders (until pass through a 100 mesh sieve) suitable for
pressing. The powder samples were mixed with each other
to prepare a known mass percentage of catalyst in diatomite
in different concentration of catalyst (0–20% by mass) to pro-
duce porous ceramics samples. The content of the catalyst in
the waste diatomite mixture was varied from 0 to 20% by
mass. The samples were compacted at 5 MPa to form cylin-
der specimens (51.8 mm (F)315 mm (H)) that were then
desiccated before testing. The compacted porous ceramic
specimens were placed on a platinum plate and burnt in an
electrically heated furnace using a ramp rate of 5oC min21.
The porous ceramic samples were then sintered at tempera-
tures between 1000 and 1270oC for 120 min. The sintered
samples were then cooled to room temperature and stored in
a desiccator for subsequent physical properties testing and
microstructure analyses.
Characterization of Sintered Porous Ceramics
Specimens
The chemical composition and physical characteristics of
the porous ceramic pellets and sintered products were ana-
lyzed. The porous ceramic samples were digested using
HNO3/HClO4/HF according to NIEA R355.00C and then ana-
lyzed with Inductively Coupled Plasma Atomic Emission Spec-
troscopy (ICP-AES) for the major elements. The NIEA R
201.14C method, Toxicity Characteristic Leaching Procedure
(TCLP), was used for heavy metal determination [18]. Sample
mechanical quality was obtained by performing crushing
strength tests. In this test, an oven-dried sample was placed in
a steel cylinder with an internal diameter of 51.8 mm and a
height of 15 mm. The samples were filled into the cylinder up
to an upper incision mark. The cylinder was covered and
pressed down using a steel puncheon until the upper level of
the porous ceramic sample was reduced by a prescribed dis-
tance. The crushing strength value was calculated as the ratio
between the load and the cross-sectional area of the cylinder
in stress units. The weight loss and absorption capacities were
measured using the NIEA R204.00T [19] method and ASTM
C556 [20], respectively. The major analyses performed on the
porous ceramics included the following:

Heavy metal concentration: The heavy metal concentra-
tions in the samples were confirmed by inductively
coupled plasma atomic emission spectroscopy (ICP-AES).
2 Month 2012 Environmental Progress & Sustainable Energy (Vol.0000, No.0000) DOI 10.1002/ep
The samples were crushed, and the heavy metals were
extracted by acid (HF: HClO4: HNO3 5 2:1:1).

Toxicity characteristic leaching procedure (TCLP): This
extraction procedure requires the preliminary evaluation
of the pH characteristics of the sample, to determine the
proper extraction fluid necessary for the experiments. In
this case, testing revealed that the #B extraction fluid (pH
2.88 6 0.05) should be used for the TCLP analysis. This
fluid was prepared by adding 5.7 mL of acetic acid to 500
mL of doubly distilled water, diluted to a volume of 1L. A
25 g sample was placed in a 1-L Erlenmeyer flask after
which 500 mL of extraction fluid was added. The samples
were agitated for 18 6 2 h using an electric vibrator. The
slurry was filtered with 6–8 lm pore size Millipore filter
paper. The leachates were preserved in 2% HNO3.

Chemical composition: The X-ray fluorescence (XRF) anal-
ysis was performed using an automated RIX 2000 spec-
trometer. Specimens were prepared for XRF analysis by
mixing 0.4 g of sample and 4 g of 100 Spectroflux at a
dilution ratio of 1:10. The homogenized mixtures were
placed in Pt–Au crucibles before being heated for 1 h at
10008C in an electrical furnace. The homogeneous melted
sample was recast into glass beads 2 mm thick and 32
mm in diameter.

Unconfined compressive strength (ASTM C39–72): Three
specimens were used for the compressive strength tests
while the fourth one was used for the microstructure ex-
amination. The average strength value from the three
specimens is presented. The coefficient of variation of
these results was less than 10%. The following formulae
were used in computing the weight loss, 24 h water
absorption rate and bulk density of sintered porous
ceramics specimens:
Weight loss ¼ fðweight of specimen before firingÞ
 ðweight of specimen after firingÞg= (1)
fweight of specimen before firingg
24 h water absorption rate ¼
fðamount of water absorbed in 24 h by saturation with dry
mass of specimenÞ  ðdry mass of specimenÞg=
fdry mass of specimeng ¼ g water absorbed=24 h ð2Þ
Bulk density ðg=cm3 Þ ¼ fdry mass of specimeng=
fðsaturated surface dry mass of specimenÞ
ðimmersed mass of dry specimenÞg ¼ g=cm3 ð3Þ

A quick thermal conductivity meter based on ASTM C
1113-90 hot-wire method was used (ASTM C 1113-90) [21].
A constant electrical current was supplied to the resistance
by using. QTM 500 device is a product of Kyoto Electron-
ics Manufacturing, Japan. Measurement range is 0.0116–6
W/ mK. Measurement precision is 65% of reading value
per reference plate. Reproducibility is 63% of reading
value per reference plate. Measurement temperature
ranges from 2100 to 1000oC (external bath or electric fur-
nace for temperature other than room). Sample size
required is two pieces of 100 3 80 3 40 mm3 thick or
more (W 3 L 3 H). Measuring time is standard 100–120 s.
This method has wide applications [22] in determining
thermal conductivity of refractory materials where, rather
than evaluating the heat flow, the temperature variation
with time at certain locations is evaluated. Transient in na-
ture, this method takes only a few minutes in contrast to
the earlier methods involving steady-state conditions.

Water absorption of the porous ceramic samples was
determined by immersing them in water at 20oC and
Figure 1. Particle size distribution of the waste diatomite
and waste catalyst.
Table 1. Chemical composition of the waste diatomite and
waste catalyst
Chemical composition Waste diatomite Waste catalyst
SiO2 (%) 94.51 6 0.23 39.3 6 0.23
Al2O3 (%) 0.87 6 0.11 59.2 6 2.38
Fe2O3 (%) 0.92 6 0.10 – Catalyst
CaO (%) 0.78 6 0.03 0.1 6 0.01
MgO (%) 0.61 6 0.09 – lyst were 1.41 and 1.11 g cm23, respectively. The pH of the
SO3 (%) 0.85 6 0.06 – waste diatomite and the waste catalyst were 7.36 and 7.45,
K2O (%) 0.58 6 0.10 0.01 6 0.00
(mean 6 standard deviation), N 5 3.
weighing after predetermined time intervals up to 24 h.
The water absorbed after 24 h was defined as the water
absorption (Wa (%)). Release of the absorbed water was
evaluated in an atmosphere with the relative humidity
controlled at 55% using a saturated Mg(NO3)2.6H2O solu-
tion. The water release rate was then evaluated from the
time at which half the absorbed water was lost (t1/2 (h))
[23].

The porosity, water absorption, bulk density, compressive
strength, and thermal conductivity of sintered samples
from the three specimens were presented, respectively.
The coefficient of variation of these results was less than
10%.

For scanning electron microscope (SEM) study of speci-
mens were first oven dried at 1058C for 24 h, and then
cooled in a desiccator. The samples were then fixed on a
sample holder, gold-coated, and examined under a Scan-
ning Electron Microscope. A Hitachi S-800 scanning elec-
tron microscope was used for SEM observation and micro-
structural determination.

The crystalline phases present in the sintered porous
ceramics samples were determined by X-ray diffraction
(XRD, Seimens FTS-40) using 30 mA and 40 kV Cu Ka
radiation. The crystalline phases were identified by com-
paring the intensities and the positions of the Bragg peaks
with the data files of the Joint Committee on Powder Dif-
fraction Standards (JCPDS).

Bonding characteristics of the specimens was analyzed
with a Fourier transformed infrared spectroscopy (FTIR,
Jasco, FT/IR-300E, Japan). Test sample was ground and
uniformly mixed with KBr at a weight ratio KBr: spec-
imen5 100:1. The mixture, 0.2 g, was pressed to a disk of
Environmental Progress & Sustainable Energy (Vol.0000, No.0000) DOI 10.1002/ep
Figure 2. X-ray diffraction patterns of waste diatomite and
waste catalyst.
13 mm in diameter for analysis. The wave numbers
ranged from 500 to 4000 cm21.
RESULTS AND DISCUSSION
Characteristics of Waste Diatomite and the Waste
The densities of the waste diatomite and the waste cata-
respectively. Figure 1 and Table 1 show the particle size dis-
tribution and chemical composition of the waste diatomite
and waste catalyst, respectively. Further X-ray diffraction
analysis showed that the waste diatomite and waste catalyst
consisted mainly of cristobalite, Al2O3, and quartz (Figure 2).
Figure 3a shows that the diatomite powder consists of
plates, shells, and broken particles. The unbroken diatomite
particle in Figure 3a exhibits an inherently intricate and
highly porous structure that is typical of diatomite. The diato-
maceous earth excavation and post-treatment process pro-
duced a large number of broken particles. The micrographs
of the catalyst under SEM are shown in Figure 3b. These
images were magnified 10003. As shown in the figure, the
catalyst is coarse, porous, and spherical; therefore, it must
have a large BET surface area.
The TCLP test results are shown in Table 2. High concen-
trations of Ni were observed in the waste catalyst samples.
The TCLP leaching concentrations for the target metals in the
waste diatomite and the waste catalyst met the current regu-
latory thresholds of the EPA and are shown in Table 2.
Mechanical Characteristics of Porous Ceramics
Table 3 shows the open porosity of the pure diatomite
specimens that were fired at various temperatures. The po-
rosity declined slowly from 1000 to 1270oC (from 66.4 to
62.3%). However, the rate of change was not constant. The
high porosity was attributed to the unique porous mineralog-
ical character of diatomite that contained 20% waste catalyst,
the porosity of which did not change considerably during
sintering. First, the open porosity declined gradually from
65.5% at 1000oC to 64.5% at 1100oC. In the second stage, the
porosity decreased from 63.8% at 1200oC to 60.1% at 1270oC,
and the rate of decline was higher than that in the first stage.
In this stage, sintering reduced the volume, and most of the
pores were closed. This indicated a simpler morphology that
was attributed to a mass diffusion transfer and pure sintering
shrinkage [24].
Month 2012 3
Figure 3. SEM Micrographs of the (a) diatomite and (b) catalyst.

Table 2. Total metals and TCLP leaching concentrations of waste diatomite and catalyst

Pb Cr Cu Zn Cd Ni
Total metal (mg kg21)
Waste diatomite N.D. N.D. N.D. N.D. N.D. N.D.
Waste catalyst N.D. N.D. N.D. 95 N.D. 4,300 6 102
TCLP (mg L21) Pb Cr Cu Zn Cd Ni
Waste diatomite N.D. N.D. N.D. N.D. N.D. N.D.
Waste catalyst N.D. N.D. N.D. N.D. N.D. 2.75 6 0.03
Regulatory limits 5 5 15 — 1 —

N.D.: Pb < 0.015 mg L21; Cr < 0.009 mg L21; Cd < 0.021 mg L21; Zn < 0.074 mg L21; Cu < 0.089 mg L21; Ni < 0.112 mg L21.
(mean 6 standard deviation), N 5 3.

Table 3. Mechanical characteristics of porous ceramics

Heating Waste catalyst replacement level (%)

Mechanic temperature
characteristic (8C) 0 5 10 15 20
Porosity (%) 1000 66.42 6 0.67 66.68 6 0.38 66.69 6 0.33 65.94 6 0.39 65.47 6 0.38
1100 65.54 6 0.41 63.52 6 0.28 63.39 6 0.16 62.51 6 0.35 64.48 6 0.53
1200 63.58 6 0.27 64.01 6 0.23 63.66 6 0.22 62.48 6 0.28 63.81 6 0.10
1270 62.34 6 0.14 60.73 6 0.54 60.57 6 0.55 59.33 6 0.24 60.14 6 0.79
Water absorption (%) 1000 89.42 6 1.21 89.47 6 1.15 88.33 6 1.17 84.70 6 1.21 83.14 6 0.37
1100 86.02 6 0.73 82.97 6 0.47 81.39 6 0.21 78.86 6 0.39 79.90 6 0.91
1200 82.28 6 0.29 81.99 6 0.42 80.42 6 0.31 77.63 6 0.38 78.18 6 0.10
1270 79.85 6 0.14 77.07 6 0.71 75.89 6 0.69 73.18 6 0.28 73.06 6 1.04
Bulk density (g cm23) 1000 0.74 6 0.003 0.75 6 0.005 0.75 6 0.006 0.78 6 0.007 0.79 6 0.003
1100 0.76 6 0.002 0.77 6 0.002 0.78 6 0.002 0.79 6 0.001 0.81 6 0.003
1200 0.77 6 0.001 0.78 6 0.001 0.79 6 0.001 0.80 6 0.001 0.82 6 0.001
1270 0.78 6 0.001 0.79 6 0.001 0.80 6 0.001 0.81 6 0.001 0.82 6 0.001
Weight loss on 1000 1.91 6 0.03 1.83 6 0.04 1.94 6 0.04 2.22 6 0.09 2.39 6 0.04
ignition (%) 1100 2.04 6 0.03 2.15 6 0.05 2.40 6 0.04 2.64 6 0.03 2.96 6 0.10
1200 1.97 6 0.02 2.36 6 0.02 2.68 6 0.02 3.01 6 0.03 3.32 6 0.10
1270 1.98 6 0.05 2.50 6 0.02 2.76 6 0.04 3.06 6 0.06 3.38 6 0.07
Compressive 1000 2.61 6 0.03 1.84 6 0.06 1.69 6 0.04 1.74 6 0.06 1.64 6 0.02
strength (MPa) 1100 4.65 6 0.02 3.28 6 0.24 3.00 6 0.15 2.95 6 0.06 2.66 6 0.21
1200 5.63 6 0.25 5.32 6 0.12 4.75 6 0.05 4.56 6 0.01 4.31 6 0.10
1270 5.85 6 0.12 5.16 6 0.45 4.70 6 0.09 4.44 6 0.07 4.21 6 0.05

(Mean 6 standard deviation), N 5 3.

4 Month 2012 Environmental Progress & Sustainable Energy (Vol.0000, No.0000) DOI 10.1002/ep

Figure 4. Thermal conductivity of porous ceramics.
The water absorption rate, which is the weight of the
moisture in the pores as a fraction of the weight of the sin-
tered specimen, is an effective index of the quality of porous
ceramics. Table 3 shows the results of the water absorption
tests on various waste catalyst-diatomite mixtures that were
heated at four temperatures. Water absorption increased from
83.1 to 89.4%, 79.9 to 86.0%, 78.2 to 82.3%, and 73.1 to
79.9%, with heating temperatures of 1000, 1100, 1200, and
1270oC, respectively. The results show that as the waste cata-
lyst content declined, the water absorption of the porous ce-
ramic samples increased. We observed a near-linear depend-
ence of water absorption on the waste catalyst contents
(from 10 to 20 wt %) in the samples of diatomite that con-
tained waste catalyst. Furthermore, the amount of water
absorbed by the porous ceramics decreased with an increase
in the heating temperature. The decline in the rate of water
absorption with increasing heating temperature (1200oC) sug-
gests that local liquid-phase sintering occurred, which con-
tributed to a decrease in pore volume and the water absorp-
tion rate. Water absorption of the materials in this study is
consistent with the trend that was first described by Furlani
et al. [25]; that is, the sintering behavior of ceramics is
affected by the formation of a ‘‘transitory liquid’’ phase,
which improves the densification of the sintered samples.
The bonding capacity of the mixture is related to the amount
of the waste catalyst added to the mixture.
Open and closed pores are typically formed during sinter-
ing. Minimal density corresponds with the maximal volume
of closed pores in the samples. Densification is a pore-filling
process that occurs during the liquid phase flow and pore
shrinkage. Table 3 shows the measurements of the bulk den-
sity of samples with various proportions of the waste catalyst,
which were fired at four temperatures. The sintered diatomite
samples typically had a bulk density of 0.74–0.78 g cm23.
The results show that the bulk density increases in conjunc-
tion with the temperature (Table 3). Heating temperature can
also influence the bulk density of the porous ceramics. The
results show that the bulk density increased in conjunction
with the waste catalyst content. Therefore, temperature is the
crucial parameter in the controlled densification of porous
ceramics and in forming monoliths with a well-defined po-
rosity.
The weight loss that occurs in a monolith during sintering
is related to the development of porosity and densification.
Both factors affected the compressive strength of the ther-
mally treated samples. Figure 7 shows the weight loss that
occurred after porous ceramic ignition and the amount of
waste catalyst added to the mixture at various heating tem-
peratures. As shown in this figure, the weight loss occurred
Environmental Progress & Sustainable Energy (Vol.0000, No.0000) DOI 10.1002/ep
when the heating temperature increased from 1000 to
1270oC, suggesting that the weight loss may have been
caused by the oxidation of organic residues of the waste di-
atomite. The weight loss of the samples after sintering may
be attributed to the release of gases through the conversion
of organic residues, mineral decomposition, or the vaporiza-
tion of volatile metals in the thermally treated samples dur-
ing the sintering process. The emission and decomposition
of these substances affected the macro properties and
microstructure of the porous ceramics. In this study, the
weight loss percentage during the process of sintering green
samples to porous ceramics was defined as the weight loss.
The weight loss of a normal sintered sample of diatomite af-
ter heating to 1000, 1100, 1200, and 1270oC was 1.91%,
1.93% and 1.97%, and 1.98%, respectively, and was attrib-
uted to the elimination of organic matter content from the
diatomite. The results show that adding waste catalyst
resulted in an increase of weight loss after ignition. This
indicates that the diatomite and waste catalyst are compati-
ble ingredients; therefore, the waste catalyst can be used as
a substitute for diatomite.
The compressive strength is the crucial index of the engi-
neering quality of porous ceramic material. Table 3 shows
the compressive strength test results for porous ceramics
made from diatomite and waste catalyst mixtures. The com-
pressive strength of the porous ceramics increased when the
heating temperature increased from 1000 to 1270oC. The
results showed that the optimal heating temperature that
maximized the compressive strength was 1270oC. The com-
pressive strength of the mixed porous ceramic samples of di-
atomite that contained the waste catalyst decreased slightly
when the heating temperature increased above 1200oC. The
porous diatomite ceramic strength decreased when up to
20% of the waste catalyst was added to the porous ceramics
that were heated to 1200oC. The waste catalyst can be con-
verted into porous ceramics by using this method. Conse-
quently, the waste catalyst can be blended with diatomite to
produce porous ceramics.
Thermal Conductivity of Porous Ceramic Samples
Figure 4 shows the variation in thermal conductivity of
waste diatomite containing waste catalyst sintered porous
ceramic samples at various temperatures. When the heat-
ing temperature was increased from 1000 to 1200oC, the
thermal conductivity of the waste diatomite sintered po-
rous ceramics was 0.278, 0.280, 0.281, and 0.282 W/mK.
Additionally, the thermal conductivity of porous ceramic
samples increased in conjunction with the heating temper-
ature. When the amount of waste catalyst was increased
from 5 to 20%, the thermal conductivity of the sintered
porous ceramics was 0.307–0.318, 0.314–0.336, 0.315–
0.347, and 0.317–0.349 W/ mK. Moreover, the thermal
conductivity of the porous ceramic samples increased in
conjunction with the waste catalyst content. This increase
was attributed to the porous structure of sintered porous
ceramic samples containing waste catalyst, resulting in a
denser structure. In addition, the thermal conductivity
decreased because of the decreasing density of the sin-
tered porous ceramic samples, which subsequently
increased the void content. The samples revealed a corre-
lation between the density and thermal conductivity for
sintered porous ceramic samples, in which the thermal
conductivity increased in conjunction with the density. In
this study, the porous ceramic samples had a thermal con-
ductivity of approximately 0.278–0.349 W/mK, which was
lower than that for the concrete (1.458 W/mK). The po-
rous ceramic samples exhibited properties of low thermal
conductivity, which may be attributed to the larger num-
ber of pores compared to those in the concrete.
Month 2012 5
Figure 5. Water-retention properties of waste diatomite containing waste catalyst sintered porous ceramics samples at various
temperatures.
Figure 6. FTIR spectral patterns of porous ceramics samples
at 1270oC.
Water-Retention Properties of Porous Ceramic Samples
The water-release parameter (t1/2) was defined by the
time required for half of the amount of water to be released
from the samples. Figure 5 shows the t1/2 values as a func-
tion of the waste catalyst content of the samples. The t1/2 val-
ues are low, with 50% of the Wa retained for 48 h in the po-
rous ceramic samples containing waste catalyst samples at a
relative humidity of 55% at 20oC; this value is lower than that
in pure diatomite porous ceramic samples when the heating
temperature reached 1000oC. Increasing the heating tempera-
6 Month 2012 Environmental Progress & Sustainable Energy (Vol.0000, No.0000) DOI 10.1002/ep
ture from 1000 to 1200oC decreased the water-retention
properties of the resulting porous ceramic samples contain-
ing waste catalyst samples. When the heating temperature
reached 1000oC, the porous ceramic samples containing 20%
waste catalyst had t1/2 values of 11 h; these values were
larger than those for the porous ceramic samples containing
5% of the waste catalyst (9 h). Because the t1/2 value of the
foamed glass sample was 4 h, the porous ceramic samples
containing the waste catalyst exhibited excellent slow water-
releasing properties, which may be attributed to the smaller
pores, compared with those in the foamed glass. The large
amounts of waste catalyst in the porous ceramic samples also
facilitated a slow water release, which yielded acceptable
water-retention properties. These properties make the porous
ceramic samples containing waste catalyst samples promising
for use as water-retaining materials to combat ‘‘heat island’’
effects.
FTIR Spectra of Porous Ceramics
Fourier transform infrared spectroscopy (FTIR) is an effec-
tive method for determining mineral composition. Vibrational
spectroscopy can help identify high-crystalline substances as
well as weak-crystalline and amorphous inorganic compo-
nents and organic substances. Figure 6 shows the FTIR spec-
tra of porous ceramic samples at 12708C. All specimens were
dried at 1058C for a few hours prior to spectroscopic mea-
surement to eliminate spurious water bands caused by mois-
ture, which may influence fundamental OH-stretching bands.
The porous ceramic samples that did not contain the waste
catalyst yielded a signal at 622 cm21, which is characteristic
of SiO  (Si, Al) vibration, suggesting that they contained
an alumino-silicate phase. The signal at 1105 cm21 indicated
the formation of Si O Si bonds. Porous ceramic samples

Figure 7. XRD patterns of porous ceramics samples at
1000oC.
Figure 8. XRD patterns of porous ceramics samples at
1100oC.
that contained waste catalyst yielded a signal at 610–710
cm21, which is characteristic of Si O  (Si, Al) vibration,
suggesting that the samples contained alumino-silicate. This
signal resulted from the formed Si O Si bonds (in the
range 900–1200 cm21), which had strong bands associated
with SiO4 tetrahedra in the other phases in the samples.
XRD Patterns of Porous Ceramics
Figures 7–10 show the XRD patterns of porous ceramics
sintered at 1000, 1100, 1200, and 1270oC. The two peaks
from the diatomite porous ceramic sintered at 1000oC show
the formation of a cristobalite phase and quartz; the cristoba-
lite content increased in conjunction with the temperature.
The intensity of the crystalline quartz peaks decreased with
the increase of the sintering temperature. Quartz remained in
the porous ceramic samples at 12008C. When the tempera-
ture reached 1200 or 1270oC, all of the quartz in the porous
ceramics that contained the waste catalyst was converted to
cristobalite, which became the major phase. This crystalliza-
tion is crucial because cristobalite has a substantially larger
chemical and thermal stability, compared with amorphous
silica [26]. The crystalline phase of porous ceramics that con-
tained the waste catalyst did not change. The only change
occurred in peak intensity; that is, at 10008C, the intensities
of the quartz (2y 5 22.5) phases were considerably lower.
Environmental Progress & Sustainable Energy (Vol.0000, No.0000) DOI 10.1002/ep
Figure 9. XRD patterns of porous ceramics samples at
1200oC.
Figure 10. XRD patterns of porous ceramics samples at
1270oC.
Scanning Electron Microscopic Microphotographs of
Porous Ceramics
Figure 11 shows the SEM microphotographs of porous ce-
ramic samples sintered at 1270oC. Figure 11a shows that a
small fraction of the diatomite powder began to melt, the liq-
uid phase accumulated in regions with a negative curvature,
and the contact points between pairs of particles formed
necks. The initially isolated diatomite particles were con-
verted into an integral body, which contained numerous
closed pores. A microstructural change was observed during
sintering below 1270oC. Cylindrical diatomite particles were
identified easily, and a number of micropores were distrib-
uted. Scanning electron microscopic measurements revealed
the waste catalyst in various proportions in the microstruc-
tures of porous ceramics (Figures 11b–11e). The catalyst
bonded the diatomite powder into relatively strong mono-
liths. However, a melt phase covered the diatomite particles
and filled the diatomite pores when the sintering temperature
was increased to 12708C. Impurities in diatomite, such as
Na2O, K2O, Al2O3, CaO, and MgO favor the formation of
low-temperature eutectics and the subsequent formation of a
melt phase in the silica-rich grains [27]. The internal pore vol-
ume of diatomite that contained 20% of the waste catalyst
was not reduced substantially after heating to 1270oC (Figure
11e). Slight fusion occurred at the particle contact points at
1270oC. The powder partially melted, and both the interpar-
ticle pores and the internal structure collapsed.
Month 2012 7
Figure 11. SEM microphotographs of porous ceramics samples.
CONCLUSIONS
This study examined potential waste diatomite and cata-
lyst reuse in the preparation of water absorption and reten-
tion of porous ceramics. The experimental results indicate
that increasing the heating temperature from 1000 to 1270oC
can increase the compressive strength of the porous
ceramics.
The porous ceramics fabricated from waste material
exhibited enhanced water absorption and retention capabil-
ities. Moreover, the results of this study also indicated that
water absorption and retention are dependent on the pore
structures. Heating temperature is the crucial parameter in
the controlled densification of porous ceramics and in form-
ing monoliths with a well-defined porosity. These structures
revealed a correlation between the density and thermal con-
ductivity for sintered porous ceramic samples, in which ther-
mal conductivity increases in conjunction with density. The
porous ceramic samples containing the waste catalyst exhib-
ited low thermal conductivity properties, which may be
attributed to the larger number of pores than those in the
concrete.
Additionally, water release (t1/2 value) by the porous ce-
ramic samples was decelerated using porous ceramic samples
containing the waste catalyst because of the synergy effect of
high water absorption by the waste catalyst. The t1/2 values
of the porous ceramic samples were higher than those in the
foamed glass material.
In summary, porous ceramic samples containing the waste
catalyst have excellent mechanical properties, making them
feasible for use in water absorption and retention of porous
ceramic applications.
ACKNOWLEDGMENT
The authors thank the National Science Council of the
Republic of China, Taiwan, for financially supporting this
research under Contract No. NSC 98-2621-M-197-001.
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