Fuel 244 (2019) 419–430

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Full Length Article

Integrated valorization of waste cooking oil and spent coffee grounds for T
biodiesel production: Blending with higher alcohols, FT–IR, TGA, DSC and
NMR characterizations
A.E. Atabania, , Sutha Shobanab, M.N. Mohammedc, Gediz Uğuzd, Gopalakrishnan Kumare, ,
⁎ ⁎

Sundaram Arvindnarayanf, Muhammad Aslamg, Ala'a H. Al-Muhtasebh

a
Green Processing, Bioremediation and Alternative Energies Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City,
Vietnam
b
Department of Chemistry and Research Centre, Aditanar College of Arts and Science, Virapandianpatnam, Tiruchendur, Tamil Nadu, India
c
Energy Division, Department of Mechanical Engineering, Faculty of Engineering, Erciyes University, 38039 Kayseri, Turkey
d
Department of Chemical Engineering, Faculty of Engineering, Ondokuz Mayıs University, 55200 Samsun, Turkey
e
Institute of Chemistry, Bioscience and Environmental Engineering, Faculty of Science and Technology, University of Stavanger, Box 8600 Forus, 4036 Stavanger, Norway
f
Department of Mechanical Engineering, R.M.K. Engineering College, R.S.M. Nagar, Kavaraipettai, Tamil Nadu, India
g
Department of Chemical Engineering, COMSATS University Islamabad (CUI), Lahore Campus, Defense Road, Off Raiwind Road, Lahore, Pakistan
h
Department of Petroleum and Chemical Engineering, College of Engineering, Sultan Qaboos University, Muscat, Oman

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: This work deals for the first time with recycling a binary blend of waste cooking oil (WCO) and spent coffee
Waste cooking oil grounds oil (SCGO) (50/50% by volume) into biodiesel. Additionally, this work aimed at valorizing both wastes
Spent coffee grounds oil while improving fatty acids composition to obtain a stabilized product due to low degree of unsaturation of
Biodiesel SCGO besides, reducing its high acid value. Furthermore, blending with Euro diesel and higher alcohols of
Higher alcohols
butanol, pentanol and hexanol to improve some biodiesel properties was investigated. Furthermore, FT–IR,
FT–IR
UV–vis., TGA, DSC and NMR analyses to assess the blends quality was examined. Results have proved the ad-
TGA
DSC vantage of pre-blending and higher alcohols addition to improve the fuel properties. The biodiesel exhibits
NMR excellent cetane number of 56.64, oxidation stability of about 6.51 h and iodine value of 83.71 (g iodine/100 g)
due to the low degree of unsaturation (89.02). Blending with higher alcohols improves density and cold flow
properties while keeping acceptable level of cetane number, flash point and higher heating value (HHV) rather
than lower alcohols. Consequently, this opens new gates for biodiesel research area. In conclusion, this work
reinforces that blending of WCO and SCGO improves biodiesel properties and add to the economy of this

⁎
Corresponding authors.
E-mail addresses: [email protected] (A.E. Atabani), [email protected] (G. Kumar).

https://doi.org/10.1016/j.fuel.2019.01.169
Received 5 December 2018; Received in revised form 25 January 2019; Accepted 30 January 2019
Available online 13 February 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
A.E. Atabani, et al. Fuel 244 (2019) 419–430

industry. Therefore, further examination on the blends effect in compression ignition diesel engines through
engine emissions and combustion characteristics is recommended.

1. Introduction compound [35], adsorbent [5,36,37], polymers [38,39] composting

[40,41], co-composting [42,43], vermicomposting [44], nanocompo-
World is producing a huge amount of waste in daily basis. These sites [45] and pulp-paper production [1]. Preliminary calculations
include municipal, food, beverage, agricultural, and industrial wastes conducted by the literature [34] indicated that converting the oil ex-
etc. Dumping these wastes directly to the landfills is very harmful if tracted from SCG to biodiesel besides utilizing the left over SCG, after
either not disposed or recycled in an appropriate manner as they are the oil extraction as fuel pellets can yield a profit of more than $8
toxic and may cause serious environmental problems [1]. This is due to million/year in the United States only (considering the waste generated
the existence of some organic compounds that demand excessive by Starbucks stores). Moreover, a summary on some SCG valorization
amounts of oxygen to degrade [2]. Creating biofuels from waste offers pathways options has been given in our previous study [2].
many environmental, social and financial benefits. Recycling of waste SCGO compared to other waste such as brown grease, pork fat
to energy and added-value products is an effective way to solve the (white grease), lard, fish oil, poultry fat for biodiesel production offers
problem of many countries that face a challenge in dealing with the many advantages due to its higher stability, well established transpor-
huge amount of wastes generated daily due to their increasing popu- tation and pleasant odour. However, the oil extraction is required to
lation, industrial growth and human consumption. Waste recycling of- process the SCG into biodiesel [2,34]. Higher alcohols such as butanol
fers many environmental, social and financial benefits [2]. In this re- (C4H10O), pentanol (C5H12O) and hexanol (C6H14O) have many ad-
gard, restaurants and beverage shops generate a huge amount of wastes vantages over lower alcohols such as methanol (CH4O) and ethanol
such as waste cooking oil (WCO), spent coffee grounds (SCG), food (C2H6O) in compression ignition (CI) engines such as having higher
waste (FW), spent tea waste (STW). Among them, WCO and SCG are flash point, density, energy density, cetane number, heating value and
two valuable wastes due to their potential characteristics. Official sta- kinematic viscosity, lower hygroscopicity and volatility and better
tistics on the production and consumption of fats and vegetable oils are miscibility with diesel and biodiesel [46]. Moreover, their positive ef-
available, commonly. Nevertheless, the actual statistics on at least an fect to reduce the high kinematic viscosity, density and cold flow
actual level of collection of WCO oils is far more erratic and in- properties has already been validated in the literature [47]. Butanol
homogeneous [3]. This is due to the absence of appropriate collection (But) is an organic alcohol with a four-carbon chain. Application of
management system in many countries. Direct disposal of WCO to the butanol as an oxygenated fuel in diesel engines has recently been re-
environment may cause serious problems such as polluting the rivers, cognized as a promising and green alternative fuel. It can be produced
drainage choking, propagations of unpleasant smell and bugs [4]. The by petrochemical, fermentative and catalytic routes [48,49]. Pentanol
classification of coffee tree and beverage preparation and its health (Pen) is an organic alcohol with a five-carbon chain that can be pro-
benefits to reduce the risk of cancer (liver, kidney, oral, breast and duced from renewable feedstock such as glucose or glycerol through
colorectal), neuro degenerative disease (Parkinson, Alzheimer and metabolic engineering or biocatalysts [46,50]. Hexanol (Hex) is an
Amyotrophic lateral sclerosis) and cardiovascular disease have been organic alcohol with a six-carbon chain that can be produced in-
explained in our recent publication [2]. Due to coffee refreshing dustrially by the oligomerization of ethanol which can be produced
properties, millions of coffee cups are consumed every day around the from crops, corns, vegetables, and other feedstocks such as wastes from
world and thus, coffee is the second largest traded commodity after agricultural food and beverage processing [51].
petroleum [1,2]. Coffee silverskin (CS) and SCG are the main coffee Our previous work [2] targets the assessment of SCG before and
industry residues, obtained during the beans roasting, and the process after the lipids extraction. All samples were tested for Scanning Electron
to prepare “instant coffee”, respectively [1]. This is responsible to Microscopy (SEM), Differential scanning calorimetry (DSC), Thermo-
generate large quantities of wastes [2]. According to the literature gravimetric analysis (TGA), X-Ray diffraction (XRD), calorific value,
[5,6], the coffee industry generates around 6 million tons of wastes per surface analysis and porosity, Fourier transform infrared spectroscopy
year. As a result, large amounts of a dark colored waste are generated as (FT–IR), density and elemental analysis. Oil was extracted and conse-
550–670 g as SCG from 1 kg of Robusta coffee. quently followed by biodiesel production and blending with Euro diesel
(D) at different percentages. Results showed that SCG before and after
the lipids extraction can be utilized as compost, as it is rich in nitrogen
2. Overview of WCO and SCGO recycling potential (16.7%). Biodiesel exhibits excellent cetane number, higher heating
and iodine values with poor cold flow properties due to the combined
Both WCO and SCG wastes can be processed in different ways. For effect of low degree of unsaturation (DU) and high long chain saturated
instance, WCO can be processed into biodiesel [7,8] whereby glycerin factor (LCSF). Furthermore, the analyses support that SCG after oil
produced as a by-product during the transesterification process (10% of extraction is an ideal material for garden fertilizer, feedstock for
transesterification) which is a valuable source for cosmetics and phar- ethanol, biogas production, and as fuel pellets.
maceutical industries besides, it can be also processed further into some This work targets to carry on our previous study where the extracted
other types of biofuels such as biogas and biohydrogen [9,10]. More- oil from SCG was blended with WCO prior to biodiesel production. This
over, WCO is averagely five times cheaper than the refined cooking oil was aimed at valorizing both wastes while improving the fatty acids
[4]. This remarkably cuts down the cost of biodiesel production as 75% composition to obtain a stabilized product due to the high saturation
of total biodiesel production cost comes from the price of feedstock level of SCGO. This will also reduce the high acid value of SCGO to a
[11]. On the other hand, SCG contains large amounts of organic com- lesser level and thus eases the biodiesel production process (Section
pounds (i.e. fatty acids, amino acids, polyphenols, minerals lignin and 3.1). The blended sample was prepared as 50/50% by volume and kept
polysaccharides [12,13] namely; galactomannans and arabinogalactans in a reagent bottle for further analyses before the biodiesel production.
[14,15]) that remain insoluble in SCG and thus can be valorized in This was followed by blending the biodiesel with D100 and higher al-
different ways. It can be recycled to produce biofuels such as biodiesel cohols of But, Pen and Hex to improve the kinematic viscosity, density
[2,16–22], fuel pellets [23,24], bio-oil [25–27], bioethanol [28,29], and cold flow properties of biodiesel. Detailed characterization of the
biogas [30,31], hydrocarbon fuels [32,33], biohydrogen [1,34] and blends using reliable, fast and cheap methods of FT–IR,
biobutanol [1] or value-added products applications such a bioactive

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A.E. Atabani, et al. Fuel 244 (2019) 419–430

Nomenclature KV Kinematic viscosity

LCSF Long chain saturated factor
B100 Biodiesel MWi Molecular weight of fatty acid
But Butanol MPn Melting point of saturated fatty acid
CI Compression ignition N No of double bonds in mono/poly unsaturated fatty acids
CN Cetane number NMR Nuclear magnetic resonance
CS Coffee silverskin OS Oxidation stability
DSC Differential scanning calorimetry Pen Pentanol
D100 Euro diesel SCGO Spent coffee grounds oil
DU Degree of unsaturation SCGOME Spent coffee grounds oil methyl ester
FAC Fatty acid composition SN Saponification number
FAMEs Fatty acid methyl esters TGA Thermogravimetric analysis
FT–IR Fourier transform infrared spectroscopy UV–vis., Ultraviolet–visible absorption spectra
GC Gas chromatography WCO Waste cooking oil
HHV Higher heating value WCOME Waste cooking oil methyl ester
Hex Hexanol i Kinematic viscosity of fatty acid at 40 °C
IV Iodine value

Ultraviolet–visible absorption spectra (UV–vis.), TGA, DSC and Nuclear heating to 60 °C (hold for 2 min), then to 200 °C with heating rate
magnetic resonance (NMR) analyses was extensively studied and pre- 10 °C/minute and finally to 240 °C with heating rate 5 °C/minute (hold
sented. Moreover, some important properties of the blends were also for 7 min). Analyses were made as per the standard of fat and oil de-
investigated as qualitative and quantitative analyses as well that can rivatives (TS EN 14103:2011).
valorize both WCO and SCGO in one pot. Consequently, such a study DU was calculated from the proportion of monounsaturated and
opens new directions for the biodiesel research area in the future. In polyunsaturated fatty acids using the following equations [4,52,54,55]:
conclusion, authors have recommended to further examining the effects
of these blends in CI ignition diesel engines through engine emissions DU = (monosaturated Cn: 1, wt %) + 2(polunsaturated Cn: 2, wt %)
and combustion characteristics. + 3(polyunsaturated Cn: 3, wt %) (1)

The proportions of saturated fatty acids (wt%) and their corre-

3. Materials and methods sponding melting points (MPn), were used to calculate LCSF as follow
[4,52,54,55]:
3.1. Materials, equipment, oil characteristics and biodiesel production
(MPn Cn wt %)
LCSF =
100 (2)
SCG was collected from Gloria Jean coffee shop (Kayseri, Turkey)
while WCO was collected from the main food Court of Erciyes Kinematic viscosity at 40 °C (KV), cetane number (CN), oxidation
University through personal communication. All the chemicals required stability (OS), higher heating value (HHV), iodine value (IV) and sa-
for oil extraction, biodiesel production and blending were obtained ponification number (SN) of WCOME/SCGOME were calculated em-
from a local chemical supplier in Kayseri. D100 was purchased from pirically using the following formulae [4,55,56]:
APET petrol station. Properties of crude oil, produced biodiesel and
blends were determined following the equipment list as given in the
ln( i ) = 12.503 + [2.496 × ln(MWi ] (0.178 × N ) (3)
literature [52]. Table 1 also shows some main properties of the waste CN = 0.1268(DU ) 10.805 (4)
cooking oil methyl ester/spent coffee ground oil methyl ester
(WCOME/SCGOME) besides a comparison with pure WCOME and OS = 0.0518(DU ) + 11.121 (5)
SCGOME. Acid value of WCO/SCGO was determined and found to be
12.1 mg KOH/g oil. Therefore, two steps of acidic esterification fol- 1794
HHV = 46.19 (0.21 × N )
lowed by alkaline transesterification were adopted to produce bio- MWi (6)
diesel. It was observed that blending reduces the extreme high acid
value of SCGO as compared to previous work [2,53] (22.3 mg KOH/ g IV = 1.0617(DU ) 10.805 (7)
oil and 14.65 mg KOH/ g oil). Table 2 shows the summary of biodiesel
production process. This process resulted in a high quality final product 560 × Ai
SN = Sum
with a biodiesel yield of more than 95%. It is noticeable that such MWi (8)
blending improves density and slightly reduces cold flow properties of where represents the kinematic viscosity of the fatty acids at 40 °C
i
SCGOME.
Table 1
3.2. Gas chromatography (GC) method of WCOME/SGCOME Properties of SCGO, WCO and WCO/SCGO and its methyl esters.
Property SCGO WCO WCO/ SCGOME WCOME WCOME/
Determination of Fatty acids composition (FAC) profile of WCOME/ SCGO SCGOME
SGCOME has been done using Perkin Elmer Clarus 680, equipped with
Density at 15 °C 932.9 915.9 923.7 891.6 883.1 885
a flame ionization detector (FID) and a BPX70 capillary column in
(kg/m3)
which 1 µL of the sample was injected following the method prescribed Cloud point (°C) −3 14 5 11 9 9
in our previous publications [52]. The carrier gas was Helium with Pour point (°C) −3 4 2 12 9 9
column flow rate, head pressure and dimension of 1.00 mL/minute Cold filter – – – 5 3 2
(column flow), 70 kPa (flow control made) and 60.0 plugging
point (°C)
mx0.25µmx0.25 mm ID respectively. The test was conducted using an
optimized in-house GC method with temperature ramp details of

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A.E. Atabani, et al. Fuel 244 (2019) 419–430

Table 2 was employed to purify the sample crystal before the background col-
Summary of biodiesel production process. lection. The scan results were processed with a computer software
Esterification Parameter Transesterification Parameter program Spectrum.

Hydrochloric acid 1% (v/v oil) Potassium hydroxide 1% (m/m oil) 3.4.2. UV–vis. Spectra
(HCL) (KOH)
UV–vis. spectra provide information about the electronic properties
Methanol (CH3OH) 100% (v/v oil) Methanol (CH3OH) 25% (v/v oil)
Reaction time 3h Reaction time 1.5 h of the oil molecules. All organic compounds absorb light in the visible
Reaction 60 °C Reaction temperature 60 °C and ultraviolet region. It is possible to see various aromatic compounds
temperature in diesel fuel sources [58]. In this study, all the samples were analyzed
by UV–vis. to obtain the spectra and the quartz cuvettes were filled with
the blends. The UV absorption spectra of the biodiesel blends were
obtained using Agilent Technologies Cary 60 UV–vis. Spectro-
MWi represents the molecular weight of the fatty acids and N re- photometer in the wavelength range of 500–200 nm at 1 nm intervals of
presents the number of double bonds in monounsaturated and poly- using standard 1 cm quartz cuvettes at room temperature.
unsaturated fatty acids.
3.4.3. Differential Scanning Calorimetric (DSC) and thermogravimetric
3.3. Fuel modification and selection of binary and ternary blends analysis (TGA) studies
DSC is used to determine the crystallization onset temperature of
Blending of WCOME/SCGOME with But, Pen, Hex and D100 was the samples and can be plotted on the graph against heat flow. The DSC
adopted in this study to modify some properties of WCOME/SCGOME. curves were obtained in a calorimeter model TA Q-2000 with RCS90
Thus, two binary blends of (D80B70) and (D70B30) and three ternary coupled with a cooling system. 3 ± 0.5 mg of each sample was loaded
blends of (D80B10But10), (D80B10Pen10) and (D80B10Hex10) were in an aluminum pan and heat flow was measured differentially by
prepared and kept in reagent bottles. All the blends show good mis- comparing the heat flow of an empty reference pan as a reference. The
cibility and stability over a long period. Properties such as density, rate of heating/cooling was 10 °C min−1 between −80 °C and 20 °C
kinematic viscosity, pour point, cloud point and cold filter plugging under inert nitrogen atmosphere (N2) with a flow rate of 50 mL min−1.
point were examined and the equipment list can be found in our pre- In this study, all the samples and blends were analyzed by TA Q-2000
vious work [52]. The densities of all the samples are predicted math- DSC under the flow of nitrogen. Each DSC test takes about 17 mins to
ematically with a polynomial curve-fitting method, a polynomial of complete. Results were processed with the help of TA Orchestrator
order k in X is expressed in the following form [57]. Version V7.2.2.1.
The thermogravimetric (TG) thermograms of WCO/SCGO,
Y = C + C1 X + C2 X 2 +Ck X k (9)
WCOME/SCGOME, D100, But100, Hex100, Pen100 and their blends
were recorded in a Shimadzu DTG 60H thermogravimetric analyzer
3.4. Spectral studies using platinum pans. 10 mg of each sample was loaded into pans. After
each analysis, platinum pans were cleaned well in order to make the
3.4.1. FT–IR spectra pans ready for the next run. In this analysis, the temperature ranges
The infrared spectra of all the samples were obtained in a Fourier from 25 to 700 °C with a heating rate of 10 °C/min under dry air at-
Transform Infrared Spectrometer by Perkin Elmer Spectrum Two. The mosphere of 100 mL /min to determine the oxidative stability. Each
supporting software was spectrum software. Each spectrum was taken sample took a period of time, almost an hour. A maximum temperature
within few seconds at the resolution of 4 cm−1 and 4 scans, in the re- of 700 °C was used as the mass remains constant until the end of the
gion of 4000–650 cm−1 and 0.5 mL per sample. Cleaning with ethanol analysis and all the chemical reactions were completed at this

Table 3
FAC, DU, LCSF, KV, CN, OS, HHV, IV and SN of WCOME/SCGOME.
FAC Analyses

Fatty acid MWi Structure N Systematic name Formula (%) DU MPn LCSF SN HHV

Myristic 228.37 14:00 0 Tetradecanoic C14H28O2 0.32 54.4 0.174 0.78 0.123
Palmitic 256.40 16:00 0 Hexadecanoic C16H32O2 32.56 62.9 20.480 71.11 12.761
Stearic 284.48 18:00 0 Octadecanoic C18H36O2 6.0 69.3 4.1580 11.81 2.393
Oleic 282.47 18:01 1 Cis-9-Octadecenoic C18H34O2 29.69 29.69 58.86 11.766
Linoleic 280.45 18:02 2 Cis-9-cis-12 Octadecadienoic C18H32O2 28.02 56.04 55.95 11.032
Linolenic 278.43 18:03 3 α-Linolenic acid C18H30O2 1.0 3.0 2.01 0.391
Arachidic 312.53 20:00 0 Eicosanoic C20H40O2 1.86 75.5 1.404 3.33 0.752
Gendoic 310.55 20:01 1 Cis-11-eicosenoic acid C20H38O2 0.29 0.29 0.52 0.117
Behenic 340.58 22:00 0 1-Docosanoic acid C22H44O2 0.26 80 0.208 0.43 0.106
Saturated 41.00 DU, LCSF, KV, CN, OS, HHV, IV and SN
Monounsaturated 29.98 DU 89.02
Polyunsaturated 29.02 LCSF 26.42
Total 100 KV at 40 °C (mm2/s) 3.88
CN 56.64
OS (h) 6.51
HHV (MJ/kg) 39.44
IV (g Iodine/100 g) 83.71
SN 204.8

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A.E. Atabani, et al. Fuel 244 (2019) 419–430

Table 4
Summary of biodiesel, biodiesel-diesel and biodiesel-diesel-higher alcohols blends properties.
Property WCOME/SCGOME B20 B30 D80B10But10 D80B10Pen10 D80Hex10B10 D100

3
Density at 15 °C (kg/m ) 885 850.1 854.1 842.5 843.3 843.5 842.5
Cloud point (°C) 9 −3 −2 −3 −3 −2 −5
Pour point (°C) 9 −6 −3 −7 −6 −9 −14
Cold filter plugging point (°C) 2 −14 −11 −22 −20 −19 −26

B ≡ WCOME/SCGOME.

Fig. 2a. Infrared spectra of D100, But100, Pen100, Hex100, WCO/SCGO and
WCOME/SCGOME.

Fig. 1. Effect of temperature range (15–40 °C) on density (kg/m3).

Table 5
Prediction of density (kg/m3) at temperature range (15–40 °C). Fig. 2b. Infrared spectra of B20D80, B30D70, B10But10D80, B10Pen10D80
and B10Hex10D80.
Sample Equation R2

WCO −0.7016x + 926.46 0.9997

SCGO −0.687x + 942.6 0.9684
temperature. TGA curves were used to analyze the onset temperature of
WCO/SCGO −0.6751x + 933.91 0.9993
WCOME −0.7711x + 894.51 0.9996
WCO/SCGO, WCOME/SCGOME, D100, But100, Hex100, Pen100 and
SCGOME −0.7219x + 902.59 0.9996 their blends.
WCOME/SCGOME −0.7411x + 896.11 1
D80B20 0.7081x + 860.81 0.9998
D70B30 −0.7086x + 864.76 1
3.4.4. 1H and 13C NMR studies
D80B10But10 −0.7322x + 853.52 1
D80B10Pen10 −0.7314x + 854.24 1 The NMR analyses for all the samples were performed using Agilent
D80B10Hex10 −0.7238x + 854.38 1 Technolohies Premium Compact NMR at 600 MHz (1H) and 150 MHz
D100 −0.7265x + 853.05 0.9986 (13C) with the residual solvent peaks as internal references.
Spectrometer equipped with suitable probes for cores of 1H, 13C, 19F,
B ≡ WCOME/SCGOME. 31
P. MeOD was used as both the solvent as well as internal standard
respectively. 1H and 13C spectra were recorded.

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A.E. Atabani, et al. Fuel 244 (2019) 419–430

Table 6
Functional group frequencies of the fuel samples [63].
Wavenumber, cm−1 Types of vibration Functional Groups

3300–3500 Stretching OeH of alcohols

2949 Asymmetrical stretching ]CeH of alkenes
2920 Asymmetrical stretching CeH of alkanes
2858 Symmetrical stretching CeH of methylene
1745 Stretching C]O of ester carbonyl functional group in FAME
1240–1030 Stretching CeO of alkoxy esters, ethers and C-O-C
722 Bending of alkenes and overlapping of rocking vibration of methylene ]CeH and e (CH2)n methylene groups of cis disubstituted alkenes and aromatic
688 Out of plane bending ]CeH of cis-disubstituted alkene and aromatics

Fig. 3. UV–vis. absorbance spectra of fuel samples.

Fig. 4a. Thermogravimetric analyzes (TGA) of fuel samples.
Table 7
Crystallizations onset temperature (°C) of fuel samples.
Sample Crystallizations onset temperature (°C)

D100 −8.02
WCOME/SCGOME −1.43
But −15.13
Pen −18.09
Hex −22.52
B10But10D80 −5.20
B10Pen10D80 −5.48
B10Hex10D80 −5.76
B20D80 −3.42
B30D70 −2.54
WCO/SCGO −1.99

4. Results and discussion

4.1. FAC, DU, LCSF, KV, CN, OS, HHV, IV and SN of WCOME/SCGOME

The results of FAC (Table 3) confirmed the existence of fatty acid Fig. 4b. Derivative Thermogravimetric analyzes (DTGA) of fuel samples.
methyl ester with saturated fatty acids having 41% of the total fatty
acid methyl ester content compared to 88.5% of SCGOME [2]. This is
respectively compared to 71.2, 10.4 h and 12.4 g iodine/100 g of
followed by a reasonable amount of both mono and polyunsaturated
SCGOME [2] all of which are satisfactory according to ASTM D6751
fatty acids (29.98% and 29.02% respectively) compared to 10.3% and
standards.
1.2% of SCGOME [2]. DU and LCSF of WCOME/SCGOME were 41.25
and 49.27 compared to 13.9 and 61.76 of SCGOME [2] respectively.
4.2. Blends properties
This excellent fatty acid profile positively affects the final fuel proper-
ties and proves the advantage of feedstock pre-blending strategy. This
Additionally, the results indicate that the advantage of higher al-
profile resulted in a cetane number of 56.64, oxidation stability of
cohols addition to the final fuel properties (Table 4). Compared to pure
6.51 h, HHV of 39.44 MJ/kg and iodine value of 83.71 g iodine/100 g
biodiesel and biodiesel-diesel blends, the three biodiesel-diesel-higher

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Table 8 alcohols blends have closer densities (842.5–843.5 kg/m3) and cold
TGA analysis of fuel samples. filter plugging points (−19 to −22 °C) to D100 (842.5 kg/m3 and
Sample name Heating Temperature Onset Mass loss −26 °C respectively). Furthermore, Fig. 1 shows the effects of tem-
rate (°C/ Ranges (°C) temperature for under perature on densities of all samples. Table 5 summarizes the formulae
min) thermal dry air to predict the density of each sample at a temperature range of about
degradation (°C) (%) 15–40 °C.
WCO/SCGO 10 30–400 240.2 99.7
WCOME/SCGOME 10 95–350 185.3 97.0 4.3. FT–IR spectral studies
But100 10 40–115 78.4 98.1
Hex100 10 50–165 102.4 99.0 FT–IR has been employed as an easy modern analytical technique to
Pen100 10 45–165 87.9 98.0
identify the existing functionals and type of binding linkages, corre-
D100 10 75–290 127.3 97.8
B30D70 10 30–345 206.5 96.4 sponding to various stretching and bending vibrations in the biodiesel
B20D80 10 75–280 167.7 97.3 samples. Oils and esters are noted as fairly strong absorbers in the in-
B10But10D80 10 30–300 166.4 96.3 frared region of the electromagnetic spectrum [59]. Biodiesel is often
B10Hex10D80 10 30–280 170.2 92.4
blended with Euro diesel to make the biodiesel blends [60]. In recent
B10Pen10D80 10 70–280 162.4 96.7
years, the addition of alcohols has been investigated to improve the
B ≡ WCOME/SCGOME. properties of the fuel used in diesel engines. Alcohols contain alkyl and
hydroxyl functional groups. As the number of carbons in the carbon
chain of alcohols increases, it is easier to blend with organic compo-
nents. Thus, biodiesel can be mixed with higher alcohols more easily
than with lower alcohols. Fuel with alcohol additive is called oxyge-
nated fuel, and this type of fuel is thought to contribute positively to-
wards the environment through engine emissions. The previous studies
focused on lower alcohols such as methanol (CH4O) and ethanol
(C2H6O). However, some issues contribute to poor fuel properties and
performance such as lower cetane number, flash point, and heat of
evaporation besides corrosion and miscibility issues [61]. Recently, the
higher alcohols such as propanol (C3H8O), butanol (C4H10O), and
pentanol (C5H12O) are getting more attention in diesel engines [62]. In
this study, WCOME/SCGOME and its blends with D100, But, Pen and
Hex was analyzed to determine the existence of methyl ester and al-
cohols functionals by FT–IR spectra. The peaks of these spectrum were
identified and interpreted and shown in Figs. 2a & 2b. The lists of
functional groups identified were shown in Table 6 [63]. This led to the
identification of functional groups in the WCOME/SCGOME and its
blends with the aid of the structure correlation chart. It can be seen
from Figs. 2a & 2b that the absorbance peak heights of each sample
were taken at nearly 1745 cm−1 where strong absorption of fatty acid
methyl esters exist. The strong characteristic absorption bands for
ν(eOeH) occurs nearly at 3324 cm−1 in But, Pen and Hex and blends
with higher alcohols (B10But10D80, B10Pen10D80, B10Hex10D80) in
different intensities of absorbance. When the biodiesel-diesel samples
were blended with different higher alcohols, the intensities of the ab-
sorbance decreased as the number of carbons increased.
The results confirmed the existence of fatty acid methyl esters
(FAME) and alcohols. The FT–IR spectrum for the samples revealed the
functional groups with their characteristics bands especially for ν (eC]
O), ν (eCH2)n, ν(eCeO), ν(C]C) and ν(CeH) in the spectrum. The
peaks for the blends show variations at nearly about 1745 and between
1240 and 1030 cm−1 which all are responsible to ν (eC]O) and ν
(eCeO) functionals respectively. The peak intensities vary according to
the biodiesel ratio. These peaks increase with the concentration of
biodiesel in each blended sample. Variations in the intensities from 722
to 688 cm−1indicate the existence of (]CeH) bending; cis-dis-
ubstituted alkenes and aromatic functionals. The intensities of peaks at
2949 cm−1, 2920 cm−1 and 2858 cm−1 are attributed to ν (CeH)alkyl &
alkenes and are found to remain unchanged in each of the blend sample,
which is an indication of the existence of D100 [64].

4.4. Uv–visible absorption studies

Fig. 3 shows a typical absorbance curves forD100, But, Pen, Hex,

WCO/SCGO, WCOME/SCGOME and the blends (B30D70, B20D80,
Fig. 5a. 1H NMR spectra of D100, WCOME/SCGOME, B20D80 and B30D70. B10But10D80, B10Hex10D80 and B10Pen10D80) in the range of

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A.E. Atabani, et al. Fuel 244 (2019) 419–430

Fig. 5b. 1H NMR spectra of D100, WCOME/SCGOME, WCO/SCGO, But, Pen, Hex, D80B10But10, D80B10Pen10 and D8010Hex10.

600–200 nm on account of INCT (Intra Charge Transfer) (n − π*) well as to study the mode of decomposition of the fuel materials. In
transitions. When the spectra were plotted, the change in suction den- addition, the DSC studies provide the cold flow properties of the fuel
sity can be ignored. The absorbance for all samples also produced very materials as a function of temperature and time; however, these studies
similar absorbance, with no statistically significant differences. It is provide the crystallization phenomenon of the fuel materials.
concluded that the absorbance in this band is not affected by the type of The crystallization onset temperatures of all the samples under N2
alcohol, as the blended biodiesel does not have chemical components atmosphere were studied using DSC and presented in Table 7. The onset
that contribute to significant absorption in this range. temperatures for WCOME/SCGOME, D100, But, Pen and Hex are
−1.43, −8.02, −15.13, −18.09 and −22.52 °C respectively and
4.5. DSC and thermal studies hence biodiesel crystallizes faster than diesel and higher alcohols. The
crystallization onset temperatures of B10But10D80, B10Pen10D80 and
Both the thermal (TGA and DSC) analysis techniques are quick, B10Hex10D80 are −5.20, −5.48 and −5.76 °C respectively, below
sensitive and relatively inexpensive that can be utilized to determine WCOME/SCGOME which signifies the addition of higher alcohols
the boiling point of methyl ester formed and also to check the chemical lowers the crystallization temperature of biodiesel. Addition of diesel
changes that occurs during transesterification reaction. From TGA and and higher alcohols reduces the crystallization of biodiesel [65]. The
DTA studies, the thermograms clearly implies that the composition crystallization onset temperature of B30D70 and B20D80 are −2.54 °C
present in the fuel materials and the formed intermediate compounds or and −3.42 °C respectively, below WCOME/SCGOME which represents
oxidative stabilized compounds during the decomposition pathways as that addition of biodiesel increases the crystallization temperature of

426
A.E. Atabani, et al. Fuel 244 (2019) 419–430

13
Fig. 6a. C NMR spectra of D100, WCOME/SCGOME, B20D80 and B30D70.

diesel. The oxidative stability of all the samples was quantified by between the curves, with small variations of Tonset between the blends.
Thermogravimetric analysis (TGA), which is a technique for char-
acterizing thermal and oxidative stability of a material (compound or 4.6. 1H and 13
C NMR spectral studies
mixture) by measuring changes in its physicochemical properties. These
properties were expressed in terms of weight change as a function of In this study, all the samples were characterized by 1H NMR spec-
increasing temperature. The oxidative stability is a quality indicator troscopy and their spectra are shown in Figs. 5a and 5b. The char-
parameter for esters. Thermogravimetric curves (TGA) show the weight acteristic peaks of methoxy protons δ(eOeCH3) were observed as a
loss in different temperatures and the first derivative of the weight loss singlet at around 3.65, 3.67 and 3.68 ppm for WCOME/SCGOME,
in relation to the temperature curves. B20D80 and B30D70, respectively. These the chemical shifts indicate
TGA/DTGA curves show that oxidative degradation occurred in a the presence of methyl esters in biodiesel. Other observed peaks were
single continuous step in the temperature range 75–240 °C for WCO/ around between 0.87 and 0.90 ppm of the terminal methyl δ (eCH3)
SCGO ester and its blends, shown in Figs. 4a and 4b respectively. In protons [65]. Certain charateristic signals obtained were ascribed to
these temperature ranges, the mass losses occur at levels of 92.4–99.7% protons α- to the methylene carbonyl groups δ (eCH2eC]Oe) at
for WCO/SCGO biodiesel and its blends. The oxidative degradation 1.88–1.96 ppm, at 2.57–2.69 ppm responsible for diallylic methylene
occurred at temperature of 78.4, 87.9, 102.4 and 127.3 °C, for But100, proton δ (eC]CeCH2eC]Ce) and at 4.17 ppm for the protons which
Pen100, Hex100 and D100 respectively. In this temperature range, the are in α- and β-position in glyceryl functionals in WCOME/SCGOME,
mass losses occur at levels of 98.198, 99and 97.8% for But100, Pen100, B20D80 samples.
Hex100 and D100 respectively. The oxidation onset temperatures were A representative spectrum of 13CNMR of all the samples are shown
represented in Table 8. It is possible to observe the great similarity in Fig. 6a and 6b, which shows the characteristic peaks of ester and

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A.E. Atabani, et al. Fuel 244 (2019) 419–430

13
Fig. 6b. C NMR spectra of D100, WCOME/SCGOME, WCO/SCGO, But, Pen, Hex, D80B10But10, D80B10Pen10 and D8010Hex10.

carbonyl δ (eCOOe) and δ (eC]Oe) at around 170 and 50 ppm, re- improves the density and cold flow properties of biodiesel while
spectively. The peaks around 130 and 125 ppm indicate the unsatura- keeping acceptable level for cetane number, flash point and HHV rather
tion in methyl esters. Other peaks at 14 ppm are due to the terminal than lower alcohols. Therefore, this work further shall be further car-
carbon of methyl groups δ (eCH3) and signals at 10–35 ppm are related ried on assessing the performance in compression ignition engines in
to methylene carbons δ (eCH2e) of long carbon chain in FAMEs [66]. the future study.

Appendix A. Supplementary data

5. Conclusion
Supplementary data to this article can be found online at https://
This experimental study aimed at recycling and valorizing the waste doi.org/10.1016/j.fuel.2019.01.169.
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