Accepted Manuscript

Sustainable Resource Opportunity for Cane Molasses: Use of Cane Molasses as a

Grinding Aid in the Production of Portland Cement

Haoxin Li, Zhengwu Jiang, Xiaojie Yang, Long Yu, Guofang Zhang, Jianguo Wu,
XiangYong Liu

PII: S0959-6526(15)00031-1
DOI: 10.1016/j.jclepro.2015.01.027
Reference: JCLP 5104

To appear in: Journal of Cleaner Production

Received Date: 3 September 2014

Revised Date: 8 January 2015
Accepted Date: 8 January 2015

Please cite this article as: Li H, Jiang Z, Yang X, Yu L, Zhang G, Wu J, Liu X, Sustainable Resource
Opportunity for Cane Molasses: Use of Cane Molasses as a Grinding Aid in the Production of Portland
Cement, Journal of Cleaner Production (2015), doi: 10.1016/j.jclepro.2015.01.027.

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 ACCEPTED MANUSCRIPT
Sustainable Resource Opportunity for Cane Molasses: Use of Cane Molasses as a Grinding Aid in
the Production of Portland Cement

Haoxin Li a Zhengwu Jiang a,* Xiaojie Yang a Long Yu a Guofang Zhang a Jianguo Wu a XiangYong Liu b
a
Key Laboratory of Advanced Civil Engineering Materials Ministry of Education, Tongji University, Shanghai, 201804, China
b
Jinan Rail Transit Co. Ltd, Jinan, 250101, China

Corresponding author

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Tel./Fax: +86 21 69584723.
E-mail addresses: jzhw@tongji.edu.cn (Z. Jiang)

Abstract: Current methods used in China have failed to recycle cane molasses in an environmentally friendly way.

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Meanwhile, it is an urgent concern to find a cheap alternative to the present Portland cement grinding aids. However, the
available literature has several limitations in properly evaluating the feasibility of using cane molasses as a Portland cement

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grinding aid. Therefore, the mixture of calcium sulphate and cement clinker is interground along with it, and mixture properties
such as grindability, setting time, compressive strength, water absorption, compatibility with water reducing admixture, and
hydration characteristics are systematically discussed and the mechanisms of these property variations are clarified. Besides,
the economic, logistical, and environmental viability are also considered. The results show that cane molasses affects the

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cement grindability, setting time, compressive strength, water absorption, compatibility, hydration characteristics and
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microstructure, and these effects are related to its content. Moderate cane molasses delays the cement setting, but it is
beneficial to the improvements of compressive strength, compatibility and microstructure. However, in addition to the fact that
compressive strength is lowered, compatibility becomes poor, the later hydration is postponed and the microstructure gets
loose, the scale of setting delay is also lessened when excessive cane molasses is used. The results also indicate it is logistically
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and economically feasible, also environmentally friendly that it is recycled as a cement grinding aid. These results are crucial
to its sustainable and effective uses as well as the reuse of the waste containing similar matters. Additionally, this study also
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helps realize the sustainable production of cement, and also to contribute to the efforts at sustainable construction.

Key words: Cane molasses; Portland cement; Grinding aid; Physical performances; Hydration characteristic
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1 Introduction
The significance of sugar is related to its potential energy contribution and its capacity to sweeten, as well it has been one
of the most important components of the human diet since it is produced in 121 countries. In 2011, sugar worldwide yield a
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total of 0.16 billion tons. China is one of the worlds major producers of sugar and about 12 million tons of sugar was
processed in 2011. Average 16 million tons of it is expected to be produced every year for the next five years. Molasses is a
by-product of sugar industry. About 0.3 ton of it will be discharged while 1 ton of sugar is processed. It is estimated that
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approximately 0.24 billion tons of molasses will be accumulatively discharged in this period. In many developed countries,
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molasses is widely used as raw materials to produce animal feed (Broderick and Radloff, 2004). Most of it also has been used
as concrete water reducing and retarding admixtures (Jumadurdiyev et al., 2005). However, it has been mainly utilized as a raw
material for the fabrication of ethyl alcohol and as a growth medium for yeast production, very little is recycled for use by
livestock in China. Unfortunately, wastewater is usually discharged in these processes (Ingaramo et al., 2009). There are many
organic substances in the wastewater, and their concentrations are high. Besides, it also contains a large amount of dark brown
pigment. It is difficult to be disposed of and is directly discharged outside without reasonable treatment on account of poor
environmental supervision and wastewater treatment technology (Liu et al., 2009). As a result, the serious environmental
problems have been resulted from this practice. The finding of a more proper method of recycling of molasses is certainly a
boon for the sugar industry as well as for the Chinese environmental protection administration. It will not only give the
Chinese sugar industry more financial benefits, but also alleviate many of its potential environmental liabilities.
On the other hand, cement is one of the most important and indispensable building materials. However, cement

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production is an energy intensive process. Thus, cement industry is also one of the main potential contributors to carbon
emissions (Chen et al., 2010). The worldwide cement yield reached up to 3.8 billion tons in 2012, but more than one half was
produced in China. About 2% of the Chinese electricity power was consumed and 0.7 billion tons of carbon dioxide (CO2) was
emitted only in the process of clinker grinding in 2012. It was reported that cement grinding aids improve the clinker grinding
process (Jankovic et al., 2004; Sohon et al., 1991), accelerate clinker crushing, eliminate agglomeration and decrease clinker
specific surface energy (Teoreanu et al., 1999; Rajendran Nair et al., 1999). Hence, they have always applied to improve
grinding efficiency and decrease the energy consumption. Polyhydric alcohols, triethanolanmine amine and
triisopropanolamine provide a good grinding effect. A considerable advantage in the grinding effect can be gained even when

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low concentrations of these compounds are added (Katsioti et al., 2009). They are usually applied as leading raw chemical
materials to compound the cement grinding aids. But they are expensive, and their prices are up to ten thousand Yuan RMB
(Renminbi) per ton in China (current exchange rate is about 6.1 Yuan RMB for one US dollar). Applications of grinding aids

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based on these materials will definitely lead to higher cement production cost. Besides, the non-renewable resources such as
petroleum have to be consumed in the production of these chemical materials. It is bound to intensify the ecological
deterioration and shortage of these non-renewable resources. But above all, waste recycling has become increasingly a popular

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trend given the increasing resource shortage resulted from exponential economic development. Wastes such as ceramics
(Medina et al., 2014), old packaging (Vargas et al., 2014), biomass ash (Pavsic et al., 2014), electroplating sludge (Li et al.,
2014), municipal solid waste incineration bottom ash (Li et al., 2012), and sugar filter mud (Li et al., 2014) have been recycled

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as raw materials or elements to fabricate various products. Gao et al. (2011) proved that beet molasses can be recycled as a
blended cement grinding aid. Although current efforts are admirable, there still remains some important points that need to be
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systematically clarified, in order to make more effective use of cane molasses as a cement grinding aid. The central reasons are
listed as follows.
(1) Chemical components of molasses vary with its raw materials because almost similar process technology is used in all
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Chinese sugar industries. The chemical components of several beet and cane molasses in China are shown in Table 1, which
was summarized by Deng (1995) and Hou (1989). One can easily observe in Table 1 that in China the chemical components
derived from beet and cane molasses differ markedly; however, when similar raw materials are employed the variance in
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outcomes is less pronounced. The total sugar content in cane molasses is usually kept more than 50%. It is higher in it than in
the beet molasses. There are normally about 20% (in mass) of inverted sugar and 5% (in mass) of un-fermentative sugar in the
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cane molasses. However, beet molasses generally does not contain them, and the types of sugar in beet molasses is almost
completely sucrose. Besides, cane molasses is slightly acidic, but the case of beet molasses is reverse. It is difficult, through the
available literature, to properly evaluate the practical effect of cane molasses as a Portland cement grinding aid for these
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differences.
Table 1 Chemical components of several beet and cane molasses in China
Molasses types
Components
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Cane molasses Beet molasses

specimens 1 2 3 1 2
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Brix (%) 85.6 85.6 82.00 81.6 79.6

Total sugar (%) 53.9 50.8 54.8 48.8 49.4
Sucrose (%) 33.9 29.8 35.8 48.8 49.3
Inverted sugar (%) 20 20 19 0 0.1
Purity (%) 62.8 59.4 59.0 59.8 62.0
Un-fermentable sugar (%) 5.1 4.6 5.1 / /
Colloid (%) 9.9 11.1 10.5 10 10
PH (%) 6.0 6.1 6.2 7.4 7.4
Sulfated ash (%) 10.3 11.1 11.1 7.3 8.9
Nitrogen (N) (%) 0.49 0.47 0.54 2.08 2.16
Phosphorus pentoxide (P2O5) (%) 0.13 0.60 0.12 0.029 0.035
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(2) The highest content of beet molasses, 0.05% (in mass), is selected, and the relative works are accordingly developed.
However, there is not any literature, which reports the works related to more cane molasses. These results are critical to inform
decisions regarding new and innovative uses of cane molasses.
(3) A water reducing agent is one of indispensable concrete components. It is mixed with other components in the
concrete production to maintain the required workability, and then other good performances, such as high compressive strength,
better resistances to chloride diffusion and seawater and lower permeability et al, are ensured. Thus the cement compatibility
with the water reducing agent plays an important role in the keeping of the good workability. However, little literature
discusses the compatibility between cement with cane molasses and the water reducing agent.

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(4) In China, cane molasses accounts for more than 90% of the molasses total yield, but beet molasses accounts for only
10%. Therefore, these efforts aimed at getting the sustainably recycled approach for cane molasses is more necessary and
pressing than that for beet molasses. What is more relevant to this study is that the property variation mechanisms of cements

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with cane molasses are not found in the current literature, and there are some doubts about the reuse of cane molasses as a
cement grinding aid.
In view of these above mentioned facts, 97% (in mass) clinker and 3% (in mass) calcium sulphate (CaSO42H2O) were

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interground with cane molasses, and the cement grindability, the setting time, the compressive strength, the water absorption,
the compatibility, and the hydration characteristics are discussed, whilst the mechanisms of these property variations are also
addressed. Besides, the economic, logistical and environmental viability of using cane molasses as a cement grinding aid are

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also considered in this paper. These results are essential in estimating the applied effect and in obtaining the reliable dosage of
cane molasses that should be used as a cement grinding aid. Clearly, these results are not just critical to the practical and
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efficacious application of cane molasses, but also to the recycling industry for wastes that contain similar materials to cane
molasses.

2 Experimental
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In this work, three essential materials, cement clinker, CaSO42H2O, and cane molasses were used, and their origins and
chemical components are listed. These methods used to analyse the components of cement clinker and cane molasses, the
particle size distribution and Blaine specific surface area of cement, grindability, setting times, compressive strength, water
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absorption, compatibility, calcium hydroxide ( Ca(OH)2) (CH) content and microstructure are also given.
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2.1 Materials
The cement clinker that was used in this study came from a cement processing facility. CaSO42H2O was chemical
reagent. Cane molasses was provided by Guangxi Yangpu Nanhua Sugar Industry Group Co., LTD. The sugar obtained from
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this company accounts for about 18% of Chinese total national yield. The raw materials used in the production of the sugar
came from sugar cane. The principal chemical components of cement clinker and cane molasses are shown in Table 2 and
Table 3. It can be observed form Table 3 that in this cane molasses, there are 20% inverted sugar and 5.1% un-fermentable
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sugar. The PH value is 6.1, and it is slightly acid. Molasses from this company represents the component characteristics of
Chinese cane molasses.
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Table 2 Principal chemical components of cement clinker (wt %)

Oxides CaO SiO2 Al2O3 Fe2O3 SO3 K 2O MgO TiO2 others LOI
Content 64.3 19.8 4.69 2.84 1.96 1.84 0.9 0.23 2.43 1.01
Table 3 Principal chemical components of cane molasses
Sugar Sucrose Inverted sugar Un-fermentable sugar Colloid
Component PH
(wt %)
Content 54 34 20 5.1 9.2 6.1

2.2 Methods
Cement clinker was ground to the 200 ASTM mesh, and the SRS3400 X-ray fluorescence spectrometer was used to
determine cement chemical components. The chemical components of the cane molasses were determined by chemical titration.
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In this procedure, the chemical reagents of methylene blue, hydrochloric acid, sodium hydroxide (NaOH) and potassium
ferricyanide, were selected. After treating the solution with an acid hydrolysis, testing was conducted to determine the total
sugar content of the cane molasses solution according to the Chinese National Standard GB/T 5009.7-2003. The hydrolysed
cane molasses was dropped into 30% NaOH solution, and then this solution was titrated by 1% potassium ferricyanide solution.
The titer was finally determined and the content of total sugar was acquired after the potassium ferricyanide was completely
reduced by the inverted sugar produced in the acid hydrolysis process. The contents of the sucrose, the inverted sugar, the
un-fermentable sugar, and the colloid were determined by using the Roe colorimetric analysis, the Lane-Eynon method, the
3,5-dinitrosalicylic acid (DNS) method, and the Dische colorimetric analysis.

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The particle size distribution of the cement was analyzed by a LS230 laser particle size analyzer. Ethyl alcohol was used
as the medium of dispersal of the cement particles. According to the Chinese National Standard GB/T 8074-2008, the cement
specific surface area was determined by the Blaine air permeability method.

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0.01, 0.02, 0.04, 0.08 and 0.1% (in mass) of the cane molasses were added to the mixture containing about 97% cement
clinker (4850 g) and 3% (150 g) CaSO42H2O. Mixture with cane molasses was ground in the ball mill to the Blaine specific
surface area of about 3800 cm2/g, and the grindabilities of mixtures with cane molasses were evaluated. The rotate speed of

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mill was 48 rpm. The ratio of mixtures to grinding ball was 1:32, and the grinder weight was 160 kg. The grinder and lining
were prepared with steel. In this study, 25 mm35 mm steel forgings were also used in addition to 40, 50, 60 and
70mm spherical grinders. The revolution of ball mill was simultaneously recorded with a counter when mixtures started to be

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ground. After grinding the cement for varying time, the Blaine specific surface areas of the cements were analyzed. The
grinding finished after Blaine specific surface areas of mixtures reached to about 3800 cm2/g. The grindabilities of the clinkers
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with cane molasses were accordingly accessed with the following equation (1)
A
G= (1)
R
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where G is the grindability index; A is the Blaine specific surface area; R is the mill revolution needed to grind the clinker to
the corresponding Blaine specific surface area.
The cement setting times were examined according to the Chinese National Standard GB/T 1346-2001. The testing of
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cement compressive strength was carried out according to the Chinese National Standard GB/T 17671-1999. 1350 g cement
was weighed. One unit of cement was mixed with three units of quartz sand and one half unit of water, and the mortars with
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the cane molasses were prepared. The mortars were placed in the 160mm40mm40 mm metal molds. Under relative
humidity of 90%, the molds were cured for 24 h at 20 0C. Once the time was up, the molds were removed, and then put into
water at 20 0C for 3, 7, and 28 days, respectively. Three prismatic specimens were tested at every hydration age, and six
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compressive strength values were acquired. Their average value was calculated as well as the compressive strength of the
cement was determined if the six values would not exceed the 90-110% average value.
The water absorptions of mortars with cane molasses were measured according to Chinese National Standard GB/T
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11970-1997. The mortars were prepared in the molds of 160mm40mm40 mm. The ratios of water/cement and sand/ cement
were kept as the constants of 0.5 and 3 respectively. The molded mortars were kept at 20 2 0C and relative humidity
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exceeding 90% for 1 day, and then removed from the molds and they continued to be kept this condition for 27 day. After
cured, these mortars were dried at the temperatures of 605 0C and 805 0C for 24 h respectively, and kept at 1055 0C for the
constant weight. Their dry weights were acquired, and they were cooled to the room temperature. The cooled mortars were put
into water at 20 2 0C for different times, and then they were taken out from the water. They were cleaned with a duster, and
their weights were tested. The following equation was used to calculate the water absorptions of the mortars with the cane
molasses.

mg m 0
WR = 100 (2)
m0
where WR is the water absorption (in mass, %); mg is the weight of mortar after dipped in the water for different time; m0 is the
weight of mortar after dried at 1055 0C for the constant weight.
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Water reducing admixtures of polycarboxylate and naphthalene used in this study were commercially acquired products.
Their solid contents accounted for about 40% (in mass) of the total mass, and their additional contents were 0.25 and 0.5% (in
mass) of the cement. Slump flows of cement pastes at 0, 30 and 60 min were determined according to the Chinese Building
Materials Industry Standard JC/T1083-2008, and an analysis was conducted of the cement compatibility with the water
admixture.
CH contents in the hardened pastes were measured by DTA-TG. A NETZSCH-STA 449 C thermal analyzer was used
with an atmosphere of oxygen-free nitrogen and at a heating rate of 10 /min. Comparison of the DTA curve areas of the
hardened pastes was conducted with that of the pure CH, CH contents in hardened pastes were determined by the equation (3).

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SCH in hardened paste
CCH = 100 (3)
Spure CH

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where CCH is the CH contents (in mass, %) in the hardened pastes; SCH in hardened paste is the DTA curve areas of hardened pastes;
Spure CH is the DTA curves area of pure CH.
A Quanta 200 FEG field emission environmental scanning electron microscope (SEM) was used to observe the

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microstructure of mortar that was cured after 28 days. The accelerating voltage was 20kV, and the magnification was 15000.

3 Results and discussions

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In this chapter, the results on grindability, setting time, compressive strength, water absorption, compatibility, CH content
in hardened paste, SEM microstructure, the economic, logistical and environmental analysis are provided and discussed.
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3.1 Grindability
Grindability is the measure of the cement clinker ability to resist grinding forces. It is an indicator to estimate the energy
required for grinding the clinker to the given Blaine specific surface area. It provides the relationship between the revolution
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and the given Blaine specific surface area. The grindability indexes of cement clinkers with cane molasses are shown in Table
4. The grindability index of control is compared with that of others. It is found from Table 4 that the cane molasses presence
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definitely results in the increase of this index, and the cane molasses is effective in the improvement of clinker grinding. The
improvement in clinker grinding quality is principally related to the increased levels of cracking of the cement particles, the
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lessening or perhaps the elimination of particle agglomeration. The clinker particles are charged with electrostatic chargers due
to calcium-oxygen (Ca-O) bond cleavage and the rubbing between the clinker and grinder, and the agglomeration is happened
(Moothedath and Ahluwalia, 1992). However, the cane molasses consists of sucrose, inverted sugar (It is mainly composed of
fructose and glucose), un-fermentable sugar (It is mainly comprised of isomaltose) and other organic substances (Feng, 2010).
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The molecular formulas of sucrose, fructose, glucose and isomaltose are given in Fig. 1. They are hydroxyl compounds as
shown in Fig. 1 and display high polarity. These hydroxyl compounds form a covering layer that is absorbent due to hydrogen
bonds on the surface of the clinker particle. It plays a role as the shield, and prevents the bond tendency of clinker particles
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with opposite charges or enables them neutralization. The agglomeration is accordingly weakened or eliminated. Besides,
colloid is also presented in the cane molasses. It has high viscosity, and helps consolidate the stability of covering layer. Thus
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clinkers with the cane molasses are provided with better grindability. More cane molasses is added, and then more is the
covering layer available. Meanwhile, more colloid is introduced, and the covering layer progressively becomes more stable.
Hence, the clinker grindability is raised as the cane molasses content increases, and the clinker with more cane molasses has
higher grindability index than those with less.
Table 4 Grindability indexes of cement clinkers with cane molasses
Cane molasses content (wt, %) 0 0.01 0.02 0.04 0.08 0.1
2
Blaine specific surface area (cm /g) 3804 3800 3816 3821 3811 3809
Mill revolutions (cycle number) 5300 4960 4700 4560 4420 4240
Grindability index 0.718 0.766 0.811 0.838 0.862 0.898

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Fig. 1 Molecular formulas of sucrose, fructose, glucose and isomaltose

3.2 Setting time

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The initial and final setting times of the cements with cane molasses are shown in Fig. 2A and B. The results indicate that
in general, cane molasses delays the setting times, and that cements containing more cane molasses show the longer setting
time. The initial and final setting times of cement with 0.1% cane molasses prolong up to 85 and 106 min. Saccharides tend to

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postpone the tricalcium silicate (C3S) hydration (Jumadurdiyev et al., 2005). C3S is the principal component phase of Portland
cement, and the regular setting, to some extent, relies on its hydration (Chen et al., 1992). As a consequence, this setting
prolongation is related to the saccharide presence. However, saccharides, specially the sucrose, also promote the hydration of

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tricalcium aluminate (C3A) (Wu et al., 1998). The effect of sucrose on setting prolongation is weakened for accelerated
hydration of C3A. Therefore, as shown in Fig. 2A and B, the fact is also found that the scale of setting prolongation is various
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with the content of the cane molasses. The scale gradually becomes larger when 0.01-0.08% cane molasses is used. When
more than 0.08% of the cane molasses is mixed, the scale begins to be lessened slowly. Even the different cases may be
observed that setting times are sharply shortened and the irregular setting or the false condensate is found while excessive cane
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molasses is added.
220
280
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200
260
Initial setting time (min)

Final setting time (min)

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180 240

220
160
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200
140
180
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120 160

0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06 0.08 0.10
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Cane molasses content (%) Cane molasses content (%)

(A) (B)
Fig. 2 Initial and final setting times of cements with cane molasses

3.3 Compressive strength

Compressive strengths of cements with cane molasses at different hydration ages are shown in Fig .3. It indicates that
cane molasses can affect the compressive strength. When less than 0.04% of the cane molasses is added, the compressive
strength is gradually raised as the increase of cane molasses content. The cement with 0.04% cane molasses is provided with
higher compressive strengths than the control at 3, 7 and 28 days, and Its compressive strengths increase by 2.9, 2.2 and 4.3
MPa at 3, 7 and 28 days. These increases come from water reducing effect of the cane molasses (Jumadurdiyev et al., 2005).
Although proper saccharide in the cane molasses puts off C3S initial hydration and accelerate C3A hydration, more mixed

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water are not consumed. The major mixed water is kept as free water and appeared in the paste mixing process, and the paste is
provided with better workability. The denser microstructure will be formed in the later cement hardening. As a result, the
cement with less than 0.04% cane molasses is provided with higher compressive strength. However, excessive cane molasses
accelerates the C3A hydration, and the more mixed water is consumed. The consistence of cement paste is raised, and paste
workability becomes poor. The inhomogeneous or loose microstructure is formed in the mortar, and then the compressive
strength is negatively affected. The compressive strength of cement with more than 0.04% cane molasses is lower than that of
the control. It is evident that enhancement in compressive strength is related to the addition of cane molasses content to the
cement.

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65

60
Compressive strength (MPa)

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55
3d
50 7d

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28d
45

40

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35
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30
0.00 0.02 0.04 0.06 0.08 0.10
Cane molasses content (%)
Fig. 3 Compressive strengths of cements with cane molasses at different hydration ages
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3.4 Water absorption

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10
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8
Water absorption (%)

0.1%
0.08%
0%
0.01%
6 0.02%
0.04%
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4
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Drawing (x start from10, y from6)

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0
0 10 20 30 40
t1/2 (min1/2)
Fig. 4 Water absorptions of mortars with cane molasses at different times1/2
Water absorptions of mortars with cane molasses at different times1/2 are presented in the Fig. 4. It is found from Fig. 4
that the mortars display different relationships between time1/2 and the corresponding water absorption. While these
relationships are linear, they have various slopes. The mortars with cane molasses show the different rates of water absorptions,
these rates are related to the content of cane molasses. Among all mortars, the mortar with 0.1% cane molasses obviously
presents a highest this rate. The following are mortars with 0.08, 0.06, 0%, 0.02 and 0.04% cane molasses. The results suggest
that cane molasses is capable of changing the pore characteristics. The mortar is not evenly stirred for the fact that more than
0.04% cane molasses cause the increase of cement water demand. The microstructure is not compacted, and then more pores
are appeared in the hardened paste. Mortar with more than 0.04% cane molasses has the higher porosity than others, and the
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rate of its water absorption is increased. However, the case is reverse when less than 0.04% cane molasses is added. Mortar can
be evenly stirred due to the reducing water effect of the cane molasses, and the microstructure is compacted. The porosity in
the hardened paste is reduced, and the rate of the water absorption is decreased. The porosity of mortar with 0.04% cane
molasses is lowest of all. The microstructure of mortar with 0.1% cane molasses displays most loosely.

3.5 Compatibility
Water reduction effect of water reducing admixture does not depend solely on its own characteristics, but on the cements
mineral composition, particle size, and other factors. Compatibility usually is a comprehensive indicator used to evaluate the
effect of the cements property on the reduction of water effect. The slump flows of cement pastes with water reducing

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admixtures of naphthalene and polycarboxylate are given in Fig .5A and 5B. They show that cane molasses can has notable
impact on the slump flow. Table 5 shows the particle size distributions of the cements with the cane molasses. As shown in the
Table 5, all cements are provided with almost similar particle size distributions. It hereby can be concluded that this impact

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does not result from the cement particle size distribution, but from cane molasses. Moderate saccharide postpones C3S
hydration, and a water reducing effect is brought into play. Hence, cement with 0.01% cane molasses is provided with slightly
higher slump flow. Cement with 0.02% cane molasses has the almost similar slump flow to the control. However, excessive

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cane molasses can lead to the accelerated hydration of the C3A. More mixed water is consumed and the cement paste is
thickened. Besides, the hydrated calcium aluminate is generated in the early process of hydration of C3A. It has high specific
surface area and many positive charges. It can adsorb a great number of water reducing agent (Bensted and Barnes, 2000).

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More hydrated calcium aluminate is produced for C3A accelerated hydration, and more water reducing admixture is absorbed.
Thus, the case changes when the content of the cane molasses is continuously increased. Slump flow of cement with 0.04%
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cane molasses is obviously decreased, and the sharp decline of slump flow is observed when 0.08 and 0.1% cane molasses is
used. It is obvious that these facts all are found in the cement pastes with these two different water reducing admixtures. Cane
molasses affects the cement compatibility with water reducing admixture.
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Table 5 Particle size distributions of cements with cane molasses

Cane molasses content (wt, %) 0 0.01 0.02 0.04 0.08 0.1
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Particle size (m) Volume percent (%)

3 13.8 13.1 13.6 13.5 13.4 13.2
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330 58.5 58.7 58.8 59.7 58.7 57.9

30-60 23.5 22.8 23.0 22.6 23.1 23.9
60 4.2 5.4 4.6 4.2 4.8 5.0
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220
Naphthalene based 240 Polycarboxylic based
200 0 min 0 min
30 min 220 30 min
180 60 min 200 60 min
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160 180
Slump flow (mm)
Slump flow (mm)

140 160
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140
120
120
100
100
80
80
60 60
40 40
0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06 0.08 0.10
Cane molasses content (%) Cane molasses content (%)

(A) (B)
Fig. 5 Slump flows of cement pastes with water reducing admixtures of naphthalene and polycarboxylate

3.6 CH content in hardened paste

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Portland cement hydration is a sequence of overlapping chemical reactions between clinker components, CaSO42H2O
and water, leading to the cement setting and eventually hardening. The continued development leads to the obtainment of
ultimate mechanical property. The key hydration product, CH is produced throughout the process and its content enhance
gradually till the process end. It, in some ways, is proportional to the cement hydration degree. It was determined in order to
detailedly investigate the impact of cane molasses on cement hydration. The CH contents in cement pastes with cane molasses
at different hydration ages are presented in Fig. 6. It is observed from results that cane molasses affects the CH content. The
CH content at 3 days is decreased by degrees as the cane molasses content increase. Obviously, saccharide presence postpones
the early hydration. However, the different case appears while the hydration time is prolonged. Although cane molasses

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postpones the early hydration, the mortar is evenly stirred for water reducing effect when the cane molasses content is less than
0.04%. Cements with 0.01, 0.02 and 0.04% cane molasses are well hydrated at the later ages. Therefore, they are provided with
higher CH content than others at 7 and 28 days. However, too much saccharide is introduced when more cane molasses is

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added, and its water requirements as well as hydration times are increased. Cement with more than 0.04% cane molasses is
unevenly mixed, and the later hydration is negatively affected. Hence, CH contents in cement pastes with 0.08 and 0.1% cane
molasses are still notably decreased even at the later hydration ages. It indicates that appropriate cane molasses helps improve

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the later hydration, but the case is reverse when excessive cane molasses is added. Even the later hydration is also delayed.
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CH content (%)

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28d
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0.00 0.02 0.04 0.06 0.08 0.10

Cane molasses (%)
Fig. 6 CH contents in cement pastes with cane molasses at different hydration ages
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3.7 SEM observation

SEM images of cement pastes with cane molasses after cured 28 days are shown in Fig. 7. Cement hydration products
such as calciumsilicate hydrate (C-S-H) gel, CH and ettringite are overlapped together, and they can be observed in the
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fracture surface micrographs. Besides, it can be obviously found that the cane molasses affects the mortar microstructure.
About 2 m pores are observed in the control (Fig. 7 (control)). One can clearly see that the hydrated products have grown
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together and filled some pores. It is seemed that these size pores are lessened in the mortar with 0.01% cane molasses (Fig. 7
(0.01%)). The pore is difficult to find, and the hardened cement pastes with 0.02 and 0.04% cane molasses show the denser
microstructures (Fig. 7 (0.02 and 0.04%)). The microstructure of the hardened paste with 0.08% cane molasses becomes sparse,
and about 4 m pores are found (Fig. 7 (0.08%)). The microstructure becomes sparser, the pore dimension is raised, and some
pore diameters reach as high as 10 m in the paste with 0.1% cane molasses (Fig. 7 (0.1%)). As implied in the water
absorptions, mortar microstructure is closely associated with the cane molasses content. 0.08-0.1% cane molasses will result in
a high water demand as well as the pastes being hard and will be difficult to stir and work. However, less than 0.4% cane
molasses displays water reducing effects and the cement with it has better workability. The denser microstructure is formed,
and the cement is provided with high compressive strength. However, the results of the cements with 0.08 and 0.1% cane
molasses are reversed, and the sparser microstructure and larger pores are appeared. They accordingly cannot get the good
compressive strength.

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(control) (0.01 %) (0.02 %)

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(0.04 %) (0.08 %) (0.1 %)
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Fig. 7 SEM images of cement pastes with cane molasses after cured 28 days

3.8 Logistics and economic analysis

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The principal origins of Chinese cane molasses are displayed in Fig. 8. As shown in Fig. 8, Guangxi, Guangdong, Yunnan
and Hainan provinces are its main origins. Those provinces are mainly distributed in the southern of China. They are also the
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important cement origins. In 2012, the cement yields of these four provinces are 0.098, 0.118, 0.05 and 0.015 billion tons
respectively. Often much of the cane molasses can be reused by local cement facilities. The rest can be loaded in the plastic
container and transported to other regions through railway, shipping and land carriage, and stored in the huge cask for the later
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use. Besides, the origins of triethanolanmine amine and triisopropanolamine, which are the main raw materials of cement
grinding aids, are mainly located in Fushun, Shanghai and Nanjing, the eastern of China. The regional distributions of cane
molasses and hydramine raw materials in China are given in Fig. 9. It can be observed from Fig. 9 that the transportation
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distances from these cities to other regions are nearly similar to that from Guangxi, Guangdong, Yunnan and Hainan. Therefore,
the transportation cannot lead to a more expensive cost and negatively affects the feasibility of cane molasses as a cement
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grinding aid. Furthermore, since the price of cane molasses is only about two thousand yuan RMB/ton, it is more cost effective
since its price is far lower than that of most other cement grinding raw materials. In recent year, many supplementary
cementitious materials, such as fly ash, calcined clay, coal gangue, slag, metakaolin and other natural pozzolans, are partially
used to replace cement clinker to produce blended cement in many countries, for the purposes of saving energy, decreasing
cost and sinking the scale of CO2 discharge (Pandey et al., 2003; Tsivilis et al., 2002). Unfortunately, the early strength
development of blended cement is markedly slower than that of ordinary Portland cement when more cement clinker is
replaced with them. This shortcoming, to some extent, restricts the replacement content, and the advantages of blended cement
cannot be fully exploited. However, less than 0.04% cane molasses can improve the early strength. Therefore, the replacement
level can be raised, and the more energy and cement production cost would be saved.

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Fig. 8 Principal origins of Chinese cane molasses

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Fig.9 Regional distributions of cane molasses and hydramine raw materials in China

3.9 Environmental analysis

Several important operations such as transportation, preparation, application, and service are involved in the process of
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the production of cane molasses to be used as a cement grinding aid. During the transportation, cane molasses can be loaded in
stout plastic casks. These casks are easily transported and handled as well as providing the benefit of not allowing for seepage
of cane molasses. The cane molasses is commonly diluted with water and thoroughly recycled, and no waste is discharged in
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this operation. Then, the diluted cane molasses is pumped to the inner part of the cement mill and ground along with the
clinker. It improves the cement clinker grindability and lowers the energy needed to grind the cement to the given specific
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surface area. Beyond simply being a cement grinding aid, the cane molasses contributes to the compressive strength increase of
the resulting finished cement. Therefore, the energy consumed to sinter the clinker can be saved. Utilization of cane molasses
as a cement grinding aid is not only beneficial to its management, but also to the reduction of CO2 emissions in the cement
industry. Cane molasses does not contain any toxic materials. Besides, only a small quantity of it is used and can be
consolidated into the cement paste. Therefore, no toxic matter is leaked during the service of cement product, and it is safe to
the environment that cane molasses is recycled as a grinding aid in the cement production process.

4. Conclusions
This paper presents the research concerning the reuse of cane molasses as a grinding aid in the production of Portland
cement. The important conclusions have been summarized as follows:
i. Cane molasses is effective in the improvement of grinding clinker.

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ii. Cane molasses prolongs the cement setting times, but the setting prolongation scale varies according to the cane
molasses content.
iii. Compressive strength of the resulting cement with less than 0.04% of cane molasses is higher than that of the
control. However, this case reverses when more than 0.04% of cane molasses is added.
iv. Cane molasses has a notable impact on the slump flow of the cement paste. Cement with less than 0.02% of cane
molasses has good compatibility with water reducing admixture. However, the slump flow of cement with more than
0.04% of cane molasses is obviously decreased, and the cement compatibility with water reducing admixture
becomes poor.

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v. CH results indicate that appropriate amounts of cane molasses can help improve the cements later hydration, but
excessive cane molasses can adversely affect the cements later hydration.
vi. Water absorption and SEM observation imply that cement paste with less than 0.04% cane molasses has the denser

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microstructure than the control. It provides a microcosmic proof for compressive strength variation of cement with
cane molasses.
vii. It is logistically, economically and environmentally feasible to recycle cane molasses as a cement grinding aid.

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In summary, it is practically feasible to recycle cane molasses as a cement grinding aid in the production of Portland
cement. The sugar industry, cement industry, and environment accordingly can all be sustainably developed. Especially, the
cement cost and the energy consumed in production can be saved, as well as the application of cane molasses helps the

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realization of sustainable construction. However, the cane molasses dosage should be selected carefully in order to fully exploit
the advantage of cane molasses. These results are useful to the cane molasses in practical application and in selection of
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reliable dosage of it as a cement grinding aid.

Acknowledgements
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The authors gratefully acknowledge the financial support provided by National Basic Research Program of China (973
Program: 2011CB013805), National Natural Science Foundation of China (51302189, 51308406), National Key Project of
Scientific and Technical Supporting Programs of China (No. 2014BAL03B02), and the Key Laboratory of Advanced Civil
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Engineering Materials (Tongji University), Ministry of Education.

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References
Bensted J, Barnes P, 2000. Structure and performance of cements-second edition. Spon press: London, Britain.
Broderick G A, Radloff W J, 2004. Effect of molasses supplementation on the production of lactating dairy cow fed diets based on alfalfa and corn silage. J.
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Dairy. Sci. 87(9), 29973009.

Chen C, Habert G, Bouzidi Y, Jullien A, 2010. Environmental impact of cement production: detail of the different processes and cement plant variability
evaluation. J.Clean. Prod. 18 (5), 47885.
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Chen Y, Odler I, 1992. On the origin of Portland cement setting. Cem. Concr. Res. 22(6), 1130-1140
Chinese National Standard, 2003. GB/T 5009.7: Determination of reducing sugar in foods. Standards Press of China, Beijing.
AC

Chinese National Standard, 2008. GB/T 8074: Testing method for specific surface of cement-Blainee method. Standards Press of China, Beijing.
Chinese National Standard, 2001. GB/T 1346: Test methods for water requirement of normal consistency, setting time and soundness of the portland cements.
Standards Press of China, Beijing.
Chinese National Standard, 1999. GB/T 17671: Method of testing cements-Determination of strength. Standards Press of China, Beijing.
Chinese National Standard, 1997. GB/T 11970: Test methods for bulk density, moisture and water absorption of aerated concrete. Standards Press of China,
Beijing.
Chinese Building Materials Industry Standard, 2008. JC/T 1083: Testing method for compatibility of cement and water reducing agent. Building Materials
Industry Press of China, Beijing.
Deng B Y, 1995. Resource utilization and environmental protection on cane sugar industry. Chinese light industry press, Beijing, China (in Chinese).
Feng H W, 2010. Desalination of sugar cane molasses by electroosmosis: (Master Thesis).Guangzhou (in Chinese).
Gao X J, Yang,Y Z, Deng H W, 2011. Utilization of beet molasses as a grinding aid in blended cements. Constr. Build. Mater. 25(9), 37823789.

12
 ACCEPTED MANUSCRIPT
Huo H Z, 1989. Resource utilization and deep processing of cane and sugar products. Guangdong Sugar Industry Association Press, Guangzhou, China (in
Chinese).
Ingaramo A, Heluane H, Colombo M, Cesca M, 2009. Water and wastewater eco-efficiency indicators for the sugar cane industry. J. Clean. Prod. 17(4),
487495.
Jankovic A, Valery W, Davis E, 2004. Cement grinding optimization. Miner.Eng. 17(1112), 10751081.
Jumadurdiyev A, Hulusi Ozkul M, Saglam A R, Parlak N, 2005. The utilization of beet molasses as a retarding and water-reducing admixture for concrete.
Cem. Concr. Res. 35(5), 874882.
Katsioti M, Tsakiridis P E, Giannatos P, 2009. Characterization of various cement grinding aids and their impact on gindability and cement performance.

PT
Constr. Build. Mater. 23(5), 1954-1959.
Li H X, Yang X J, Xu W, Wu J G, Xu J C, Zhang G F, Xia Y B, 2014. Application of dry composite electroplating sludge into preparation of cement-based
decorative mortar as green pigment. J. Clean. Prod. 66, 101-106.

RI
Li H X, Xu W, Yang X J, Wu J G, 2014. Preparation of Portland cement with sugar filter mud as lime-based raw material. J.Clean.Prod.66, 107-112.
Li X G, Lv Y, Ma B G, Chen Q B, Yin X B, Jiang S W, 2012. Utilization of municipal solid waste incineration bottom ash in blended cement. J.Clean.Prod.32,
96-100.

SC
Liu W, Liu Y, Liu S, Jiang X, 2009. The progress of research on treating molasses waste water and resources. China. Res. Compr.Util. 27, 39-41 (in Chinese).
Medina C, Frias M, Sanchez de Rojas M I, 2014. Leaching in concretes containing recycled ceramic aggregate from the sanitary ware industry. J.Clean. Prod.
66, 85-91.

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Moothedath S K, Ahluwalia S C, 1992. Mechanism of action of grinding aids in comminution. Powder Technol. 71(3), 229-237.
Pandey S P, Singh A K, Sharma R L, Tiwari A K, 2003. Studies on high-performance blended multiblended cements and their durability characteristics. Cem.
AN
Concr. Res. 33(9), 14331436.
Pavsic P, Mladenovic A, Mauko A, Kramar S, Dolenec M, Voncina E, Vrtac K P, Bukovec P, 2014. Sewage sludge/biomass ash based products for
sustainable construction. J.Clean. Prod. 67(15), 117-124.
M

Rajendran Nair P B, Paramasivam R, 1999. An analysis of the influence of grinding aids on the breakage process of calcite in media mills. Adv.
Powder.Tecnol. 10(3), 223-243.
Sohoni S, Sridhar R, Mandal G, 1991. The effect of grinding aids on the fine grinding of limestone, quartz and Portland cement clinker. Powder.Technol.
D

67(3), 277286.
Teoreanu I, Guslicov G, 1999. Mechanisms and effects of additives from the dihydroxy-compound class on Portland cement grinding. Cem.Concr. Res. 29(9),
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915.
Tsivilis S, Chaniotakis E, Kakali G, Batis G, 2002. An analysis of the properties of Portland limestone cements and concrete. Cem. Concr. Compos. 24(3-4),
371378.
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Vargas A, Silva B V, Rocha M R, Pelisser F, 2014. Precast slabs using recyclable packaging as flooring support elements. J.Clean. Prod. 66, 92-100.
Wu J W, Wang P M, 1998. Mechanism of regulation set of sucrose in Portland cement. J. Chin. Ceram. Soc. 26(2): 164-170 (in Chinese).

Abbreviation
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CO2: carbon dioxide

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RMB: Renminbi
US: United State
LOI: Loss on ignition
CaSO42H2O: calcium sulphate
N: Nitrogen
P2O5:Phosphorus pentoxide
ASTM: American Society for Testing Material
DNS: 3,5-dinitrosalicylic acid
NaOH: sodium hydroxide
CH: Calcium hydroxide, Ca(OH)2
DTA: Differential Thermal Analysis

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TG: Thermogravimetry
SEM: Scanning Electron Microscope
C3S: tricalcium silicate
C3A: tricalcium aluminate
C-S-H: calciumsilicate hydrate
CaO: calcium oxide
SiO2: silicon dioxide
Al2O3: aluminium oxide

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Fe2O3: ferric oxide
SO3: sulfur trioxide
K2O: potassium oxide

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MgO: magnesium oxide
TiO2: titanium oxide

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Highlights

Cane molasses improves the cement clinker grindability. Cane molasses affects cement
setting time and microstructure. Proper cane molasses increases the cement compressive
strength. It has notable impact on the cement compatibility. It is logistical and economically
feasible, also environmentally friendly.

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