Journal of Environmental Management 184 (2016) 545e551

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Journal of Environmental Management

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Research article

Investigation on the potential of waste cooking oil as a grinding aid in

Portland cement
Haoxin Li, Jianfeng Zhao, Yuyan Huang, Zhengwu Jiang*, Xiaojie Yang, Zhenghong Yang,
Qing Chen
Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, Tongji University, Shanghai, 201804, China

a r t i c l e i n f o a b s t r a c t

Article history: Although there are several methods for managing waste cooking oil (WCO), a signicant result has not
Received 27 March 2016 been achieved in China. A new method is required for safe WCO management that minimizes the
Received in revised form environmental threat. In this context, this work was developed in which cement clinker and gypsum
13 October 2016
were interground with various WCOs, and their properties, such as grindability, water-cement ratio
Accepted 15 October 2016
required to achieve a normal consistency, setting times, compressive strength, contents of calcium hy-
Available online 25 October 2016
droxide and ettringite in the hardened paste, microstructure and economic and environmental consid-
erations, were addressed in detail. The results show that, overall, WCO favorably improves cement
Keywords:
Waste cooking oil
grinding. WCO prolonged the cement setting times and resulted in longer setting times. Additionally,
Portland cement more remarkable effects were found in cements in which WCO contained more unsaturated fatty acid.
Grinding aid WCOs increased the cement strength. However, this enhancement was rated with respect to the WCO
Compressive strength contents and components. WCOs decreased the CH and AFt contents in the cement hardened paste. Even
Calcium hydroxide the AFt content at later ages was reduced when WCO was used. WCO also densify microstructure of the
Consistency hardened cement paste. It is economically and environmentally feasible to use WCOs as grinding aids in
the cement grinding process. These results contribute to the application of WCOs as grinding aids and to
the safe management of WCO.
2016 Elsevier Ltd. All rights reserved.

1. Introduction developing country, China has made great progress in environ-

Waste cooking oil (WCO) mainly refers to frying and cooking oil
used at high temperatures, edible fat mixed within kitchen waste
and oily waste water directly discharged into the sewer
(Sheinbaum-Pardo et al., 2013). The discharge of WCO into drains or
sewers leads to blockages (Iglesias et al., 2012). If WCO is dumped
into a municipal solid waste landll or municipal sewage treatment
plants, it creates operation problems and pollutes water and soil
(Farooq et al., 2013). WCO use in any form in food may lead many
harmful diseases to humans, such as dyspepsia, diarrhea, stom-
achache or more serious diseases, such as intestinal or gastric
cancer (Liang et al., 2013; Chuah et al., 2015). WCO has emerged as a
serious environmental and food-safety issue. China is the largest
WCO producer in the world, and 500 million tons of WCO are
produced each year in the catering industry. As a principal
* Corresponding author.
E-mail address: jzhw@tongji.edu.cn (Z. Jiang).
mental management and food safety (Lu and Wu, 2014). However,
the Chinese government still faces serious problems in ensuring
environmental and food safety, especially in preventing WCO from
reaching the dinner table. WCO has been used as an ingredient in
animal feed in some countries, although it is banned in Europe
because of animal health hazards (EC/1774/2002). WCO is also used
in soap manufacture and in chemical industries (Thamsiriroj and
Murphy, 2010). In recent years, primary research aims have been
recovery of WCO as biofuel (Eguchi at al., 2015; Zhang et al., 2014;
Polczmann et al., 2015). There are well-developed regulations and
scal levy policies to increase this recovery rate in the US, Germany
and Japan (Zhang et al., 2014). In China, the government ofcially
began an implementation program and authorized some districts
or cities as pilots to promote this conversion. Although various
policies were implemented, the recovery rate in China is still low.
The recovery rates of some cities, such as Beijing and Nanjing, are
even less than 50%. The Chinese government has to increase food
and environment safety regulations, while encouraging the devel-
opment of new resources for WCO to better settle the problems that

http://dx.doi.org/10.1016/j.jenvman.2016.10.027
0301-4797/ 2016 Elsevier Ltd. All rights reserved.
546 H. Li et al. / Journal of Environmental Management 184 (2016) 545e551
result from WCO. Additionally, the current management methods
for WCO, such as applications in the production of the soap,
chemicals, biofuels, bio-lubricants (Borugadda and Goud, 2015) and
bio-otation agents (Yi et al., 2015), are technologically compli-
cated. Certain processes, such as degumming, destaining, dehy-
dration and chemical catalytic reactions, among others, are
required. Large capital has to be invested, and signicant energy is
also consumed in these processes. Moreover, additional wastes are
also produced from these processes. A simple and operable method
that is used to effectively manage WCO is expected to be imple-
mented in China or other developing countries, such as India,
Russian, Vietnam, Brazil and so on. This method will diversify the
safe management of WCO and relieve the current pressure of safe
WCO disposal.
In recent years, sustainable development and natural resource
preservation have become global issues (Sabine, 2013). The cement
industry, which is an important consumptive industry for raw
materials and energy, has integrated these issues into its develop-
ment policy (Schneider et al., 2011). In addition to the use of solid
waste to replace traditional materials or fuel in the production
process (Li et al., 2012; Rodriguez et al., 2013), cement grinding aids
are also used to improve the clinker grinding process (Sohoni et al.,
1991), accelerate clinker crushing, eliminate agglomeration and
decrease clinker-specic surface energy (Teoreanu and Guslicov,
1999; Rajendran Nair and Paramasivam, 1999). It is reported that
saturated and unsaturated fatty acids can be used as cement
grinding aids as well as to increase the cement neness and
improve the cement grinding efciency (Albayrak and Yasar, 2005).
However, they are typically made from natural raw materials and
must be compounded through several processes. To do this, natural
resources and energy have to be provided and consumed. Addi-
tionally, these acids are expensive and their cost is approximately
$1 per kg. Moreover, saturated fatty acid denitely increases the
compressive strength of cement. However, unsaturated fatty acid
decreases its compressive strength. The main substance compo-
nents of WCO are saturated and unsaturated fatty acids. Therefore,
at least in theory, WCO can be used as an alternative cement
grinding aid based on the saturated and unsaturated fatty acids
used in the cement grinding process. However, WCO is typically a
mixture of saturated and unsaturated fatty acids. WCO is mainly
composed of 10e20% (wt,%) saturated fatty acids and 80e90% un-
saturated fatty acids. Although several research efforts have been
reported in the literature, it is difcult to evaluate the potential to
create cement grinding aids from waste cooking oil due to the
mixing of saturated and unsaturated fatty acids in WCO. There are
still important points that require clarication. These points are
crucial to make effective use of WCO in the cement grinding pro-
cess. Therefore, this study was developed, and the possibility of
using waste cooking oil as a grinding aid in the production of
Portland cement is assessed in this study.
2. Experimental
2.1. Materials
The cement clinker that was used in this study came from
Hailuo Cement Company Ltd in Shanghai (China). CaSO4
2H2O
was the chemical reagent. The chemical component of the
cement clinker is given in Table 1. Three WCOs (WCO1, WCO2
Table 1
Chemical components of cement clinker (wt%).
Oxides CaO SiO2 Al2O3 Fe2O3 SO3 K2O MgO TiO2 Others
Content 63.5 19.7 5.3 4.2 2.1 1.8 0.9 0.2 1.4
and WCO3), in which saturated fatty acids were approximately
10%, 15% and 21% and unsaturated fatty acids were approximately
90%, 85% and 79%, respectively, were selected. These WCOs were
provided by Sichuan Zhongsen Building Materials Company Ltd
(China). The oating impurities in the WCOs were removed by
ltration.
2.2. Methods
Cement clinker was ground to ASTM 200 mesh, and a SRS3400
X-ray uorescence spectrometer was used to determine the
chemical components of the cement.
The particle size distribution of the cement was analyzed using a
LS230 laser particle size analyzer. Ethyl alcohol was used as the
medium of dispersing the cement particles. According to the
Chinese National Standard GB/T 8074-2008, the cement specic
surface area was determined using the Blaine air permeability
method.
To make the mixtures, 0.025 and 0.1% WCO1, WCO2 and WCO3
were added to 5 kg of total mixture. These mixtures contained
approximately 97% cement clinker (4850 g) and 3% (150 g)
CaSO4$2H2O. Then, these mixtures were interground with WCO
using a ball mill and were ground to approximately 3500 cm2/g.
The ball mill was prepared with steel, and the grinder weight was
160 kg. The mixture-to-grinder ratio was 1:32. In this experiment,
the grinders were 25 mm  35 mm steel forgings and 40, 50,
60 and 70 mm steel balls. The mill revolution was simulta-
neously recorded with a counter when mixture grinding began. The
Blaine specic surface areas were analyzed after grinding for
various times. The grinding was complete when the Blaine specic
surface area of the mixtures achieved the goal surface area. The
grindabilities of the clinker with WCO were evaluated using the
following Equation (1)
A
G (1)
R
where G is the grindability index; A is the Blaine specic surface
area; and R is the mill revolution needed to grind the clinker to the
corresponding Blaine specic surface area.
The water-to-cement ratio for a normal consistency
and the setting time were examined according to the Chinese
National Standard GB/T 1346-2001. Mortar prisms
(160 mm  40 mm  40 mm) were cast using a cement:sand:-
water weight ratio of 1:3.0:0.5. After 24 h in a moist cabinet, they
were removed from the molds and cured in water under stan-
dard conditions (20 2  C, 90% relative humidity). At 3 and 28
days, three prismatic specimens were pressed into six pieces, and
then, the compressive strength was tested on six prisms ac-
cording to the Chinese standard GB/T17671-1999. Six compres-
sive strength values were acquired. Their average value was
calculated, and the compressive strengths of the cement was
determined if these six compressive strength values did not
exceed 90e110% of the average values.
To test the CH content in the hardened pastes and to further
clarify the inuence mechanism of WCO on the cement strength, a
NETZSCH-STA 449 C thermal analyzer was used. The differential
thermal analysis-thermogravimetry (DTA-TG) method was also
used, and an oxygen-free nitrogen atmosphere and a heating rate of
10 /min were established. Comparison of the DTA curve areas of the
hardened pastes was conducted with pure CH. The CH content in
hardened pastes was determined using Equation (2). In this testing,
LOI
the hardened pastes were placed in ethyl alcohol to stop hydration
after they were hydrated for 3 and 28 d, and the pastes were ground
0.9
into powders.
 H. Li et al. / Journal of Environmental Management 184 (2016) 545e551 547

SCH in hardened paste
CCH  100
Spure CH
where CCH is the CH content (wt, %) of the hardened paste; SCH in
is the DTA curve area of the hardened pastes; and Spure
hardened paste
CH is the DTA curve area of the pure CH.
With the goal of further studying the inuence of WCO on C3A
hydration, a D/max 2550 X-ray powder diffractometer (XRD) was
used to test the AFt content of the hardened pastes. The 2q range
was 8.5e9.5 in 0.02 steps with 4 s per step. The radiation was
CuKa at a wavelength of 0.1541 nm (40 kV). The AFt content of the
hardened paste was determined using Equation (3) by comparing
the XRD area of pure AFt with the XRD area of the hardened paste in
the scope of 8.5e9.5 . In this testing procedure, hardened pastes
were placed in ethyl alcohol to stop hydration after they were hy-
drated for 3 and 28 d and were then ground into powders.
SAFt in hardened paste
CAFt  100
Spure AFt
where CAFt is the AFt content (wt, %) of the hardened paste; SAFt in
is the XRD curve area of the hardened pastes; and Spure
hardened paste
AFt is the XRD curve area of the pure AFt.
The hardened mortars were placed in ethyl alcohol after they
were hydrated for 28 d. Their hydration was stopped, and their
microstructural characteristics were observe. In this testing, a
Quanta 200 FEG eld emission environmental scanning electron
microscope (SEM) was used. The accelerating voltage was 20 kV,
and the magnication was 4000.
compared with the control. This result implies that WCO improves
cement clinker grinding and lowers cement clinker's ability to
(2)
resist the grinding force. Additionally, fewer revolutions were
required for the cement clinker with WCO compared with the
control. Therefore, energy consumption during cement grinding is
reduced because fewer revolutions are required for cements with
WCO. These functions are attributed to WCO's molecular form and
component structure. WCO is composed of unsaturated and satu-
rated fatty acids. These fatty acids commonly have carboxy groups
and have high polarity. In the cement clinker grinding process,
these fatty acids can form a covering lm that is absorbed on
cement grains or can ll cement particle pores or cracks. WCOs play
a role as shields and guards against bonds of the cement grains with
opposite charges and also enable neutralization. As a result,
agglomeration as a result of the appearance of an electrostatic
charge, which is due to rubbing between the clinker and grinder, is
weakened or eliminated. Moreover, WCO is typically viscous and
can stably adhere to cement grains, and this covering lm appeared
to be stable. Therefore, WCO increases cement clinker grindability
(3)
and improves the grinding process. However, this index is
decreased when more WCO is used in the grinding process. This is
caused by ow velocity alteration of cement grains. The ow ve-
locity of the cement grain increased due to the strong polarity from
the addition of more WCO. The effective contact between the
cement grain and grinder declined, and then, the cement grind-
ability and grinding efciency decreased when more WCO was
added. Still, 0.1% WCO improved cement grinding and its efciency
compared with the control.
3.2. Water-to-cement ratio to achieve normal consistency

3. Results and discussions
3.1. Grindability
Cement grinding is a high energy consuming process. In this
process, approximately one-third of the total energy consumed in
cement production is required to grind cement to a specic surface
area. This energy consumption is frequently related to the cement
clinker grindability and grinding mill. To save energy, application of
grinding aids during this process is typically very important in
addition to the other aspects of grinding technology, such as the use
of a roller press. The grindability is the measure of the cement
clinker's ability to resist grinding forces and can be used as an in-
dicator to estimate the energy required to grind the clinker to a
given Blaine specic surface area; grindability provides the rela-
tionship between the mill revolution and the given Blaine specic
surface area. In this work, the grindability indexes of cement clin-
kers with various WCOs were calculated according to equation (1)
and are shown in Table 2. WCO leads to an increase of this index
The experimental result of the water-to-cement ratio required
to achieve normal consistency is also shown in Table 2. Overall, the
water requirement to achieve a normal cement paste consistency
decreased when WCO was used. To further investigate this phe-
nomenon, the particle size distributions and volume percentages of
cements ground with different WCOs were also determined in
addition to the their specic surface areas. As shown in Table 2 and
Fig. 1, the particle size volume percentage and specic surface area
of all cements were observed to be similar. Additionally, all cements
with WCO had the same particle size distribution as the control.
The water-to-cement ratio required to achieve a normal cement
paste consistency is commonly related to the cement mineral
component and particle characteristics, such as the particle size
and specic surface area. However, all of the cements had the same
mineral components and similar particle characteristics. Therefore,
this variation in the water-to-cement ratio did not result from the
cement particle characteristics but from the use of WCO. WCO
forms a covering lm and absorbs on cement particles, or WCO can
enter the pores or cracks of cement. Moreover, their insolubilities

Table 2
Grindability indexes, normal consistency and particle size of cement clinkers with WCO.

Specimens Control WCO1 WCO2 WCO3

WCO content (wt%) 0 0.025 0.1 0.025 0.1 0.025 0.1

2
Blaine specic surface area (cm /g) 3488 3501 3512 3508 3496 3514 3503
Mill revolutions (cycle number) 4600 4230 4370 4200 4300 4220 4250
Grindability index 0.758 0.828 0.804 0.835 0.813 0.833 0.824
Normal consistency (%) 30.1 28.2 26.5 28.4 27.1 28.7 27.8
Particle size (mm) Volume percent (%)
3 12.5 12.6 12.3 12.5 12.4 12.3 12.2
3  30 54.8 55.2 54.9 55.1 55.9 55 54.2
30e60 24.6 24.3 24 24.2 23.8 24.3 25
60 8.1 7.9 8.8 8.2 7.9 8.4 8.6
548 H. Li et al. / Journal of Environmental Management 184 (2016) 545e551
Fig. 1. Particle size distributions of the cements with various WCOs.
contribute to the slowing of cement hydration, especially the hy-
dration of tricalcium aluminate (C3A), and prevent mixing water's
absorption of the cement particle (Albayrak and Yasar, 2005; Rixom
and Mailvaganam, 1999). Therefore, the water-to-cement ratio
required to achieve a normal consistency were reduced when
various WCOs were used in the cement clinker grinding process.
Additionally, the increase in the water-to-cement ratios required to
achieve normal consistencies in cements with WCO varied with the
WCO dosage and fatty acid components. At the same dosage, the
cements with 0.1% WCO had a lower water-to-cement ratio than
the cements with 0.025% WCO. WCO1 obviously had the greatest
water-cement ratio compared with WCO2 and WCO3 when the
same amount was mixed in the grinding process. More lms were
formed or more WCOs entered into cement pores and cracks when
0.1% WCO was added during the cement grinding process.
The contributions of WCO on preventing cement hydration and
absorption of mixing water on cement particles were more
remarkable. Therefore, cements with more WCO had a lower water-
to-cement ratio requirement to achieve normal consistency. Addi-
tionally, WCO3 has the greatest content of saturated fatty acids. The
saturated fatty acids in WCO typically have more carbon atoms and
longer carbon chains in the molecular structure and have greater
insolubility than unsaturated fatty acids (Rixom and Mailvaganam,
1999). This WCO provides a more signicant contribution with
respect to delaying cement hydration and preventing mixing water
absorption on cement particles. Therefore, the water-to-cement
ratio required to achieve a normal cement consistency varied
with the type of WCO used. WCO3 had the lowest water-to-cement
ratio requirement to achieve normal consistency, followed by
WCO2 and WCO1.
3.3. Setting time
The initial and nal setting times of the cements with WCO
are given in Table 3. The results indicate that, in general, WCO
Table 3
Setting times and compressive strengths of cement with WCO.
Specimens Control WCO1
WCO content (wt%) 0 0.025
Setting time (min) Initial 92 128
Final 164 216
Compressive strength (MPa) 3d 25.2 25.6
28d 56.8 57.2
delays the cement setting times and the setting times of the
cements vary with the WCO dosage and constituent. Saturated
and unsaturated fatty acids tend to postpone tricalcium silicate
(C3S) and C3A hydration (Rixom and Mailvaganam, 1999). C3S and
C3A are the principal component phases of Portland cement, and
regular setting, to some extent, relies on their hydration. As a
result, the setting time of cement with WCO is delayed and is
longer than cement without WCO. More fatty acid markedly af-
fects cement hydration. Therefore, cements with 0.1% WCO had a
longer setting time than cements with 0.025% WCO. Unsaturated
fatty acids have been reported to delay the C3A hydration more
signicantly than saturated fatty acids (Rixom and Mailvaganam,
1999). WCO1 contained more unsaturated fatty acids than WCO2
and WCO3. Cement with WCO1 had the longest setting time.
Cements with same contents of WCO2 and WCO3 followed.
Therefore, as shown in Table 3, the initial and nal setting times
of cements with 0.025% and 0.1% WCO1 were increases up to 36,
90, 52 and 87 min. However, the initial and nal setting times of
cements with same amount of WO2 and WCO3 delayed
the setting time by 29, 89, 22, 61, 47, 75, 41 and 62 min,
respectively.
3.4. Compressive strength
The compressive strengths of cements with various WCOs at 3
and 28 d are listed in Table 3. WCO affects the compressive
strength. Moreover, the compressive strength varies with the
WCO content and composition. Given the same WCO composi-
tion, the compressive strengths at 3 and 28 d increased as the
WCO dosage increased. All cements with 0.1% WCO had a greater
compressive strength at all ages compared with cement with
0.025% WCO. Although WCO had a more notable impact on
cement hydration, the lower water-to-cement ratio required to
achieve a normal consistency is found when more WCO is used in
the cement grinding process. Therefore, more mixed water is not
consumed and exists as free water, and this water appeared
during the mixing process, and the cement paste had better
workability during the mixing process. Therefore, a more
compact microstructure was formed in the subsequent setting
and hardening processes. Cements with 0.1% WCO have a greater
compressive strength than cements with 0.025% WCO. In the
case of the same WCO dosage, the cement with WCO3 has the
greatest compressive strength at all ages compared with WCO1
and WCO2. The cements ground with WCO with more saturated
fatty acids had greater compressive strengths because the un-
saturated fatty acids postpone cement hydration more notably
than the saturated fatty acids and because of the molecule
structure and chemical properties of the unsaturated fatty acids.
Unsaturated fatty acids commonly have a double bond. This
double bond readily oxidizes with dissolved oxygen in tap water
during the curing period and causes microscopic cracks in the
hardened paste (Albayrak and Yasar, 2005). Therefore, cements
ground with WCOs that have more unsaturated fatty acids have a
lower compressive strength.
WCO2 WCO3
0.1 0.025 0.1 0.025 0.1
182 121 171 114 153
251 211 239 205 226
27.4 25.8 27.6 26.3 28.1
58.1 57.3 58.3 57.8 59.4
 H. Li et al. / Journal of Environmental Management 184 (2016) 545e551
3.5. CH and AFt contents in the hardened paste
Portland cement hydration goes through a series of overlapping
chemical reactions between the clinker components, which are
CaSO4$2H2O and water, and these reactions lead to the production
of hydration products, such as CH, AFt and calciumesilicateehy-
drate (C-S-H) gel. The cement nally sets and eventually hardens.
The continued development contributes to the ultimate mechanical
properties. CH and AFt are the major crystalline phases among
the cement hydration products. They are produced throughout the
hydration process. Their contents, to some extent, provide the
cement hydration characteristics, and they were determined to
investigate the effects of WCO on cement hydration. The CH and AFt
contents at 3 and 28 d are displayed in Table 4. The results indicate
that WCO has a notable impact on the CH and AFt contents. The CH
content, at early hydration, decreased with the increase in the WCO
content. However, at 28 d, this was reversed; the CH content
increased as the WCO content increased. Additionally, for the same
dosage, cement with less unsaturated fatty acids, such as WCO2 and
WCO3, has a greater CH content than WCO1 at all ages. WCO delays
C3S hydration, but the mortars are evenly stirred because of the
lower water-to-cement ratio required to achieve a normal consis-
tency when more WCO is added. Cements with more WCO are well
hydrated at later ages. Therefore, at early ages, cements with more
WCO had a reduced CH content, whereas cements had a greater CH
content during later ages. A different observation for AFt is made in
this work that, at all hydration ages, no matter how much WCO was
added to the cement clinker grinding process, the AFt content
decreased compared with the control. Moreover, the AFt content
notably decreased when more WCO was added. The AFt content at
3 d in the cement with 0.1% WCO1 was reduced by approximately
35% compared with the control. At 28 d, the AFt was reduced by
approximately 45% compared with the control. Even the cement
with 0.025% WCO3 resulted in only 5% AFt at 3 d and approximately
3.1% at 28 d. Additionally, from the AFt results and given the same
dosage, cements with high unsaturated fatty acids had a lower AFt
content at all hydration ages. This result indicates that WCO affects
C3A hydration and AFt formation at all hydration ages. Moreover,
the presence of more unsaturated fatty acids WCO results in a more
notable suppression of WCO on AFt production, and C3A hydration
is observed. This effect is mainly achieved by the appearance of
unsaturated fatty acids in WCO. Rixom and Mailvaganam (Rixom
and Mailvaganam, 1999) also reported that unsaturated fatty
acids have an inverse effect on C3A hydration and AFt formation.
The results of this work are in agreement with this previous report.
3.6. SEM observations
After curing using standard conditions for 28 d, hardened pastes
form the control and cements with 0.025% WCO1, 0.1% WCO1 and
0.1% WCO3 were selected, and their fracture surfaces were
observed using a Quanta 200 FEG eld emission environmental
scanning electron microscope, and the SEM images are given in
Fig. 2. From these images, WCO's effect on the microstructure of the
Table 4
CH and AFt contents in the hardened pastes of cement with WCO at 3 and 28 d.
Specimens Control WCO1
WCO content (wt%) 0 0.025
CH content (%) 3d 17.8 16.9
28d 20.4 20.5
AFt content (%) 3d 8.4 6.1
28d 5.1 4.2
549
paste can be observed. Larger pores of approximately 20 nm are
found, as shown in regions A and B in the fracture surface of the
control (Fig. 2(control)). This pore size is obviously greater
compared with the pores found in the fracture surfaces of cements
with 0.025% WCO1, 0.1% WCO1 and 0.1% WCO3. Additionally, the
control also has more pores than the other pastes. The control has a
sparsest microstructure. The cements with WCO have a lower
water-to-cement ratio requirement to achieve normal consistency.
Therefore, these pastes can be more evenly stirred during paste
mixing, and denser microstructures are formed at later hydration
ages. The lower water-to-cement ratio required to achieve normal
consistency is obtained when more WCO is added during the
grinding process. Therefore, the cement with 0.1% WCO1 resulted
in a denser microstructure compared with the cement with 0.025%
WCO1 (Fig. 2(0.025% WCO1 and 0.1% WCO1)). Among the cements
with 0.1% WCO1 and 0.1% WCO3, the hardened paste of the cement
with 0.1% WCO shows a denser microstructure. Larger pores are
difcult to nd within its microstructure, and the pores are obvi-
ously reduced (Fig. 2(0.1% WCO)). There are more saturated fatty
acids in WCO3. The saturated fatty acids ll the pores of the
hardened cement paste and make the microstructure of the cement
paste denser. However, WCO1 contains more unsaturated fatty
acids. WC01 is oxidized during later hydration of the cement paste,
which results in pores in the hardened paste. Therefore, hardened
cement paste with 0.1% WCO3 has the densest microstructure.
However, this is opposite of the results using the cement paste with
0.1% WCO1. This result indicates that the microstructure of the
hardened cement paste was also related to the WCO content and
composition. The compressive strength varies with the WCO con-
tent and composition.
3.7. Economic and environmental considerations
A variety of grinding aids, such as triethylenetetramine, tetrae-
thylenepentamine, glycol, aliphatic amines, and polyhydric alco-
hols, or a mixture of several of these components, are commonly
used in the cement grinding process to improve the grinding ef-
ciency and lower carbon dioxide release due to the energy con-
sumption (Albayrak and Yasar, 2005). The prices of these
components and their mixtures are expensive. Polyhydric alcohol,
which is the cheapest component, costs approximately $1 per kg.
Approximately 0.02e0.03% polyhydric alcohol has to be added to
the grinding process if it is used alone. This dosage is similar to the
lowest content of WCO as a cement grinding aid. However, WCO
has a low cost, and its price is approximately $0.3 per kg. Addi-
tionally, WCO improves the cement strength. Various supplemen-
tary cementitious materials, such as y ash, calcined clay, coal
gangue, slag, metakaolin and other natural pozzolans, are partially
used to replace cement clinker, and blended cement is produced to
save energy as well as decrease costs and carbon dioxide release
(Jiang et al., 2015). This replacement frequently leads to an early
strength increase in the blended cement. This problem can be
resolved, and more supplementary cementitious materials can be
used to improve the early strength that results from WCO use. The
WCO2 WCO3
0.1 0.025 0.1 0.025 0.1
16.1 17.1 16.5 17.3 16.7
21.7 20.6 21.9 20.8 22.3
5.3 6.7 5.7 7.2 5.9
2.9 4.5 3.1 4.6 3.4
550 H. Li et al. / Journal of Environmental Management 184 (2016) 545e551
Fig. 2. SEM images of cement pastes made from various WCOs after curing for 28 days.
cement price is, thus, further reduced. In terms of the economy, the
utilization of WCO as a cement grinding aid is obviously feasible.
WCO improves the cement grinding process and increase the
grindability and grinding efciency. Therefore, energy consumption
from the cement grinding can be reserved for WCO use, and the
carbon dioxide release from this process can be lowered to achieve
reduced energy consumption. Moreover, energy consumption
during clinker sintering is also conserved when using more sup-
plementary cementitious materials and less cement clinker. WCO is
environmentally friendly when used as a cement grinding aid and
considering environmental efciency.
4. Conclusions
In the present work, the potential of WCO as a Portland cement
grinding aid is accessed, and the following important conclusions
can be drawn.
C WCO increases cement grindability and effectively and ef-
ciently improves the cement grinding process. However,
more WCO reduces this improvement.
C WCO prolongs the cement setting time. More WCO results in
a longer setting time. Additionally, a more remarkable effect
was observed in the cements in which WCO contained more
unsaturated fatty acids.
C WCO reduces the water-to-cement ratio required to achieve
a normal consistency.
C WCO increases the cement strength, and this enhancement is
related to the WCO content and composition.
C WCO decreases the CH and AFt contents in the hardened
cement paste. Even the AFt content at later hydration ages is
reduced when using WCO.
C SEM images indicate that WCO increases the density of the
cement hardened paste microstructure. However, more un-
saturated fatty acids in WCO contribute to the fact that, with
the same WCO dosage, cements with WCO that contained
more saturated fatty acids had a denser microstructure
compared with cements with more unsaturated fatty acids.
C WCO is also economically and environmentally feasible to be
used as a grinding aid in the cement grinding process.
Overall, WCO has the potential to be used as a cement grinding
aid with respect to technical, economic and environmental
considerations.
Acknowledgements
The authors gratefully acknowledge the nancial support pro-
vided by the National Natural Science Foundation of China (No.
51132010, 51302189, 51578412 and 51308406), the National Key
Project of Scientic and Technical Supporting Programs of China
(No. 2014BAL03B02), the Fundamental Research Funds for the
Central Universities, and the Key Laboratory of Advanced Civil En-
gineering Materials (Tongji University), Ministry of Education.
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