International Journal of Green Energy

ISSN: 1543-5075 (Print) 1543-5083 (Online) Journal homepage: http://www.tandfonline.com/loi/ljge20

Promotional Effect of Transition Metal Doping on

the Properties of KF/Cao Catalyst for Biodiesel
Synthesis

Lingmei Yang, Pengmei Lv, Zhongming Wang, Zhenhong Yuan, Wen Luo,
Huiwen Li, Luo Yu & Hongzhe Sun

To cite this article: Lingmei Yang, Pengmei Lv, Zhongming Wang, Zhenhong Yuan, Wen Luo,
Huiwen Li, Luo Yu & Hongzhe Sun (2017): Promotional Effect of Transition Metal Doping on the
Properties of KF/Cao Catalyst for Biodiesel Synthesis, International Journal of Green Energy, DOI:
10.1080/15435075.2017.1330752

To link to this article: http://dx.doi.org/10.1080/15435075.2017.1330752

Accepted author version posted online: 19

May 2017.

Submit your article to this journal

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=ljge20

Download by: [Eastern Michigan University] Date: 19 May 2017, At: 03:01
 Promotional effect of transition metal doping on the
properties of KF/CaO catalyst for biodiesel synthesis
Lingmei Yang a,b*, Pengmei Lv a, Zhongming Wanga,,Zhenhong Yuan a ,c,Wen Luo a, Huiwen
Li a, Luo Yud and Hongzhe Sunb

t
a
Key Laboratory of Renewable Energy, Chinese Academy of Sciences

ip
Guangdong Key Laboratory of New and Renewable Energy Research and Development

cr
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangdong
Province, Guangzhou 510640 , P.R China ;

us
b
School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangdong
Province, Guangzhou ,510600 P.R China
c
Collaborative Innovation Centre of Biomass Energy, Henan Province, Zhengzhou 450002, Chin
an
a.
d
Environmental Protection Bureau of Shuangtaizi District Panjin , Liaoni Province,124000,P.R
China
M

ABSTRACT :
ed

A series of heterogeneous KF/CaO catalysts modified with transition metals (lanthanum, cerium,

and zirconium) were prepared via wet impregnation method and applied to the
pt

trsansesterification process of waste cooking oil (WCO) as feedstock with methanol to biodiesel
ce

production .The structure, performance of the solid catalysts was characterized by X-ray

diffraction (XRD), temperature programmed desorption of CO2(CO2-TPD),scanning electron

Ac

microscopy (SEM) and energy-dispersive spectroscopy(EDS).The effect of methanol/oil molar

1
ratio, 1reaction time, reaction temperature, catalyst amount and stability was investigated. The

results showed that 10 wt% of lanthanum, cerium, and zirconium improved the catalytic activity

of KF/CaO catalyst. The maximum catalytic activity using the lanthanum doping of 10wt% on

KF/CaO catalyst was reached 98.7 % under the optimal reaction condition of methanol/oil molar

t
ratio of 12:1, reaction for 1 h at reaction temperature of 65 °C, and 4% (wt/wt oil ) catalyst

ip
amount .And the FAME yield of KF/CaO/La catalyst remained higher than 95% after 10 cycles.

cr
The promotional effect of lanthanum doping could be attributed to the enhancement of the

us
2+
basicity strength of KF/CaO catalyst and block the leach of Ca in the transesterification

reaction.
an
Keywords: Biodiesel , waste cooking oil, transesterification, heterogeneous catalyst, transition

metal
M

1. Introduction
ed

Owing to increasing price of petroleum and being exhausted of traditional fossil fuels
pt

together with pollution of environment, the search for clean, renewable fuels has gained much
ce

attention. Biodiesel, as a renewable energy source, has combustion properties similar to those of

petrochemical materials (Vyas, Verma, and Subrahmanyam 2010; Patel and Sankhavara 2017;
Ac

1
*Correspondence to : Lingmei Yang, Guangzhou Institute of Energy Conversion, Chinese

Academy of Sciences, Guangzhou Guangdong, 510640 P.R China .E-Mail:

[email protected]

2
Mahmudul et al. 2017). Biodiesel, namely fatty acid methyl/ethyl esters (FAME or FAEE), can

be produced via reacting a vegetable oil or animal fat with methanol or ethanol in the presence of

a catalyst to form methyl or ethyl esters and glycerin(Zhang et al. 2012; Verma and Sharma

2016). At present, biodiesel is mainly prepared by homogeneous catalysts, such as NaOH ,KOH

t
or sodium alcoholate ,sulfuric acid et al(Li et al. 2012; Deshmane and Adewuyi 2013). However,

ip
these homogeneous catalysts, although effective, are shown to be sensitive to water and free fatty

cr
acid (FFA) present in the feedstock to form unwanted soap by-products, which makes the

us
product separation difficult and also reduces the performance of the catalysts. Unlike

homogeneous catalysts, heterogeneous catalysts are easy separating by simple method and can
an
be reused and regenerated(Lam, Lee, and Mohamed 2010; Leung, Wu and Leung 2010; Borges

and Díaz 2012) . Therefore, the development of heterogeneous catalysts is of great importance.
M

Heterogeneous catalysts used for biodiesel production comprised of solid acid and solid

base catalysts. Solid base catalysts generally offer higher conversion at relatively lower
ed

temperature compared with solid acid catalysts. At present, a number of different solid base
pt

catalysts for biodiesel synthesis have been investigated, including alkaline metal oxides(Ren et

al. 2012; Atadashi et al 2013), alkaline earth oxides(Refaat 2011), basic hydrotalcite(Wang et al.
ce

2015), basic zeolites(Sun et al. 2015; Volli and Purkait. 2015), and ion exchange resins (Steene,

Clercq and Thybaut 2014).Calcium oxide (Kouzu et al. 2008; Marinković et al. 2016; Banković–
Ac

Ilić et al. 2017) is the most widely utilized solid base catalysts due to its many advantages, which

include long catalytic life, good catalytic activity, and mild reaction conditions. Yoosuk et

al.(2010)have also used a calcite natural source to produce CaO. The ME content as high as 95.7

wt.% can be obtained over CaO600 under suitable conditions, that is, with a methanol/oil molar

3
ratio of 15, a catalyst weight of 7 wt.%, a reaction temperature of 60 °C, and a reaction time of

45 min.

Generally, mixed metal oxides and modified mixed metal oxides could show higher activity

than their single constituent metal oxides. Besides CaO-based mixed oxides were intended to

t
ip
reduce the leaching by the interaction of CaO with other metal oxides. For example, Yan et

cr
al.(2010)prepared of Ca-La mixed metal oxide catalysts by four different method . There was a

strong interaction between calcium and lanthanum species by ammonia-ethanol-carbon dioxide

us
precipitation method. The addition of lanthanum can increase basic strength and specific surface

area which conduce to catalytic activity in the transesterification reaction for biodiesel
an
production. The CaO-CeO2(Wong et al. 2015) mixed metal oxide catalyst was prepared by wet

impregnation method for biodiesel synthesis. The biodiesel yield of 95 % was achieved by 50Ca-
M

Ce mixed oxide catalyst. Meantime, the 50Ca-Ce mixed oxide catalyst has higher stability than

CaO catalyst and comparatively lower leaching of CaO into biodiesel production. Blocky shapes
ed

Ca-Mg(Fan et al. 2016) mixed oxides catalyst with a Ca-Mg ratio of 1:3 reached the biodiesel
pt

yield of 98.4% under the optimal reaction conditions. At the same time, the Ca-Mg catalyst has

better water resistance compared to pure calcium oxide catalyst.

ce

Supported solid base catalysts have been receiving wide attention because of their strong
Ac

alkalinity, large specific surface area, and high catalytic activity. Puna et al. (2014) found lithium

modified lime catalyst by wet impregnation had higher activity than the bare CaO. Because the

Li modified lime catalyst improved the surface basicity of the catalyst. However Li doped lime

catalysts presented a faster deactivation because of formation of Ca-diglycerol phase. Kesić et

4
al.(2012) synthesized of CaO-ZnO catalyst via boll milling method for biodiesel production. The

highest yield of FAME was reached 97.5% after 4 h reaction of sunflower oil and methanol

molar ratio of 1:10 in a batch reactor at 60 °C .However, the CaO·ZnO catalysts are practically

insoluble in reaction medium. To reduce the leaching and improve the stability of CaO-based

t
catalysts, The CaO-MoO3-SBA-15 (Xie and Zhao 2014) catalyst was prepared by incipient

ip
impregnation method and the catalyst can reusable five cycles with no appreciable loss in

cr
catalytic activity. After transeaterification reaction, the calcium and molybdenum concentration

us
of produced biodiesel was only 21 ppm and 13 ppm. Wen et al.(2010) found that prepared the

KF/CaO catalyst exhibited higher activity than the calcium oxide catalyst for the synthesis of
an
biodiesel. At the same time, the new crystal phase of KCaF3 in KF/CaO catalyst can

enhancement of catalytic activity and good stability. Because the new crystal phase of KCaF3 has
M
a strong attraction to CH3O– which facilitates the reaction rate of transesterification. But some

common problems such as reusability at short reaction time and active sites leaching have been in
ed

these catalysts.
pt

Transition metal resources are abundant in China and commonly used in catalytic

modification, which may further advance the development of solid basic catalysts. Especially some
ce

transition metals have strong basicity and in the catalytic process can promote the oxygen

transfer. In the present study, solid base catalysts were prepared by loading CaO and KF with
Ac

transition metals (La, Ce, Zr). The solid catalysts were characterized by power X-ray diffraction

(XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and CO2-

temperature programmed desorption (CO2-TPD).

5
2. Experimental sections

2.1. Materials and reagents

t
The waste cooking oil (WCO) was obtained from Zhongke Ltd., Wenzhou in China. The

ip
acid value of the cooking oil determined by titrimetric method was found to be 2.6 mg KOH/g. It

cr
contained 0.08% (wt) water and its molecular mass was 889 g/mol. The internal standard for gas

chromatography was methyl heptadecanoate (chromatographically pure, Sigma-Aldrich).

us
Methanol, calcium oxide, lanthanum nitrate, zirconium oxychloride, cerous chloride, and
an
potassium fluoride were analytically pure and purchased from Sinopharm Chemical Reagent Co.,

Ltd.
M

2.2 Catalyst preparation

ed

Several KF/CaO catalysts with different transition metals were prepared by a wet

impregnation method. In a typical procedure, 10 g of CaO and 1 g of transition metal salts (from
pt

La(NO3)3·nH2O, ZrOCl2·8H2O, or CeCl3·7H2O) were immersed in 10 mL of distilled water.

ce

Then, 2.5 g of KF was added to this suspension, and it was magnetically stirred for 1 h at 30 °C.

The solution was subsequently dried at 105°C for 24 h. Finally, the dried material was calcined
Ac

at 600°C for 4 h in a muffle furnace.

The catalyst without added transition metal is simply denoted as KF/CaO. The catalysts

impregnated with 10 wt% transition metal salts are denoted as KF/CaO/M (M=La, Ce, Zr).A

6
series of KF/CaO/La catalysts with different amount of lanthanum contents (5 wt%,10 wt%,15

wt%,20 wt%) were prepared and applied for biodiesel production .

2.3. Catalyst characterization

t
ip
XRD measurements were performed on a PANalytical X’Pert Pro X-ray diffractometer

(PANalytical, Holland) at room temperature, which utilizes monochromatic CuKα radiation (λ

cr
=0.15418 nm), a working voltage of 40 kV, working current of 40 mA, scanning 2θ range from

us
10–80°, and scanning step length of 0.0167 °. The peaks were identified using the Powder

Diffraction File (PDF) database created by the International Centre for Diffraction Data (ICDD).
an
The surface areas and pore sizes of the catalysts were carried out according to the
M
multipoint N2 adsorption–desorption method using an instrument of ASAP 2010 apparatus. Prior

to measurements, the samples were out-gassed overnight under vacuum at 100 °C.
ed

The CO2-TPD was used to determine the basic strength and basicity of the sample. The

catalysts (approximately 0.2 g) were pretreated under a helium stream (50 mL·min−1) at 600 °C
pt

for 30 min . Then, the temperature was decreased to 100 °C, and a flow of pure CO2
ce

(50mL·min−1) was subsequently introduced to the samples for 1 h. The sample was flushed with

helium for 30 min before the CO2 desorption analysis. The analysis of CO2 desorption was then
Ac

carried out between100 -900°C (10 °C·min-1) under helium flow (50 mL min-1) and detected by

thermal conductivity detector (TCD).

7
 The sample morphology and elemental composition were analyzed at room temperature on

a Hitachi S-4800 SEM system equipped with an EDS detector. The accelerating voltage was 3

KV.

The contents of Ca ion was analyzed using Inductively Coupled Plasma – Optical Emission

t
ip
Spectrometer (ICP-OES) (OPTIMA 8000 ).

cr
2.4. Transesterification process

us
Fig. 1 shows a schematic diagram of the transesterification system. All experiments were carried
out in a 250 mL three-necked flask equipped with a magnetic stirrer and a water-cooled
condenser. Appropriate amounts of methanol, waste cooking oil, and the catalyst were added to
an
the reaction flask and stirred at 600 rpm. After the reactions, the solid catalyst was separated
from the reaction mixture by centrifugation, and the residual methanol was separated from the
liquid phase via rotary evaporation. Then, the liquid was put into a separation funnel and kept at
M
ambient temperature for 24 h, after which two liquid phases appeared. The upper layer was
biodiesel with some traces of unreacted oil and methanol, and the lower layer was glycerol. The
composition of the fatty acid methyl esters was determined by a Shimadzu GC2010 series gas
chromatograph equipped with a FID detector. The experiments were carried out in five times,
ed

repeated measurement of the FAME yield showed the percentage of error associated with this
measurement was ±1%.

3. Results and discussion

pt
ce

3.1. Structural properties of KF/CaO/M solid base catalysts

Ac

Powder XRD patterns of the KF/CaO catalysts with different transition metals to determine

the effect of the transition metals on KF/CaO catalyst are illustrated in Figure. 2. For KF

support, no obvious diffraction peak appeared in the XRD pattern, thus implying that the KF in

the KF/CaO catalysts was mainly present in an amorphous state. As shown in Figure. 2, the

8
transition metal salts of La, Ce, and Zr were added, the XRD crystalline phase structures of the

KF/CaO/M catalysts were not altered. Two crystal phases can be observed for the KF/CaO

catalysts doping transition metal. Typical XRD diffraction peaks appear at 2θ angles of 37.36° ,

53.85° , 64.12° , and 67.30°, which can be attributed to the crystal structure of CaO (according to

t
the PDF database entry 00-004-0777). The solid catalyst also exhibited XRD diffraction peaks at

ip
2θ angles of 28.75° , 32.20° , 33.93° , 41.19° , 46.13° , and 51.16°,which could be attributable

cr
to the crystal phase structure of KCaF3 (according to the PDF database entry 00-049-1737). The

us
average crystallite size of the KF/CaO and the KF/CaO/M catalysts was calculated by using

Debye-Scherer’s equation. The average crystallite size for KF/CaO and KF/CaO/M catalysts of
an
CaO based on crystal plane (200) was calculated and listed in Table 1. The crystallite size of

CaO in KF/CaO catalyst was 58.6 nm . While, the crystallite sizes of CaO were 59.0 nm, 47.1
M
nm and 60.7 nm for the KF/CaO/Zr, KF/CaO/La, KF/CaO/Ce catalysts, respectively. It is proved

that the catalytic activity phase of CaO in KF/CaO/La catalyst is more diffuse and highly
ed

dispersed than KF/CaO catalyst.

pt

Figure. 3 depicts the SEM image of KF/CaO and KF/CaO/M catalysts. An irregular lamellar
structure can be observed in the SEM image of the KF/CaO catalyst (Figure. 3), and the joints
contained a small amount of pores. The KF/CaO/La catalyst had a granular elliptical structure
ce

with fine particles on the surface, indicating that a small amount of KCaF3 is loaded on the
surface of the catalyst. The KF/CaO/Ce catalyst had an irregular elliptical structure contained a
small amount of pores. The KF/CaO/Zr catalyst had the cube-like structure with small particles
on the surface.
Ac

3.2 Surface properties of KF/CaO/M solid bases

The total basicity and basic sites distributions of the KF/CaO/M catalysts were evaluated by

using temperature programmed desorption of CO2 (CO2-TPD). The CO2-TPD profiles are shown

9
in Figure. 4, while the total amount of basicity of the catalysts is displayed in Table 1,

respectively. The KF/CaO catalyst observe an intense CO2-desorption peak at 793 °C of a strong

basic strength. The KF/CaO/La, KF/CaO/Zr and the KF/CaO/Ce catalysts have a intense

desorption peak with a peak temperature of 813 °C,762 °C and 826 °C respectively. According

t
to Di Serio et al.(2006), the narrower band at higher temperature (>550 °C) can be attributed to

ip
the presence of much stronger basic sites. The derived KF/CaO provided strong basic sites

cr
(>550°C ) with a basic amount of 1058.2 umol/g; while the KF/CaO/La, KF/CaO/Ce,

us
KF/CaO/Zr provided strong basic sites (>550 °C ) with a basic amount of 3504.6 umol/g, 3053.9

umol/g, 1563.8 umol/g, respectively. The improved basicity may be due to the synergic effect
an
between CaO and transition metals.

BET surface area of the KF/CaO and KF/CaO with different transition metals was given in
M

Table 2. As can be seen in Table 2, the surface area of CaO is only 20.5 m2/g, the KF/CaO

catalyst has a larger surface area of 98.7 m2/g. The catalysts promoted with different transition
ed

metals have higher surface area than the KF/CaO catalyst. The KF/CaO/La catalyst shows the
pt

highest specific surface area (117.4 m2/g), and the lowest pore diameter (19.4 nm) . This is in

favor of the increase in the catalytic activity because of the multiple contacts between reagent
ce

and the catalyst.

Ac

Table 3 illustrates the elemental contents of O, F, Si, K, Ca, and transition metals on the

catalytic surface by EDS analysis. As is shown in Table 3 , F, K, and Ca contents at the selected

points on the surface were 25.6 wt%, 17.3 wt%, and 26.7 wt%, respectively, for KF/CaO catalyst.

Upon addition of the transition metals of lanthanum, cerium, and zirconium, the Ca content

10
increased, which in turn corresponded to increased activity. Additionally, the concentrations of F

and K on the surface were increased in the KF/CaO/La catalyst (with respect to KF/CaO).While,

the crystal phase of KCaF3 was formed during the impregnation stage (Di serio et al.

2006).These results indicate an increase in the crystalline phase of KCaF3 during the

t
impregnation stage.

ip
cr
3.3 Catalytic activity

us
3.3.1 Effect of different transition metals
an
The catalytic tansesterification activity of KF/CaO and tansition metals (lanthanum, cerium,

and zirconium)-doped KF/CaO catalysts was shown in Figure.5 As observed, transition metal
M
(lanthanum, cerium, and zirconium)-doped KF/CaO catalysts, KF/CaO/M, demonstrated

superior activity over transition metal-free KF/CaO (95.1–98.7% vs. 91.5% yield of FAME).
ed

KF/CaO/La produced the highest yield of fatty acid methyl ester at 98.7% at 65 °C, molar ratio

of methanol to oil of 12:1, reaction time 1 h and 4 wt% catalyst loading. Transesterification
pt

activity is highly depended on the basicity of the catalysts, the correlation between the basicity of

catalysts and FAME yield is depicted in Figure. 5. The experimental result suggested that the
ce

amount and the strength of basic sites strongly corresponded to the activity of the catalysts;
Ac

namely the higher basic amount brought about the higher biodiesel yield. We can conclude from

this the KF/CaO/La catalyst has more basic sites, which is beneficial for the transesterification-

based catalysis synthesis of biodiesel.

Catalytic activities of KF/CaO/La catalysts containing different lanthanum contents on

11
transesterification of WCO were also investigated under conditions of 4wt% of catalyst,

methanol to oil molar ratio of 12:1,reaction temperature of 65 °C and reaction time of 1 h (Fig 6).

As illustrated in Figure.6, it is not worthy that the biodiesel yield increased gradually from 90.5 %

to 98.7% as lanthanum adding in KF/CaO/La catalysts on transesterification increased in the

t
range of 0–10 wt% content. However, when the contents of lanthanum were 15wt% or 20wt%,

ip
the catalytic activity of the KF/CaO/La catalyst begins to dramatically decline. While 10wt%

cr
KF/CaO/La catalyst, the catalytic activity reached a balance. Hence, 10wt% KF/CaO/La catalyst

us
was the optimum catalyst with the highest FAME yield of 98.7% .

3.3.2 Influence of the reaction parameters

an
The effect of catalyst amount on the yield of FAME in transesterification of WCO with
M
KF/CaO/La catalyst was investigated. The results are shown in Figure.7a. Figure. 7a displayed

that when the catalyst amount of KF/CaO/La catalyst was between 1% and 5% w/w of WCO, the
ed

biodiesel yield increased steeply, reaching the peak at 4 wt%. When the catalyst amount was

from 1wt% to 3wt%, the contact of the substrates and catalyst was not sufficient, and thereby the
pt

progress of transesterification was not reached equilibrium which resulting in low yield of fatty
ce

acid methyl esters (FAME). When the amount of catalyst was reached to 4 wt.%, a yield of

FAME of 98.7 % was obtained with KF/CaO/La catalyst at 65 °C with 12:1 methanol oil molar
Ac

ratio for 1h .Therefore, The 4 wt% is considered as the optimal catalyst amount on the

transesterification reaction .

Figure. 7b illustrates the impact of the methanol/oil molar ratio on the yield of FAME .As can be
seen from Figure. 7b, the methanol/oil molar ratio was varied from 6:1 to 18:1.When the
methanol/oil molar ratio was increased from 6:1 to 12:1, the yield of FAME was considerably

12
enhanced from 81.4% to 98.7% .When the alcohol–oil molar ratio was more than 12:1, the
increase of the FAME contents was not significant. Therefore the methanol/oil molar ratio of
12:1 was a suitable molar ratio for synthesis of biodiesel.

Figure.7c showed the effect of reaction temperature on yield of FAME with 4% w/w catalyst and
12:1 alcohol–oil molar ratio. From Figure. 7c, it could be seen that the biodiesel yield was
increased with the rise of temperature from 50 °C to 65 °C, since the reaction could not reach
equilibrium.

t
ip
To study the influence of reaction time on synthesis of biodiesel, the experiments were

conducted using examined with 4% w/w catalyst and 12:1 methanol–oil molar ratio at 65 °C.

cr
The results are shown in Figure. 7d. From Figure. 7d ,a yield of 40.5% was obtained at the end of

us
20 minute and the transesterification reaction was reached to a maximum yield at the end of 1 h.

It is clear that after 1 h of reaction time there is no considerable effect on biodiesel yield. Thus 1
an
h can be chosen as a suitable reaction time for the transesterification reaction.
M
In conclusion, the optimum experimental conditions of transesterification were 4 wt.% of

catalyst amount, 12:1 of methanol/oil molar ratio, 65 °C of reaction temperature and 1 h of

ed

reaction time.

3.3.3 Stability and recyclability of the catalyst

pt
ce

In view of economy, the reusability of the catalyst is of great importance for industrial

applications. After the reaction completed, the reaction mixture was centrifuged and separated to
Ac

recover the catalysts for reuse and to investigate its lifetime and stability. Prior to each reaction,

the same amounts of WCO and methanol were added. Figure. 8 showed the effect of repeated

use of the KF/CaO/La catalyst on the transesterification reaction. The results indicate that the

KF/CaO/La-catalyzed synthesis of biodiesel still produced a yield in excess of 95% after 10

13
cycles only after 1h reaction time. Therefore, KF/CaO/La can contribute much to decreasing the

cost of biodiesel production due to its long catalyst lifetime and short reaction time. In addition,

the leached metals Ca2+ in biodiesel phase after removal of the KF/CaO/La catalyst was

measured by ICP analysis .The result depicted the calcium content of produced biodiesel was

t
14.3 ppm .Compared with concentrations of dissolved Ca2+ from KF/CaO ,the Ca2+ content of

ip
produced biodiesel in KF/CaO/La catalyst was smaller than KF/CaO (33.7 ppm).The KF/CaO/La

cr
catalyst was more stable and less activity sites leaching. The KCaF3 has excellent stability in

us
methanol (free Ca2+ concentration in methanol is less than 1 ppm) (Hu et al. 2011). The crystal

phase of KCaF3 make the KF/CaO/La catalyst more stable.

an
3.4. Catalytic mechanism
M

The effects of transition metals on the loading of KF in a calcium oxide catalyst were

studied. The addition of lanthanum led to the formation of more active crystalline phases of
ed

KCaF3. KCaF3 is more efficient for the transesterification reaction because fluoride ions are

more electronegative than oxygen ions. Calcium ions in KCaF3 have higher Lewis acidity and a
pt

strong attraction to CH3O– . At the same time, the fluoride ions have high Lewis basicity and
ce

strongly adsorb hydrogen ions. Therefore, the presence of KCaF3 species provides for an easier

conversion of methanol to CH3O–. The surface of the catalyst has more CH3O– , which facilitates
Ac

the catalysis of reactions with carbonyl carbon and thereby accelerates the reaction rate of

transesterification.

14
4. Conclusions

KF/CaO-based catalysts that were prepared by transition metal (La, Ce, Zr) impregnation

were examined for their activity in the heterogeneous catalysis for the transesterification

t
synthesis of biodiesel. The KF/CaO catalyst loaded with 10wt% La(NO3)3.nH2O was found to be

ip
superior among the tested variants. The catalyst also exhibited relatively good reusability since

cr
the yield of fatty acid methyl esters remained greater than 95% even after its tenth use (98.7% for

us
the first use) only after 1h reaction. Characterizations of the catalysts revealed that the addition

of transition metals did not alter the structure of the catalysts, whereas the addition of lanthanum
an
did highly dispersed and increased the alkalinity in the catalysts. The crystalline phase of KCaF3

enhanced the catalytic activity and decrease the leached metals Ca2+.The increased alkalinity of
M
the catalysts is advantageous to transesterification. KF/CaO/La used in the preparation of

biodiesel illustrates a good prospect of development and application.

ed

AUTHOR INFORMATION
pt

Notes
ce

The authors declare no competing financial interest.

Ac

Funding

The financial support received from National Natural Science Foundation of China

(No.21576260,), Special Funds of Applied Science and Technology Research of Guangdong

15
Province (No. 2015B020241002), Natural Science Foundation of Guangdong Province

(No.2016A030308004 and No.2015A030313720) is much appreciated.

References

t
Atadashi, I.M., M.K. Aroua, A.R. A Aziz, and N.M.N. Sulaiman.2013. The effects of catalysts in

ip
biodiesel production: A review. Journal of Industrial and Engineering Chemistry 19:14-26.

cr
doi:10.1016/j.jiec.2012.07.009.

us
Banković–Ilić, I. B., M. R. Miladinović, O. S. Stamenković, and V. B. Veljković. 2017.

Application of nano CaO-based catalysts in biodiesel synthesis. Renewable and Sustainable

an
Energy Reviews 72:746-760. doi:10.1016/j.rser.2017.01.076.
M
Borges, M.E., L. Díaz . 2012. Recent developments on heterogeneous catalysts for biodiesel

production by oil esterification and transesterification reactions: A review. Renewable and

ed

Sustainable Energy Reviews 16:2839-2849. doi:10.1016/j.rser.2012.01.071.

Deshmane, V. G., and Y. G. Adewuyi.2013.Synthesis and kinetics of biodiesel formation via

pt

calcium methoxide base catalyzed transesterification reaction in the absence and presence of
ce

ultrasound. Fuel 107:474–482 . doi:10.1016/j.fuel.2012.12.080.

Di serio, M. , M. Ledda, M. Cozzolino , G. Minutillo , R. Tesser , and E.Santacesaria.2006.

Ac

Transesterification of soybean oil to biodiesel by using heterogeneous basic catalysts. Ind Eng

Chem Res 45:3009-3014 . doi:10.1021/ie051402o.

16
Fan, M. M. , Y. L. Liu , P. B. Zhang, and P. P. Jiang. 2016.Blocky shapes Ca-Mg mixed oxides

as a water-resistant catalyst for effective synthesis of biodiesel by transesterification.Fuel

Processing Technology.149:163-168 doi:10.1016/j.fuproc.2016.03.029.

Hu, S. Y., Y. P. Guan, Y. Wang, and H. Y. Han.2011. , .Nano-magnetic catalyst KF/CaO–

t
ip
Fe3O4 for biodiesel production. Applied Energy 88: 2685-2690 .

cr
Kesić, Ž. , V. Lukić , D. Brkić , J. Rogan, M. Zdujić , H. Liu , and D. Skala . 2012.

us
Mechanochemical preparation and characterization of CaO·ZnO used as catalyst for biodiesel

synthesis. Applied Catalysis A: General 427–428: 58–65 . doi:10.1016/j.apenergy.2011.02.012.

an
Kouzu, M., T. Kasuno, M. Tajika,S. Yamanaka, and J. Hidaka.2008. Active phase of calcium

oxide used as solid base catalyst for transesterification of soybean oil with refluxing methanol.
M

Appl Catal A 334:357–365 . doi:10.1016/j.apcata.2007.10.023.

ed

Lam, M. K., K. T. Lee , and A. R. Mohamed. 2010. Homogeneous, heterogeneous and

enzymatic catalysis for transesterification of high free fatty acid oil (waste cooking oil) to
pt

biodiesel: A review.Biotechnology Advance 28:500-518. doi: 10.1016/j.biotechadv.2010.03.002.

ce

Leung, D. Y. C. , X. Wu, and M. K. H. Leung.2010.A review on biodiesel production using

catalyzed transesterification. Applied Energy 87:1083-1095. doi:10.1016/j.apenergy.2009.10.006.

Ac

Li, Y., H.J. Guo, Z. Zhu, Y. Feng, and S.H. Liu.2012. Ethylene glycol monomethyl ether

cottonseed oil monoester: properties evaluation as biofuel. Int J Green Energy 9:376–387 .

doi:10.1080/15435075.2011.621483.

17
Mahmudul, H.M., F.Y. Hagos, R. Mamat, A. A. Adam, W.F.W. Ishak, and R. Alenezi. 2017.

Production, characterization and performance of biodiesel as an alternative fuel in diesel engines

– A review. Renewable and Sustainable Energy Reviews. 72:497-509.

doi:10.1016/j.rser.2017.01.001.

t
ip
Marinković, D. M., M. V. Stanković, A. V. Veličković, J. M. Avramović, M. R. Miladinović, O.

cr
O. Stamenković, V. B. Veljković, and D. M. Jovanović. 2016. Calcium oxide as a promising

heterogeneous catalyst for biodiesel production: Current state and perspectives. Renewable and

us
Sustainable Energy Reviews 56:1387-1408. doi:10.1016/j.rser.2015.12.007.
an
Patel, R.L. ,and C.D. Sankhavara. 2017. Biodiesel production from Karanja oil and its use in

diesel engine: A review. Renewable and Sustainable Energy Reviews 71:464-474.

M
doi:10.1016/j.rser.2016.12.075.

Puna, J. F., J. F. Gomes, J. C.Bordado, M. J N Correia, A. P. S.Dias.2014 .Biodiesel production

ed

over lithium modified lime catalysts: Activity and deactivation. Applied Catalysis A:
pt

General.470:451– 457. doi: 10.1016/j.apcata.2013.11.022.

ce

Refaat, A. A.2011. Biodiesel production using solid metal oxide catalysts .Int J Environ SciTe.

8,203-221 . doi: 10.1007/BF03326210.

Ac

Ren, Y. B., B. Q. He, F.Yan , H. Wang, Y.Cheng , L. G. Lin , Y. H. Feng ,and J. X. Li. 2012.

Continuous biodiesel production in a fixed bed reactor packed with anion-exchange resin as

heterogeneous catalyst. Bioresource Technology 113:19-22 . doi:10.1016/j.biortech.2011.10.103.

18
Steene, E.V. D. ,Clercq, J. D., and Thybaut,J.W. 2014.Ion-exchange resin catalyzed

transesterification of ethyl acetate with methanol: Gel versus macroporous resins.Chemical

Engineering Journal 242:170-179. doi:10.1016/j.cej.2013.12.025.

Sun, K., J. Lu, L. L. Ma, Y. Han, Z. J. Fu, and J. C. Ding .2015. A comparative study on the

t
ip
catalytic performance of different types of zeolites for biodiesel production. Fuel 158:848-854.

cr
doi:10.1016/j.fuel.2015.06.048.

us
Verma,P., and M.P. Sharma. 2016. Review of process parameters for biodiesel production from

different feedstocks. Renewable and Sustainable Energy Reviews 62: 1063-1071.

an
doi:10.1016/j.rser.2016.04.054.

Volli, V., and M.K. Purkait. 2015. Selective preparation of zeolite X and A from flyash and its
M

use as catalyst forbiodiesel production. Journal of Hazardous Materials 297:101-111.

doi:10.1016/j.jhazmat.2015.04.066.
ed

Vyas, A, P, J. L. Verma, and N. Subrahmanyam. 2010.A review on FAME production processes.

pt

Fuel. 89:1-9. doi:10.1016/j.fuel.2009.08.014

ce

Wang, Y. T. , Z. Fang , F. Zhang , and B.J. Xue .2015. One-step production of biodiesel from

oils with high acid value by activated Mg–Al hydrotalcite nanoparticles. Bioresource Technology
Ac

193:84-89. doi:10.1016/j.biortech.2015.06.059.

Wong, Y. C. , Y. P. Tan, Y. H. Taufiq-Yap , I. Ramli. , and H.S. Tee. 2015. Biodiesel

production via transesterification of palm oil by using CaO–CeO2 mixed oxide catalysts. Fuel

162:288-293. doi:10.1016/j.fuel.2015.09.012.

19
Wen, L. B. , Y. Wang, D. L. Lu. , S. Y. Hu, and H.Y. Han.2010. Preparation of KF/CaO

nanocatalyst and its application in biodiesel production from Chinese tallow seed oil. Fuel

89:2267-2271. doi:10.1016/j.fuel.2010.01.028

Xie ,W. L., and L. L. Zhao.2014. Heterogeneous CaO–MoO3–SBA-15 catalysts for biodiesel

t
ip
production from soybean oil. Energy Conversion and Management79:34-42 .

cr
doi:10.1016/j.enconman.2013.11.041

us
Yan, S., M. Kim, S. Mohan, S. O. Salley ,and K. Y. S. Ng.2010. Effects of preparative

parameters on the structure and performance of Ca–La metal oxide catalysts for oil
an
transesterification. Applied Catalysis A 373:104-111. doi:10.1016/j.apcata.2009.11.001

Yoosuk, B., P. Udomsap, B. Puttasawat, and P. Krasae. 2010. Modification of calcite by

M

hydration-dehydration method for heterogeneous biodiesel production process: the effects of

water on properties and activity. Chemical Engineering Journal 162:135–141.

ed

doi:10.1016/j.cej.2010.05.013.
pt

Zhang, J., X. J. Wang, H. J. Guo, S. H Liu, and J. Ma . 2012. Synthesis and properties of a novel

ethylene glycol monobutyl ether palm oil monoester biofuel. Int J Green Energy 9:573-583.
ce

doi:10.1080/15435075.2011.625581.
Ac

20
Table 1. Crystallite size of CaO, and basicity of the KF/CaO and KF/CaO/M catalysts

XRD analysis TPD analysis

Catalysts crystallite size of CaO

t
Surface amount of basic Peak temperature
on (200) plane (nm)

ip
site(umol.g-1)
( )

cr
us
KF/CaO 58.6 1058.2 793
an
KF/CaO/Zr 59.0 1563.8 762
M

KF/CaO/La 47.1 3504.6 813

ed

KF/CaO/Ce 60.7 3053.9 826

pt
ce
Ac

21
 Table 2 . BET surface areas , pore diameter of the CaO, KF/CaO and KF/CaO/M catalysts

Catalysts SBET(m2.g-1) Pore diameter (nm)

CaO 20.5 16.0

t
ip
KF/CaO 98.7 29.6

cr
us
KF/CaO/La 117.4 19.4
an
KF/CaO/Ce 113.7 24.9
M
KF/CaO/Zr 107.8 32.8
ed
pt
ce
Ac

22
Table 3. EDS analysis of the surface of catalysts particles

Wt%

Catalysts

t
O F Si K Ca transition metal

ip
cr
KF/CaO 29.8±2.9 25.6±3.1 0.1±0 17.3±0.6 26.7±2.8

us
KF/CaO/La 21.4±3.6 26.5±1.8 18.7±1.3 31.9±3.1 1.5(La) ±0.5
an
KF/CaO/Ce
M
24.8±2.7 26.8±3.7 0.4±0.1 16.7±0.8 30.2±2.1 1.1(Ce) ±0.3
ed

KF/CaO/Zr 20.3±1.8 29.1±2.3 0.8±0.3 19.8±1.6 28.9±1.9 1.1 (Zr) ±0.2

pt
ce
Ac

23
Fig 1 Schematic view of the laboratory reactor.

1. Programmable logic Controller 2. Reactor 3. Pump 4. Rotary evaporator 5. Hot oil inlet 6.

Hot oil outlet 7 Water in 8 Water out

t
ip
cr
us
an
M
ed
pt
ce
Ac

24
 t
ip
Figure. 2. XRD patterns of KF/CaO catalysts with different transition metals

cr
us
an
M
ed
pt
ce
Ac

25
Figure. 3. SEM images of the KF/CaO and KF/CaO/M catalysts

t
ip
cr
us
an
M
ed
pt
ce
Ac

26
Figure. 4. CO2-TPD profiles of the KF/CaO and KF/CaO/M catalysts

t
ip
cr
us
an
M
ed
pt
ce
Ac

27
Figure. 5 Correlation between total basicity and catalytic activity of KF/CaO/M catalysts.

Reaction conditions: methanol/oil molar ratio of 12:1, 4% (w/w of oil) catalyst;65°C,and 1h

reaction time.

t
ip
cr
us
an
M
ed
pt
ce
Ac

28
Figure 6. Transesterification activities of KF/CaO catalysts as a function of lanthanum contents.

Reaction conditions: methanol/oil molar ratio of 12:1, 4% (w/w of oil) catalyst;65°C,and 1h

reaction time.

t
ip
cr
us
an
M
ed
pt
ce
Ac

29
Figure.7 Influence of reaction parameters : (a) amount of the catalyst, (b) methanol-to-oil molar

ratio, (c) reaction temperature and (d) reaction time on transesterification reaction over

KF/CaO/La catalysts.

t
ip
cr
us
an
M
ed
pt
ce

Reaction conditions for (a); molar ratio of methanol to oil of 12:1, reaction time of 1 h, and
Ac

reaction temperature of 65 °C (b); the amount of catalyst 4.0 %, reaction time of 1h, and reaction

temperature of 65 °C (c);molar ratio of methanol to oil of 12:1, amount of catalyst of 4.0 wt%

and reaction time of 1 h (d);the amount of catalyst 4.0 %, molar ratio of methanol to oil of

12:1,and reaction temperature of 65 °C

30
Figure. 8. Reusability of the KF/CaO/La catalyst .

Reaction conditions: methanol/oil molar ratio of 12:1, 4% (w/w of oil) catalyst;65°C,and 1h

reaction time.

t
ip
cr
us
an
M
ed
pt
ce
Ac

31