Accepted Manuscript

Title: Enhanced deacidification of acidic oil catalyzed by

sulfonated granular activated carbon using microwave
irradiation for biodiesel production

Authors: Weidong Lu, Md. Asraful Alam, Chaosheng Wu,

Zhongming Wang, Haoping Wei

PII: S0255-2701(18)30867-5
DOI: https://doi.org/10.1016/j.cep.2018.10.019
Reference: CEP 7413

To appear in: Chemical Engineering and Processing

Received date: 20 July 2018

Revised date: 25 September 2018
Accepted date: 29 October 2018

Please cite this article as: Lu W, Alam MA, Wu C, Wang Z, Wei H, Enhanced
deacidification of acidic oil catalyzed by sulfonated granular activated carbon using
microwave irradiation for biodiesel production, Chemical Engineering and Processing
- Process Intensification (2018), https://doi.org/10.1016/j.cep.2018.10.019

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Enhanced deacidification of acidic oil catalyzed by sulfonated granular activated
carbon using microwave irradiation for biodiesel production

Weidong Lu1*, Md. Asraful Alam2*, Chaosheng Wu1, Zhongming Wang2 , Haoping Wei1

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School of Chemistry and Environmental Engineering, Shaoguan University, Shaoguan 512005, China.

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Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of

Sciences, Guangzhou 510640, China

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*Corresponding author(s), Tel.: +86-751-8120118, Fax: +86-751-8120118, Email addresses:

alam@ms.giec.ac.cn (M. A Alam); luwd@sgu.edu.cn (W. Lu).
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Graphical Abstract

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Highlighted points:
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1. Enhanced deacidification rate was obtained using SGAC as catalysis with

microwave irradiation;
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2. Process variables were optimized using response surface methodology;

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3. A 93.26% deacidification rate was achieved in 10 min with microwave heating.

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Abstract:
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Deacidification is a dispensable procedure prior to alkali catalyzed transestrification of acidic oil

for biodiesel production. In this study, effect of microwave irradiation on sulfonated granular

activated carbon (SGAC) catalyzed deacidification of acidic oil was evaluated. Process variables

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of deacidification were optimized using response surface methodology (RSM). Results showed

that microwave irradiation could enhance deacidification efficiency in comparison with

conventional heating and a significant mathematical model was obtained to predict

deacidification rate of acidified oil catalyzed by SGAC under microwave heating. Optimum

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process variables were achieved according to the mathematical model, they were reaction

temperature 65 ºC, methanol to oil ration 2 (wt/wt), and catalyst loading 5.0 % (wt% oil mass).

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Finally, the optimum process variables were confirmed by experiments, in which average

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deacidification rate of 93.26% was obtained.

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Key words: Response surface methodology; Sulfonated catalyst; Microwave irradiation;

Deacidification; Waste oil; Biodiesel.

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1. Introduction

Energy demand and consumption soaring in the past decades and the demand grew at an
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average annual rate of 1.5 percent during 2007-2017. Great concern was also rising because of

fossil energy depletion and environmental pollution becoming global issues. In order to mitigate

the dependence on fossil fuel, biological energy, such as biodiesel, bioethanol, and biogas have

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been acknowledged to be good alternatives to conventional fuel, since bioenergy can be carbon

neutral and plays an important role in the reduction of greenhouse gas emissions[1]. Moreover,

biodiesel demonstrates similar chemical properties to petroleum diesel which facilitates it as a

blended component used in vehicle engine[2,3]. In addition, biodiesel shows superiority in

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remarkable abatement of particulate matter[4], total hydrocarbons (THC) and carbon monoxide

(CO) emissions in comparison to fossil diesel[5].

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Chemically, biodiesel is a mixture of methyl esters with long-chain fatty acids and is usually

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prepared from non-hazardous, biological resources such as vegetable oils, used cooking oils,

animal fats, various kind of biomass and microalgae etc. and produced based on the following

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reaction and either acid or base catalysts classically used to accelerate the reaction rate and [6,7].
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It is commonly accepted that waste oil/used cooking oil is not suitable for human consumption

and is one of most suitable feedstocks for biodiesel production without competing with food/feed

crops[8]. In addition, biodiesel production from waste oil can make the best recovery of resource

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and its usage significantly reduces the cost of biodiesel production and will protect the

environment from untreated dumping[6]. However, the quality of waste oil may cause concern

because its chemical properties which depend on the fresh oil contents and it may contain

various undesired impurity, such as free fatty acids, water etc.

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Base catalysts usually have much higher efficiency in assisting transesterification reaction

than acid catalysts. However, waste oil or fats are habitually associated with higher acid value

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and water content, which is not suitable for base catalyst since saponification reaction will occur

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between base catalysts and free fatty acid in waste oil[9,10]. The water can hydrolyze the

triglycerides into diglycerides and procedure more free fatty acids. Above reactions conditions

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are undesirable and reduce the yield of the biodiesel production, hence, pre-esterification
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(deacidification) should be carried out prior to alkali catalyzed transesterification to inhibit the
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saponification reaction.
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Heterogeneous catalysis is widely applied in chemical industry due to incomparable

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advantages over homogeneous catalyst in chemical reaction process such as improved selectivity,
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easy catalyst separation from reaction mixture, simplified process and abatement of acid

wastewater[11]. Therefore, a few attempts have been tried to find economic and feasible
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approaches to reduce the acid value of waste oil for biodiesel production using heterogeneous
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catalysts. For example, Syazwan[12] used sulfated calcined angel wing shell (CAWS) catalysts

to esterify palm fatty acid distillate (PFAD) in supercritical methanol and obtained 98% fatty
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acid methyl esters (FAME) yield at the optimum methanol/PFAD molar ratio of 6:1, 2 wt.%

catalyst loading, 290 ºC in 15 min. González [13] achieved a maximum FAME yield of 90%,

when the reaction was carried out at 140 ºC for 15 min in a microwave reactor use sulfonated

biochar-based catalyst. Ezebor [14] achieved esterification of free fatty acids in oil matrices from

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42% to less than 1 wt.% in just 15 min using oil palm trunk and sugarcane bagasse derived solid

acid catalysts. Gan et al.[15] investigated esterification rate of free fatty acid (FFA) in waste

cooking oil using ion exchange resins, achieving a maximum FFA conversion of 60.2%.

However, the efficiency of heterogeneous catalysts in catalyzing esterification of FFA in acidic

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oil is lower than that of homogeneous catalysts with traditional heating, such as water or oil bath.

In order to increase the catalyzing efficiency in FFA esterfication, microwave (MW) heating has

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attracted much attention in recent years due to the advantages associated with dielectric heating

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effects[16,17]. Microwave heating is a multiphysics phenomenon that involves the conversion of

electromagnetic energy into heat[18]. Microwave can interact directly with the organic

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molecules, especially polar molecules, creating rotational motion, which instantaneously

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generates heat inside the reaction vessel [19,20]. Thus, microwave-assisted technique can
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increasing processing rates and substantially shortening reaction times by up to 80% compared to
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conduction and convention heating and is consider a powerful technique for process

intensification.
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For instance, Zhang et al.[21] studied the traditional heating and microwave assisted method

for esterification of FFAs from waste cooking oil (WCO) using cation ion exchange resin
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particles (CERP)/PES catalytic membrane as catalyst. Results showed that microwave

irradiation exhibited a remarkable enhanced effect for esterification compared with that of
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traditional heating method. However, the feedstock of (CERP)/PES was fossil based while
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SGAC employed in this study was bio-based, which can be derived from biological waste,

thus is renewable and potentially economical[22,23]. In addition, the correlation and optimum

process variables had not been determined, which is crucial for high target product yield and

cost-effectiveness in scaling up of the process.

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 Hence, three objectives were proposed in this study: (1) Evaluation the potential of

microwave assisted SGAC catalyzed deacidification of acid oil in comparison with conventional

heating method; (2) Elucidate the effect of process variables on the Deacidification rate (DR). (3)

Optimization of microwave assisted SGAC catalyzed deacidification of acidic oil using response

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surface methodology.

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2. Materials and Methods

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2.1Materials

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Acid oil was synthesized by mixing soybean oil (Luhua Group, Shandong, China) and oleic

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acid (A.R., Spartan Reagent Co., Ltd, Dongguan, Guangdong, China) at a ratio of 5:2 on weight
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basis. Granular activated carbon and p-Toluenesulfonic acid (PTSA) were purchased from
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Gongyi Aolin Filter Medium Co. Ltd and Shanghai Macklin Biochemical Co., Ltd, China,

respectively. All the reagents were used without further purification.

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2.2 Methods

2.2.1 Catalyst preparation

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Total 50g granular activated carbon was saturated with 100 ml 25% (wt%) PTSA aqueous
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solution and stirred and heated at 120 ºC for 5 h in an oil bath pot (Gongyi Yuhua equipment Co.

Ltd, Hengnan, China). Afterwards, the sulfonated granular activated carbon was washed
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repeatedly with hot distilled water (exceeding 80 ºC) until the filtrate was neutral and then dried

at 105 ºC till to mass constant for further use.

2.2.2 Microwave-assisted SGAC catalyzed deacidification of acidic oil

Microwave irradiation for the deacidification process in this study was provided by a

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microwave reactor (MAS-II, Sineo Microwave Chemical Technology Co., Ltd., Shanghai,

China). The reactor photo is shown in Fig. 1. In the reaction system, a thermal couple was

employed to detect the reaction temperature which used as feedback to adjust the microwave

heating power. In addition, a serpentine condenser was facilitated to condense back the methanol

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vapor. For each deacidification experiment, approximately 25g acidic oil, a pre-determined

amount of methanol, and SGAC were introduced into a 250 mL three-necked round-bottom

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flask. A reaction temperature (55~80 ºC) and reaction time (2~10 min) were set to and the

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reaction mixture were mixed with continuous magnetically stir (300 rpm) available in the

microwave reactor. After reaction proceeded to the pre-set time, reaction mixtures were cooled

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with tap water and then transferred to a separating funnel overnight to form two phases. Lower

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phase was collected for acid value determination, upper phase was recycled by distillation. Acid
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value (AV) of the mixture was determined according to the state standard of China
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(GB5009.229-2016).
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Deacidification rate (DR, %) was calculated according to the following equation,

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AV i  AV
DR (%) 
f
 100 % (1)
AV
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Where, AV i , AV f refer to the initial acid value and final acid value, respectively.
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Please insert Fig. 1 here

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2.2.3 Experimental design

Firstly, the effect of reaction process variables, including reaction time, reaction

temperature, alcohol to oil ratio and catalyst loading were investigated and obtained an optimum

range of each variable. Afterwards, the reaction process variables were optimized using RSM.

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For the RSM experiment, a total of 17 experimental runs of three independent variables was

designed with Box-Behnken design [24] using the Design-Expert software (Version 8.0.6.1, Stat-

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Ease, Inc., USA). The DR was taken as the response of the design experiment. Regression

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analysis was performed for the experimental data, and the following equation (Eq. 2) was

expressed by an empirical second order polynomial model.Eq.

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3 3 3

Y  0   iX i   N
 ii X
2
i    ij X j (2)
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i 1 i 1 i 1
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where Y is the predicted response;  0 is a constant;  i is the linear coefficient;  ii is the quadratic
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coefficient;  ij is the interaction coefficient of the variables i and j ; X i and X j are independent
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variables. Finally, lipid extraction experiments were carried out under the optimal extraction

condition obtained by the RSM predictive equation. The validity of the mathematical model was
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verified by comparing the experimental data and predicted values. Finally, comparison of

microwave assisted and conventional heating method in deacidification efficiency was carried
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out.
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2.2.4 Statistical analysis

All the experiments were carried out in triplicate and average values as well as standard

deviations were reported. The results were performed with EXCEL (Microsoft Office Enterprise,

2016) and origin pro 9.1 (Origin Lab, USA) and analysis of variance (ANOVA) was determined

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wherever applicable.

3. Results and discussion

3.1 Single factor experiments

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Deacidification of acidic oil is an esterfication reaction between FFA and alcohol, which is a

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reversible reaction. According to previous studies [25,26], esterification reaction rate was

generally affected by several typical variables, such as reaction time, reaction temperature,

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alcohol to oil ratio and ratio of catalyst loading. Therefore, it is of great importance to conduct

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single-factor experiment to evaluate effect of various process variables on the DR in order to

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screen the parameters of significance and obtain their optimal range in which the highest DR
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could possibly achieve. In our present study we also evaluated the effect of reaction time,
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reaction temperature, methanol to oil ratio, catalyst loading prior to optimize by RSM.
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3.1.1 Effect of reaction time

Deacidification experiments were carried out at different reaction time (2, 4, 6, 8, and 10
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min) while other variables were set as follows: reaction temperature 60 ºC, alcohol/oil 2:1
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(wt/wt) and catalyst loading 5% (wt% on the basis of oil mass). The effect of reaction time on

DR was plotted in Fig. 2. It can be observed from Fig. 1 that the results indicate that the acid
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removal rate was influenced by the time and DR increased steadily with extended reaction time

from 2 min to 10 min and a maximum fatty acid conversion rate (95.4%) was reached when the
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reaction time was 10 min. Afterwards, no significant increase of DR was observed. Therefore,

reaction time of 10 min was selected in the subsequent single factor experiments.

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 Please insert Fig. 2 here

3.1.2 Effect of reaction temperature

The reaction temperature is a crucial parameter in heterogeneous reactions as it controls the

reaction kinetics as well as diffusion rates of reactants and products [27,28]. In this study, effect

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of temperature on DR of acidic oil was carried out at the temperature ranging from 55 ºC to 80

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ºC, while other reaction variables were set as follows: reaction time 10 min, alcohol/oil 2:1, and

catalyst loading 5%. The effect of reaction temperature on DR was illustrated in Fig 3, which

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showed that DR increased when temperature elevated from 55 ºC to 65 ºC and consequently

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achieved a maximum DR of 90.80%, which could be attributed to the reactant molecules had

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obtained adequate energy to cross over the energy barrier thus enhancing reaction rate and
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conversion. However, DR declined when the reaction temperature was higher than 65 ºC. Hence,
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65 ºC was employed as the reaction temperature in the subsequent experiments, considering from

the conversion percentage of reactants and process economic perspective.

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Please insert Fig. 3 here

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3.1.3 Effect of methanol to oil ratio

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Methanol to acid molar ratio has significant impacts on both esterification kinetic and
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subsequent product separation and purification. Hence, it is crucial to study the effect of initial

methanol/oil ratio on DR. Theoretically, the reaction involved in deacidification of acidic oil
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requires one mole of methanol for each mole of oleic acid. However, in order to obtain higher

ester yield, excess alcohol is used to drive the reaction toward forward reaction. Fig. 4 showed

the effect of alcohol to oil ratio on the DR of acidic oil catalyzed by SGAC with microwave

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irradiation. As shown in Fig.4, the DR value increased as the alcohol to acid ratio raised from 1

to 2, which could be attributed to more alcohol facilitate the esterification toward forward

reaction. However, a reduction of DR was observed when the alcohol to oil higher than 2.0,

which was probably due to the dilution effect of large excess alcohol on catalyst active sites.

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Moreover, extremely excessive alcohol used is not facilitated to the separation of target product

from reaction mixtures. Finally, a maximum DR of 89.40% was obtained when alcohol to acid

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ratio was 2 with a catalyst loading of 5.0 % (w/w), reaction temperature of 65 ºC and reaction

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time of 10 min. Consequently, an alcohol to oil ratio of 2 was used in the subsequent single

factor experiments.

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Please insert Fig. 4 here
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3.1.4 Effect of catalyst loading
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Fig. 5 presented the effect of catalyst loading on DR of microwave aided sulfonated

granular activated carbon catalyzed deacidification. The experiments were carried out at the
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catalyst loading at the range of 3.0 % to 7.0 %, while reaction time, reaction temperature and
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alcohol to oil ratio was set at 10 min, 60 ºC and 2:1, respectively. It could be clearly observed
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that DR increased steadily when the catalyst loading was no more than 5%, which was due to

more available active sites as catalyst loading raised, resulting in higher reaction rate and
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equilibrium conversion[29]. Yet, a further increase of the amount of the catalyst beyond 5%

showed no dramatic increase of DR, which could be attributed to higher catalyst loading would
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facilitate faster reaction rate and generate more water in a short time. Excess water could

deactivate the active site of catalyst due to hydration occurred [30, 31]. Hence, a catalyst loading

of 5% could possibly be the optimal amount of the catalyst in acidic oil deacidification.

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Consequently, an reaction temperature range of 60~70 ºC, alcohol to oil ratio range of 1.5~2.5,

and catalyst loading range of 3~7% were selected for RSM experiments based on results from

the single factor experiments.

Please insert Fig. 5 here

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3.2 Optimization of acidic oil deacidification process by RSM

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According to the single factor experiments, three variables (reaction time, reaction

temperature, and catalyst loading) were screened to be optimized by RSM. A 17-runs design of

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RSM was proposed with the assistance of Design Expert 8.0. The layout of 17 runs using RSM

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was shown in Table 1 in actual and coded variables. The RSM experiment results were listed in

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Table 2, which include the design, observed responses and the predicted values.
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Please insert Table 1 and Table 2 here

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3.2.1 Model Development

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Table 1 illustrates the independent variables and the corresponding levels in actual and
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coded factor for the RSM experiment. The RSM experimentally-obtained results and

statistically-predicted values are presented in Table 2. Each experimentally-obtained value is the

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average of duplicate independent runs. It can be observed that the response varied greatly from

74.6% to 96.6%. Moreover, the response obtained allows us to determine a typical quadratic

model (Eq. (2)) expressed in terms of code factors using multiple regression analysis.

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DR= 94 . 72 + 3 . 66 X 1 + 2 . 41 X 2 + 2 . 67 X 3 -1 . 70 X 1 X 2
2 2 2
- 2 . 63 X 1 X 3 -1.18 X 2 X 3 - 3 . 59 X 1 - 3 . 19 X 2 - 7 . 11 X 3 ( 2)

where DR is the deacidification rate, X1, X2 and X3 are the coded variables for reaction

temperature, alcohol to oil ratio, and catalyst loading, respectively.

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The maximum DR of 94.72% was found from the fitted model under the variables as

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follows: reaction temperature 65.0 ºC, alcohol to oil ratio 2:1, and catalyst loading 5.0 % on the

basis of the fitted model.

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The quality of the models developed can be evaluated based on the correlation coefficient

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R2 and also on the lack-of fit value[32]. Table 3 illustrates the regression data for DR for the
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developed predictive model. The determination coefficient (R2=0.9276) by analysis of variance
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(ANOVA) of the fitted model, implies that only 0.0724% of the total variation could not be
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explained by the model. The value of the adjusted determination coefficient (Adj R2=0.8346)
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also verifies the high significance of the model, indicating acceptable deviations between the
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experimental value and the predicted data. Moreover, the fitness of the model was studied

through lack of fit test. The F value of 9.97 and p value of 0.0031 further confirm the validity of
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the model. Thus the model is adequate for prediction in the range of experimental variables. As

shown in Table 3, values of ‘Prob > F’ of X1, X2, and X3 were all less than 0.05, indicating model
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terms are significant. Based on the ‘Prof > F’ value, it could be considered that reaction

temperature (X1) was the most significant independent variable affecting DR with a p-value less
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than 0.0051. The higher the reaction temperature was, the greater DR could be. The catalyst

loading (X3) also exerted a positive individual influence on the DR. This implies that an increase

in the catalyst loading could improve the DR. In addition, the reaction temperature and catalyst

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loading exerted significant quadratic effects (Table 3). However, other terms (X1X2, X2X3 and

X1X3) were statistically insignificant, suggesting an absence of interaction between the variables

(p>0.05) on DR. To understand the mutual effect of the corresponding parameters, the regression

model was represented in terms of response surface plots (3D) in Fig. 6. Fig. 6(a) illustrates the

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combined effects of the reaction temperature and alcohol/oil on the DR. It showed that the

interaction between the two selected variables has little influence on the DR. With regard to the

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correlation between reaction time and catalyst loading (Fig. 6(b)), it is apparent that the DR

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value is dramatically enhanced as the catalyst loading increases up to approximately 6.0% and

then decreases with further increments of this value at a given reaction temperature. However, no

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dramatic improvement in DR could be obtained with higher reaction temperature, while keeping

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catalyst loading constant. Moreover, no significant interactions were observed between these two
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variables, as demonstrated by its p-value of 0.08. Similarly, no dramatic interaction between
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alcohol/oil and the catalyst loading was observed on the DR, as illustrated in Fig. 6(c).
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Please insert Table 3 here

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Please insert Fig. 6 here

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3.2.2 Validation of the Model

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According to the above results, the optimum extraction conditions were obtained as follows:

reaction temperature 65 ºC, alcohol/oil 2:1, and catalyst loading 5.0%. The predicted DR was

94.72 % under the optimum conditions, according to the model. To confirm these conclusions,

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experiments based on the model predicted optimal parameters were performed and the DR was

determined. The experimental value was 93.26%, which shows good agreement with the

predicted value. Moreover, the verification experiments also proved that the predicted values of

DR from the fitted model could be satisfactorily achieved within a 95% confidence interval of

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experimental values and consequently demonstrating the RSM model is satisfactory.

4. FTIR characterization of SGAC

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FTIR spectra of SGAC catalysis before and after used for deacidification were detected. As

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shown in Fig. 7, bands at 1259 cm−1 for —SO3H stretching vibration demonstrate successful

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introduction of -SO3H from sulphonic in the toluene-p-sulfonic acid group form onto the

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granular activated carbon as indicated by the curve of FTIR spectrum of SGAC before used. In
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addition, adsorption peak at around 1259 cm-1 could also been observed in the spectrum of
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SGAC after used, which validated that most of the SO3-H were still on the granular activated

carbon. A strong adsorption peak obesrved at 1637 cm−1 could be attributed to the existence of
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phenyl group, which proof the linkage between benzene structure and activate carbon [33].
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Please insert Fig. 7 here

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5. Comparison of various catalysts and heating methods

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Table 4 lists the major results of DR achieved using different kinds of waste oils and

catalysts by the mentioned authors in comparison with the results achieved in the present study.

From Table 4, it can be clearly seen that various heterogeneous catalysts and heating methods

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had been employed in the study of acidic oil deacidification process. According to the reports

listed in Table 4, the DR achieved using heterogeneous catalysts ranged from 55~98.4% [14,21]

with different reaction time. Nevertheless, it took a very long time (more than 4 hours) to achieve

a high DR (more than 90%) in the esterification reaction heated by conventional method (i.e.

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water/oil/air bath), except the report by Otadi et al.[31], who used silica sulfuric acid as catalyst

and obtained DR more than 90% in 30 min with water bath heating. However, the initial acid

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value of the waste cooking oil in the study of Otadi[31] was only 7.1 mgKOH/g oil. It should be

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pointed out that the acid value of the acidic oil in this study was as high as 56.38 mgKOH/g oil.

Higher initial acid value in the waste oil meant excess water generated in the deacidification

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process, which will decrease the forward reaction rate, as water had not been removed from the

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reaction system in batch reaction. However, much higher efficiency in deacidification was
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achieved using microwave or ultrasound heating, for example, according to the report by
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Zhang[21], a 97.4% DR was obtained in 1.5 h, compared to that of 4 h to achieved DR of 98.4%

with CERP/PES membranes as heterogeneous catalyst. In addition, in the present study,

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comparisons were conducted in deacidification process heated by water bath and microwave. As
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illustrated in Table 4, DR value of 93.26% had been achieved in 10 min with microwave
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irradiation, compared to a 89.98% DR value in 1 hour with water bath heating using SGAC as

catalyst. Moreover, self-catalyze (without SGAC addition) effect was evaluated and results were
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shown in Table 4, DR of 57.60% and 60.40% could be achieved in 1 hour and 10 min,

respectively, indicating SGAC dramatically increase the deacidification efficiency. The

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mechanisms of accelerated deacidification with microwave heating compared to water bath

heating were: (1) super heating (forming molecular radiators) and selective heating effect on

methanol which made a rapid temperature rise available, which is facilitate to achieved a higher

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reaction yield with less reaction time[37]; (2) local temperature gradients and internal

evaporation during microwave irradiation can promote transport of reactants and energy, which

is beneficial to the fully contact of methanol and SGAC[38]; (3) nanobubble is formed and

surface tension of acid oil is reduced by microwave heating, which makes the fully contact of

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reactants in the system[39]; and (4) the collapse of nanobubbles or water (generated during the

reaction) cluster can release huge energy in a confined space.

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6. Conclusions

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Microwave irradiation significantly enhanced the deacidification efficiency in the process of

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acidic oil deacidification catalyzed by SGAC compared to that of water bath heating. In addition,

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an RSM model, validated by experimental results was proposed to predict the DR of acidic oil
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esterified by SGAC with microwave heating. The optimum reaction variable were as follows:
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reaction temperature 60 ºC, alcohol to oil ratio 2:1 and catalyst loading 5%, in which, a DR of

93.26% was achieved based on the response surface methodology. Finally, microwave irradiation
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showed great potential to be a good alternative heating method in accelerating the deacidification
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process of acidfied oil catalyzed by sulfonated granular activated carbon to traditional heating

method, such as water/oil/air bath. However, further work is required to investigate the scale up
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feasibility and accurate economic analysis of the process.

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Acknowledgment
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This research was supported by Guangdong Provincial Key Laboratory of New and

Renewable Energy Research and Development (No. Y707s31001) and National Natural Science

Foundation of China for Young International Scientists (21650110457). Our research is also

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supported by National key research and development program-China (2016YFB0601004).

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List of Figure and Figure Captions

Fig. 1 Microwave reactor set up

Fig. 2 Effect of reaction time on deacidification rate (DR)

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Fig. 3 Effect of reaction temperature on deacidification rate (DR)

Fig. 4 Effect of methanol to oil ration on deacidification rate (DR)

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Fig. 5 Effect of catalyst loading on deacidification rate (DR)

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Fig. 6 Response surface plots (3D) and contour plots (2D) showing the mutual effect of (a)

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reaction temperature and alcohol/oil; (b) reaction temperature and catalyst dosage; (c) alcohol/oil

and catalyst dosage on the DR

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Fig. 7 FTIR spectrum of SGAC before and after used
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List of Table and Table Captions

Table 1 Factors and levels for RSM, BBD matrix (in actual and coded levels of three variables)
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Table 2 Experimental runs and corresponding results regarding BBD

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Table 3 Analysis of variance (ANVOA) of the model developed

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Table 4 Summary of recent studies comparing catalysts and heating methods for waste oil

deacidification

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 Process variables
Condenser pipe displaying screen

Camera

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Parameter

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setting panel

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Microwave
reactor

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Fig.1 Microwave reactor set up
Flask
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Fig. 2 Effect of reaction time on DR

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A
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 Fig. 3 Effect of reaction temperature on DR

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Fig. 4 Effect of methanol to oil ration on DR

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Fig.5 Effect of catalyst loading on DR

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(a)
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 (b)

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(c)

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A
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Fig.6 Response surface plots (3D) and contour plots (2D) showing the mutual effect of (a)
reaction temperature and alcohol/oil; (b) reaction temperature and catalyst dosage; (c) alcohol/oil
and catalyst dosage on the DR.
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Fig. 7 FTIR spectrum of SGAC before and after used

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N
A
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Table 1 Factors and levels for RSM, BBD matrix (in actual and coded levels of three
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variables)
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Levels
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Process variables Coded Symbols

-1 0 +1
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Reaction temperature (ºC) X1 60 65 70

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Alcohol/oil(wt/wt) X2 1.5 2.0 2.5

Catalyst dosage (%) X3 3.0 5.0 7.0

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Note: All experiment data presented in the table was average value of duplicate experiments

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 Table 2 Experimental runs and corresponding results regarding BBD

Run X1 /ºC X2 /wt/wt X3 /% DR /%

1 70 1.5 5 90.6

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2 70 2 7 88.2

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3 65 1.5 7 85.7

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4 60 1.5 5 80.4

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5 65 2 5 96.3

6
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65 2 5 88.7
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7 65 1.5 3 78.4
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8 65 2 5 96.6
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9 65 2.5 3 85.5
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10 60 2 7 85.6

11 65 2 5 96.1
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12 65 2 5 95.9
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13 60 2 3 74.6

14 70 2 3 87.7

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 15 60 2.5 5 88.7

16 70 2.5 5 92.1

17 65 2.5 7 88.1

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Note: All experiment data presented in the table was average value of duplicate experiments

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Table 3 Analysis of variance (ANVOA) of the model developed

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Sum of Mean F p-value
Source df
Squares Square
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Value Prob > F
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Model 595.29 9 66.14 9.97 0.0031 significant

X1
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107.31 1 107.31 16.17 0.0051

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X2 46.56 1 46.56 7.02 0.033

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X3 57.25 1 57.25 8.63 0.0218

X1X2 11.56 1 11.56 1.74 0.2284

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X1X3 27.56 1 27.56 4.15 0.0809

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X2X3 5.52 1 5.52 0.83 0.392

2
X 1
54.11 1 54.11 8.15 0.0245

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 2
X 2
42.71 1 42.71 6.44 0.0388

2
X 3
212.85 1 212.85 32.08 0.0008

Residual 46.45 7 6.64

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Lack of Fit 0.88 3 0.29 0.026 0.9935 not significant

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Pure Error 45.57 4 11.39

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Cor Total 641.74 16

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Std. Dev. 2.58 R-Squared 0.9276
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Adj R-
Mean 88.19 0.8346
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Squared
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Pred R-
C.V. % 2.92 0.867
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Squared

Adeq
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PRESS 85.32 9.95

Precision
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A

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Table 4 Summary of recent studies comparing catalysts and heating methods for waste oil deacidification

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Feedstocks Catalyst Heating method Reaction time DR/% References

waste cooking oil sulfonated biomass water bath 14~18 h 55~58 Ezebor et al.[14]

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waste cooking oil Amberlyst-15 heating mantle 1h 60.2 Gan et al. [15]

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waste cooking oil silica sulfuric acid Water bath 30 min 90 Otadi et al. [31]

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waste cooking palm oil activated carbon supported KF Oil bath 1h 83 Hameed[34]

Water bath 4h 98.4

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waste cooking oil CERP/PES membranes Zhang et al. [21]
Microwave 1.5 h 97.4
ED
oleic acid sulfonated coal Ultrasound 1h 91.4 Yu et al. [29]

waste fish oil sulfonated activated carbon Ultrasound 1h 88 Sobati et al. [35]
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oleic acid and cottonseed

sulfonated and carbonized vegetable oil asphalt Oil bath 6h 93.9 Shu et al. [36]
oil
E

Water bath 1h 89.98

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With sulfonated activated carbon

Microwave 10 min 93.26
acidic oil
Present study
(synthetic waste oil)
A

Water bath 1h 57.60

no sulfonated activated carbon
Microwave 10 min 60.40

36