1 Analyzing the combustion and emissions of a DI diesel engine powered

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2 by primary alcohol (methanol, ethanol, n-butanol)/diesel blend
3 with aluminum nano-additives

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4 Qingshan Chen, Chenfang Wang*, Kun Shao, Yi Liu, Xuefeng Chen, Yejian Qian

5 School of Automotive and Transportation Engineering, Hefei University of Technology, No.93 Tunxi Road,

6 Hefei, 230009, China

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7 *Corresponding author. Chenfang Wang

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8 E-mail and Postal addresses:

9 wang@hfut.edu.cn (C.-F. Wang); School of Automotive and Transportation Engineering, Hefei University
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10 of Technology, No.93 Tunxi Road, Hefei, 230009, PR China
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11 Abstract: The study investigates the effects of the primary alcohol (methanol, ethanol, n-butanol) and

12 aluminum (Al2O3) nano-additive on combustion and emission characteristics of a direct injection diesel

13 engine at 30% (low) and 80% (high) engine loads of a constant engine speed. The alcohol/diesel
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14 nanofuels were made by adding Al2O3 nanoparticles (25, 100 ppm) into the alcohol/diesel blend (the

same oxygen content level) with ultrasonic mixing and surfactant assistance. The results revealed that
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15

16 an extension in the ignition delay was induced by the substitution of primary alcohol fuel, among

17 which methanol showed the most apparent regardless of engine load. Under high load, the addition of
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18 methanol in diesel aroused the most obvious promotion effects on peak heat release rate (CGPmax) and

19 peak cylinder gas pressure (HRRmax), while under low load, the addition of n-butanol had the most
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20 obvious promotion effect. The addition of Al2O3 nanoparticles to the alcohol/diesel blend significantly

21 improved the combustion process, with the results of decreased ignition delay, increased CGPmax and
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22 HRRmax, and shortened combustion duration, especially for the cases in high nanoparticles dosage (with

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23 a few exceptions). Under both loading conditions, the addition of methanol led to the least emissions

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24 of CO, NOX, and smoke opacity among the three alcohol fuels, while HC emissions presented just the

25 opposite trends. Compared to pure diesel fuel, the engine powered by alcohol/diesel nanofuels emitted

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26 less CO, HC, and smoke emissions with a reduction amplitude of 36.2-77.8%, -8.8-10.7%, and 24.2-

27 55.6%, respectively. However, Al2O3 nanoparticles addition brought more NOX emission with the

28 increment of 6.2-17.5%, especially for the methanol/diesel nanofuels.

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29 Keywords: Al2O3 Nanoparticles; Alcohols; Diesel Engine; Combustion; Emissions

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30 1. Introduction

31 In recent years, due to the shortage of oil supply and serious environmental pollution, more and
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32 more researchers are interested in the field of clean and renewable alternative fuels powered by internal
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33 combustion engines (ICEs) [1-3]. With the advantages of abundant output, higher oxygen content,

34 liquid at atmospheric temperature and pressure, and good economy, alcohol fuels have been considered

35 to be one of the most promising alternative fuels [4-6]. Among these, methanol, ethanol, and n-butanol
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36 as the low carbon alcohols, have been widely studied by researchers in recent years and are being

applied in the market in China. These three alcohol fuels can be easily employed in spark-ignition
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37

38 engines because of their high octane numbers [7, 8]. However, these alcohol fuels cannot be directly

39 used in diesel engines without auxiliary ignition measures, mainly due to their low viscosity and cetane
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40 values. Hence, they have been mostly employed in diesel engines with direct mixing [9-11] and dual-

41 fuel mode (port injection and direct injection) [4, 12, 13]. By comparison, direct blending with diesel
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42 fuel is a desired method for diesel engines because few modifications to the existing engines are

43 required. Studies have shown that the alcohol blending in diesel can optimize in-cylinder combustion,
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44 improve engine combustion thermal efficiency (BTE), and reduce NOX and PM emissions, but it will

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45 result in increased HC and CO emissions [4, 6, 13-20].

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46 In recent years, nanoparticle materials technology has made great progress, and nanoparticle

47 additive is widely popular in the field of ICEs because of their excellent physicochemical properties

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48 [5, 21]. Researchers have applied nanoparticles to internal combustion engines as fuel additives with

49 numerous encouraging results. Berner et al. [22] pointed out that the use of metal nanopowders (such

50 as aluminum, magnesium, Al/Mg alloy, boron, zirconium, titanium, etc) not only contributed to the

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51 effective mixing of components but also made them in close contact with each other, promoting the

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52 diffusion of reactants to the surface and increasing their reactivity. The facts revealed from the above

53 study indicated that mixing biodiesel with metal nanopowders had a significant impact on fuel
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54 performance and combustion characteristics. Sajith et al. [23] carried out experiments on a diesel
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55 engine by using jatropha biodiesel with CeO2 nanoparticle additives in the range of 20 to 80 ppm. The

56 results showed that the BTE of the engine shows a general increasing trend with the increase of the

57 nanoparticles content. Compared to neat biodiesel, Kumar et al. [24] reported that the addition of
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58 ferrofluid to Pongamia biodiesel reduced the ignition delay of the fuel, resulting in lower brake specific

fuel consumption (BSFC). In addition, due to the increase in the combustion efficiency, fuel water
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59

60 content, and viscosity, it changed fuel propagation momentum, which may improve combustion

61 efficiency and promote cloud-like atomization of emulsified moisture during the injection. As
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62 observed, with the addition of ferrofluid additives, BSFC of B20-1 (20 vol% Pongamia biodiesel + 80

63 vol% diesel + 1 Vol % ferrofluid) is up to 11.1% lower than pure B20 fuel blend under full load
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64 conditions. Compared with B20, B20-1.5F and B20-0.5F reduced BSFC by 6.7% and 4.8% at full load,

65 respectively. EI-Seesy et al. [25] added the graphene nanoplatelets (GNPs) in the dosages of 25, 50,
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66 75, and 100 mg/L of JB20 (20 vol% Jatropha methyl ester + 80 vol% diesel). These blends were

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67 investigated under various engine loads and speeds. The results presented that adding GNPs at 50-75

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68 mg/L of JB20 can achieve an increase of 25% in BTE and a reduction of 20% in BSFC compared to

69 those of pure JB20. Selvan et al. [26] carried out the experiments to research the emission

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70 characteristics of a direct injection (DI) diesel engine running on diesel-biodiesel-ethanol blends with

71 cerium oxide nanoparticles additive. The experiment shows that cerium oxide can be used as an

72 additive to reduce emissions significantly, such as CO emissions. Among the nanoparticle additives,

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73 nano Al2O3-additive has been more widely studied because of its low cost, excellent catalytic

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74 combustion, and emission reduction performance. Basha et al. [27] mixed Al2O3 nanoparticles in

75 water-diesel emulsion fuel and tested it on a single-cylinder four-stroke diesel engine. They found that
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76 the engine got apparent improved performance, and emitted less HC, NOX, and soot, but more CO.
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77 Shaafi et al. [28] researched the effect of Al2O3 nanoparticles, isopropanol, and ethanol as additives on

78 soybean biodiesel-diesel blended fuel. The results showed that the maximum combustion pressure and

79 the peak heat release rate (HRRmax) increased, and the brake thermal efficiency increased.
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80 The above studies are mainly related to the addition of nanoparticles to biodiesel. It can be seen

that the existing studies rarely focus on the application of nanoparticles to alcohol fuels. In recent
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82 years, alcohol fuels, such as methanol, ethanol, n-butanol, and other alternative fuels, have been studied

83 in an endless way. It is reported that the addition of nanoparticles into methanol-diesel dual fuel or
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84 methanol/diesel blend fuel can obtain good combustion and emission performance in the DI engine [9,

85 15, 29, 30]. Yet, few research achievements have been made on the application of nanomaterials to
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86 alcohols with different chain lengths, and the performance effects of different alcohol nanofluids in

87 internal combustion engines are unknown. In addition, among many metal nanoparticles, alumina
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88 nanoparticles is a versatile catalytic material, which is widely used alone or together with other metals

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89 to enhance the oxidation reaction of CO, volatile organic compounds, and soot particles. Due to its

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90 versatility and sophisticated synthesis technology, the price of Al2O3 nanoparticles is relatively low as

91 fuel additives for internal combustion engines (the price comparison is illustrated in the article [6]). In

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92 view of this, this study will use nano-alumina particles as additives for different alcohol fuels to test

93 the combustion and emission characteristics of the primary alcohol (methanol, ethanol, n-

94 butanol)/diesel blend with nano-Al2O3 additives in internal combustion engines. The research results

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95 are expected to provide theoretical guidance for the application of alcohol alternative fuels and fuel

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96 additives in diesel engines.

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98
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99 2. Materials and methods

100 2.1. Experimental set-up

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101 The experiments are conducted on a four-stroke, water-cooled, single-cylinder, DI diesel engine

102 (ZS1100, China Changzhou Diesel Engine Co. LTD), and the specifications are summarized in Table
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103 1.

104 Table 1
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105 The test engine specifications

Engine specifications
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Engine type Four-stroke

Number of cylinders 1
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Displacement (L) 0.903

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 Compression ratio 17.5

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Bore×Stoke (mm) 100×115

Injection nozzle (mm/number) 0.32/4

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Maximum toque (N·m) 50.6@1760rpm

Rated power (kW) 11.32kW@ 2200rpm

106

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107

108 Fig. 1. Set-up of the experimental arrangement

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109

110
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111

112
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113 Table 2 Resolution and uncertainties of the main measurement apparatuses

Measurement apparatuses Rosolution Uncertainties

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Dynamometer

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 Speed measurement 1 rpm ±0.4%

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Torque measurement 0.01 N·m ±0.2%

Pressure transducer 0.01 MPa ±0.22%

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Gas analyzer

CO measurement 0.01% ˂0.1%

THC measurement 2 ppm ˂0.1%

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NOx measurement 1 ppm ˂0.1%

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Opacity smoke meter 0.1% 0.1%

114 Fig. 1 shows the test bench of the equipment. Engine speed and load were measured and regulated
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115 by an eddy current dynamometer. The piezoelectric signal in the engine combustion process was
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116 obtained by a piezoelectric pressure sensor installed on the cylinder head (6118CF, Kistler), and then

117 transmitted to the combustion analyzer (Kibox 283A, Kistler) for analysis, to obtain the combustion

118 characteristic parameters, i.e. average cylinder gas pressure (CGP), instantaneous heat release rate
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119 (HRR), ignition delay (ID) and combustion duration (CD). To eliminate the effect of cycle-to-cycle
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120 variations, 150 consecutive cycles of in-cylinder pressure were used for combustion analysis in this

121 study. This paper focuses on THC, CO, NOX, and smoke emissions. The first three were obtained by
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122 the gas analyzer (MEXA-584L, HORIBA), and the last was obtained by an opaque smoke meter

123 (Dismoke 4000, AVL). The resolution and uncertainty of the main test instrument used in the
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124 experiment are shown in Table 2. According to the method suggested in [31], the total percentage

125 uncertainty of experimental ωExp is assessed as 0.54%.

126
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127

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128

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129

130

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131 2.2. Experimental methods and fuel preparation

132 Table 3 Physiochemical properties of oxygenated fuels [32]

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Properties Diesel Methanol Ethanol n-Butanol

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Chemical formula C12-C25 CH4O C2H6O C4H10O

Chemical structure er -

Density (g/mL@15℃) 0.83 0.79 0.803 0.810

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Viscosity (mm2/s@40℃) 3.35 0.59 1.08 2.22

Cetane number (CN, Calculated cetane index) 50.2 3 9 25

Boiling point (℃) 188-343 64.8 78.4 117.7

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Flashing point (℃) 78 11 13 35

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Auto-ignition temperature (℃) 235 470 420 345

Heat of evaporation (kJ/kg) 260 1110 900 707

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Lower heating value (LHV, MJ/kg) 42.8 20.3 27 33.1

LBV (m/s) - 52.3 39 -

Octane number (ON) - 110 103 96

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C wt.% 87.4 37.5 52.2 64.9

H wt.% 12.6 12.5 13.0 13.5

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O wt.% 0 50 34.8 21.6

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 Stoichiometric air-fuel ratio 14.5 6.5 9 11.2

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133

134 The engine ran at 1200 rpm with the engine torque of 13.5 and 36 N·M, corresponding to 30 and

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135 80% of the full load, respectively. For each fuel, the injection pressure and timing were kept at about

136 18 MPa and –20◦ crank angle after top dead center, respectively. In this study, the National–VI diesel

137 fuel and three primary alcohol fuels methanol, ethanol and n-butanol (analytical grade,＞99.5% purity)

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138 were employed and Table 3 shows the properties of each fuel. The fuel tested in this paper includes

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139 base diesel (D100), three alcohol/diesel fuels (ADFs), and six alcohol/diesel nanofluid fuels (ANFs).

140 These ADFs kept the same oxygen content of 3.3%, i.e. M7 (7 vol.% methanol mixed with 93 vol.%
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141 diesel fuel), E10 (10 vol.% ethanol mixed with 90 vol.% diesel fuel), and Bu16 (16 vol.% n-butanol
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142 mixed with 84 vol.% diesel fuel). The ANFs were formulated from aluminum nanoparticles and ADF

143 labeled M7Al25, M7Al100, E10Al25, E10Al100, Bu16Al25, and Bu16Al100. In this study, the

144 abbreviations are defined as: M7 with alumina nanoparticles in the dosage of 25 ppm mass proportion
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145 is shorted as M7Al25. Similarly, E10Al25 and Bu16Al100 respectively denote the ANF with 25 and
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146 100ppm alumina nanoparticles added to E10 and Bu16. The primary properties of the alumina

147 nanoparticle additive are presented in Table 4. The aluminum nanoparticle additive used in this study
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148 is the same as that in [9], where its related morphology and chemical test results are presented.

149 The fuel preparation was carried out in the environment of a dust-free and constant temperature
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150 laboratory. During the preparation process, ADF was mixed with 2000 ppm surfactant Triton X100

151 (Sigma Aldrich, cat# 93426 100 mL) for 30 min with the help of mechanical stirrers. Then a certain

152 dose of alumina nanoparticles (25 or 100ppm) was added to the solution for ultrasonic treatment for
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153 30 min to obtain the desired ANF. In this study, six ANFs prepared by this method could maintain no

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154 stratification and turbidity for about one week in the laboratory environment. It is worth noting that

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155 once the content of nanoparticles in ANF exceeds 100ppm, the stability of the prepared nanofuel will

156 be greatly reduced.

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157 Table 4 The nanoparticle additive specification

Average particle Specific surface Bulk density Purity Appearance

Nanoparticles
size (nm) area(m2·g-1) (g·cm-3) (%) (Color)

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Alumina White

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30 160 3.9 3N
(Al2O3)

158 In this work, each test fuel was prepared just before the experiment. A stirrer was built into the
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159 fuel mailbox to ensure the possible stratification of the fuel. Before each exchange of new fuel, the
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160 engine should run for at least half an hour to ensure that the previous residual fuel had been all

161 consumed. At the same time, after an exchange of the new fuel, the test can be started only after

162 continuous observation of engine load and emissions without significant fluctuations, to avoid any
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163 pollution. During the experiment, the coolant temperature and oil temperature were kept at 80±5 ◦C
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164 and 90±5 ◦C, respectively, to ensure repeatability and comparability of measurements. In addition, the

165 exhaust temperature and oil pressure were monitored to ensure the normal state of the engine operation.
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166 3. Results and discussion

167 3.1. Combustion characteristics

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 D100
M7 M7Al25 M7Al100
E10 E10Al25 E10Al100

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Bu16 Bu16Al25 Bu16Al100
70 1200rmp 160
(a)
30% of full load
140

Heat Release Rate (J/℃A)

Cylinder Pressure (bar)
60 120

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100
50
80

40 60

40
30
20

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0
20

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-10 -5 0 5 10 15 20
168 Crank Angle (CA ATDC)

169

D100
M7
E10
Bu16
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M7Al25
E10Al25
Bu16Al25
M7Al100
E10Al100
Bu16Al100
160
80 1200rmp (b)
80% of full load
140

Heat Release Rate (J/℃A)

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Cylinder Pressure (bar)

70
120

60 100

80
50
60
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40
40

30 20
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0
20
-10 -5 0 5 10 15 20
170 Crank Angle (CA ATDC)

171 Fig. 2. Variations of CGP and HRR vs. crank angle.

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172 The cylinder gas pressure (CGP) and heat release rate (HRR) for different test fuels at low and

173 high loading conditions are shown in Fig. 2. It can be seen that all tested fuels present similar HRR
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174 curves, indicating that the fuels have undergone similar combustion processes, namely a premixed

175 combustion stage and a diffusion combustion stage. As observed, the addition of alcohol fuel and/or
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176 aluminum nanoparticles causes significant changes in ignition delay (ID), the peak CGP (CGPmax),

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177 peak HRR (HRR max), and combustion duration (CD).

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19.0
D100
M7 M7Al25 M7Al100
18.5 E10 E10Al25 E10Al100
Bu16 Bu16Al25 Bu16Al100
Ignition delay (°CA) 18.0

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17.5

17.0

16.5

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16.0

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15.5

15.0
30 80

178 Engine Load (%)

179
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Fig. 3. Ignition delay for each fuel with different engine loads.

180 Fig. 3 presents the ignition delay for each test fuel under both loading conditions. The ignition
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181 delay is characterized as the period of injection start and the start of discernible heat release, which

182 usually refers to the crank angle corresponding to 5% of the total heat released. As observed, each
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183 ADF possesses a longer ID than that of D100. The delayed ignition delay can be clarified by the

184 following two reasons. One is because of the considerably high latent vaporization heat (see Table 3)
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185 of the alcohol fuels, which leads to significantly lower the cylinder charge temperature and lessens the

186 precombustion reactions [33]. The other reason is that the alcohol fuel has much lower CN and higher
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187 ON values than those for diesel fuel, which restrains the auto-ignition of the fuel mixture [34-36]. The

188 same reasons can be used to explain the largest ignition delay by methanol addition than the cases of
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189 ethanol and n-butanol addition [4, 37]. With respect to the low loading condition, the high combustion

190 temperature under high load may diminish the above-mentioned cooling and resistance effects and
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191 results in the drop in ID increment. As observed, with the nanoparticles added, the IDs of the ANFs

192 are shorter than those for the ADFs under both engine loads. The reduction in ignition delay presents

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193 more significance at high nanoparticle doses. This is due to its large specific surface area and heat

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194 transfer characteristics, which ensure the formation of a combustible mixture at the early stage of

195 ignition delay [38, 39]. Moreover, the Al2O3 nanoparticles can act as a fuel-borne catalyst, which is

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196 promised to lower the fuel activation energy by decreasing the temperature of fuel molecules’

197 oxidation [40]. As calculated, compared to base diesel, the ignition delay period is cut down by 1.4%

198 for M7Al100, 1.9% for E10Al100 and 2.2% for Bu16Al100 at low load, while by 0.5% for M7Al100,

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199 2.9% for E10Al100 and 3.7% for Bu16Al100 at high load, respectively. The result indicates that the

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200 addition of nano-alumina particles to the alcohol/diesel mixture can obtain a shorter combustion delay

201 period than that of base diesel, and a more significant improvement in the initiation of combustion
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202 occurs in the n-butanol/diesel blend under both loading conditions.

90
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D100
M7 M7Al25 M7Al100
85 E10 E10Al25 E10Al100
Bu16 Bu16Al25 Bu16Al100

80
CGPmax (bar)

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70

65
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60

55

50
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30 80

203 Engine Load (%)

204 Fig. 4. CGPmax for each fuel with different engine loads.
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205
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 90
D100
M7 M7Al25 M7Al100

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85
E10 E10Al25 E10Al100
Bu16 Bu16Al25 Bu16Al100
80

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HRRmax (J/deg) 70

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65

60

55

50

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45

40

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30 80

206 Engine Load (%)

207 Fig. 5. HRRmax for each fuel with different engine loads.

208
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Compared to base diesel, the burning of each alcohol/diesel blend causes an increase in HRRmax

209 and CGPmax under both engine loads (see Fig. 4 and Fig. 5). The reason for this observation could be
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210 aroused from the relative longer IDs under these conditions, during which a more combustible mixture

211 can be formed and the burning rate increases significantly [41, 42]. Moreover, the fuel-borne oxygen
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212 nature of the alcohol fuels also improves the entire combustion process, with the results of shortened

213 combustion durations (described below). As you can see, at low load, due to the strongest cooling
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214 effects along with its lowest heat value, methanol results in the least amount of HRRmax and CGPmax

215 increment, followed by ethanol and butanol. While at a high load, the increase of HRRmax and CGPmax
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216 after adding methanol is the most significant among the three alcohol additives. This founding is

217 probably because methanol has higher oxygen content than ethanol and butanol, which can improve
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218 the in-cylinder oxygen-deficient combustion atmosphere under a high load [4, 20]. In addition, under

219 high load, the influence of methanol's higher vaporization latent heat on temperature is suppressed, but
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220 this property along with the lower density and viscosity (relative to ethanol and butanol) can promote

221 the formation of a more combustible mixture in the combustion process, thus more optimizing the in-

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222 cylinder combustion process. Additionally, the addition of aluminum nanoparticles to each

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223 alcohol/diesel blend significantly improves the combustion process with the result of increased CGPmax,

224 especially for the cases in high nanoparticles dosage. As observed, with aluminum nanoparticle

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225 additive inclusion in methanol/diesel and ethanol/diesel mixture, the HRRmax increases, especially

226 under low load conditions. This demonstrates that under low loading conditions, the addition of

227 nanoparticles to the methanol/diesel and ethanol/diesel mixture encourages the formation of a more

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228 combustible mixture during the combustion delay period. As calculated, the maximum increment of

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229 9.8% and 11.5% can be observed for the M7Al100 and E10Al100 relative to M7 and E10, respectively.

230 Interestingly, the addition of nanoparticles to n-butanol/diesel does not increase HRRmax under low
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231 load. Under high load, the HRRmax increases when 25ppm alumina is added to the three alcohol/diesel
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232 mixtures, while when the addition of nanoparticles increases to 100ppm, the HRRmax decreases slightly.

233 This result may be related to the interaction between the properties of nanoparticles themselves. The

234 large specific surface area of nanoparticles can increase the contact area between air and fuel to form
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235 a more combustible mixture, which may increase the amount of combustible mixture in the combustion

delay period [43, 44], while the excellent thermal conductivity property and fuel borne catalyst
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236

237 performance of nanoparticles can promote faster combustion (i.e. shortened ignition delay) with the

238 reduced formation of combustible mixture gas during the combustion delay period [45, 46]. From the
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239 current result, it may be inferred that the former plays a dominant role under low load, while the latter

240 plays a dominant role under high load.

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 46
D100
M7 M7Al25 M7Al100
44

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Combustion duration (°CA)
E10 E10Al25 E10Al100
Bu16 Bu16Al25 Bu16Al100
42

40

38

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36

34

24

22

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20

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30 80

241 Engine Load (%)

242 Fig. 6. Combustion duration for each fuel with different engine loads.

243
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The crank angle between the ignition timing and CA95 (at which 95% heat has been released) is

244 employed to evaluate the combustion duration (CD). The obtained results of CDs for different fuels
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245 are shown in Fig. 6. In order to meet the requirements of power output at high loads, more fuel needs

246 to be injected, and the duration of combustion increases. It can be seen that adding methanol, ethanol,
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247 and n-butanol can effectively shorten the duration of combustion. This is because the vaporization

248 characteristics and inherent oxygen-containing characteristics of alcohol fuel effectively shorten the
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249 combustion time and promote the propagation of laminar flame [5]. The shorter the burn duration

250 indicates better engine performance, owing to more fuel burned near the top dead center and being
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251 more complete burning [47, 48]. The results show that, compared with the high load, each primary

252 alcohol fuel has a better reduction effect on the combustion duration under a low load. However, under
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253 each engine loading condition, there was little difference in the optimization effect of the three primary

254 alcohol fuels on the combustion duration. By adding nanoparticles to the alcohol/diesel blend, the
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255 engine shows a decreasing trend in the combustion duration, and the decrement increases with the

256 higher nanoparticle addition. There are two reasons for this result. First, the fuel combustion rate can

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257 be enhanced by the catalytic properties and high specific surface area of nanoparticles [43, 44].

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258 Secondly, nanoparticles can be used as oxygen aid to improve the combustion in the fuel-rich zone in

259 the diffusion combustion stage and reduces the combustion duration [49]. Specifically, the addition of

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260 100ppm Al2O3 nanoparticles into methanol, ethanol, and n-butanol decreases the combustion duration

261 by 4.7%, 3.4%, and 2.3% at low load, and 8.6%, 9.2%, and 7.7% at high load, respectively. This

262 suggests that compared with the low load condition, the addition of nanoparticles has a more significant

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263 effect on combustion process optimization under high load. Similar studies [30, 50] also show that the

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264 catalytic effect of nanoparticles shows superior performance at high temperatures. Additionally,

265 compared with the methanol and ethanol, the combination of nanoparticles and n-butanol has a
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266 relatively weak optimization effect on the combustion process under two loads, owing to the no
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267 significantly reduced combustion duration with n-butanol/diesel nanofluids with respect to

268 methanol/diesel and ethanol/diesel nanofluids.

269 3.2 Emission characteristics

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270 3.2.1 CO emissions

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 1.2
D100
M7 M7Al25 M7Al100

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E10 E10Al25 E10Al100
1.0 Bu16 Bu16Al25 Bu16Al100

CO Emissions (vol%)
0.8

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0.6

0.4

0.1

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0.0
30 80

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271 Engine Load (%)

272 Fig. 7. CO emissions for each fuel with different engine loads.

273 Fig. 7 shows the CO emission from the combustion of different fuels under both engine loads. CO
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274 emission is the product of fuel incomplete combustion and it’s largely governed by factors such as
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275 temperature in the ignition chamber, fuel physical and concoction properties, the proportion of air and

276 fuel, and the measure of time accessible for complete burning [47]. As shown, for each test fuel, the

277 CO emission rises with the rise in engine load. It is supposed to be the fact that the drop in air-fuel
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278 ratio at high load causes more CO emission. Furthermore, with the addition of alcohol fuel, it shows a

steady decrease in the amount of CO emission. This finding can be interpreted as the presence of
tn

279

280 oxygen content in the alcohol fuels, which could effectively reduce the local injection rich zone

281 (mainly forming CO), and improve the post-flame oxidation of CO during the late combustion process
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282 [51]. The methanol/diesel mixture produces the lowest CO emission at both loads. This finding can be

283 interpreted as the fact that among the three primary alcohol fuels, methanol has the highest oxygen
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284 content. As can be seen from the figure, adding Al2O3 nanoparticles to a diesel/ethanol mixture can

285 reduce CO emission, and with adding amount increasing, CO decreases more significantly. The lower
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286 CO emission with nanoparticles-added blend may be ascribed to the following three aspects. First, the

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4122891
287 catalytic effect of nanoparticles can provide oxygen molecules that can facilitate converting CO

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288 molecules into CO2 molecules. Secondly, the interaction of nanoparticles may break fuel uniformity

289 during the fuel injection process, along with the raised chemical reactivity by the large surface-contact

iew
290 areas of nanoparticles to improve air-fuel mixing and combustion [24, 52]. Thirdly, the improvement

291 of cylinder gas pressure and combustion temperature caused by the nanoparticles’ addition is also

292 influential factors to bring down CO emissions [53]. In detail, the CO emissions from M7Al100,

v
293 E10Al100, and Bu16Al100 are 66.7%/39.1%, 57.1%/42.7% and 50.0%/26.6% less than that from M7,

re
294 E10, and Bu16 at low/high loads, respectively. The comparative results show that more apparent

295 decreases can be observed at low loading conditions, indicating that the nanoparticles are more
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296 effective to enhance the combustion in the cylinder under low-temperature conditions. Moreover,
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297 based on the data of high and low loading conditions, nano aluminum particles used in methanol can

298 more effectively reduce CO emissions, followed by ethanol and n-butanol.

299 3.2.2 THC emissions

ot

60
tn

D100
M7 M7Al25 M7Al100
E10 E10Al25 E10Al100
50 Bu16 Bu16Al25 Bu16Al100
THC Emissions (ppm)

40
rin

30

20
ep

10

0
Pr

30 80

300 Engine Load (%)

301 Fig. 8. HC emissions for each fuel with different engine loads.

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4122891
302 Fig. 8 shows a representation of total hydrocarbon emission (THC) for different engine loads.

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303 Notably, for each test fuel, hydrocarbon emission increases with engine load, because more fuel needs

304 to be consumed at higher fuel-air ratio conditions. The HC emission for each alcohol/diesel blend is

iew
305 higher than that for the neat diesel. The increased HC emission may be since it tends to form a thinner

306 air-fuel mixture due to the high oxygen content of methanol. The thin air-fuel mixture is not conducive

307 to flame propagation, thus increasing emissions of incompletely burned hydrocarbons [54]. In addition,

v
308 some thin fuel/air mixtures may not burn at all to escape during scavenging [55, 56]. By comparison,

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309 the increase in HC emission for each alcohol/diesel mixture is more pronounced at low load than in

310 the corresponding case in high load. This is because the high vaporization latent heat of alcohol/diesel
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311 mixture will result in lower droplet evaporation efficiency and incomplete combustion near low-
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312 temperature walls, to increase HC emissions at low load [57]. While these effects were weakened at

313 high loading condition. As calculated, the burning of methanol/diesel produces more HC emission than

314 ethanol/diesel and butanol/diesel, which can be probably mainly due to the lowest boiling point (i.e.
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315 the strongest volatility) and low heat value (see Table 3). These may result in more methanol being

discharged from the cylinder during the scavenging phase. As observed, regardless of engine load and
tn

316

317 fuel type, the addition of Al2O3 nanoparticles can decrease HC emissions, and more apparent

318 decrement appears in the case of high nanoparticle concentrations. The reason is that the catalytic
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319 effect and the oxygen buffer effect of Al2O3 nanoparticles enhance more complete combustion [58].

320 In addition, the lower hydrocarbon emissions may be related to the relatively low activation energy of
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321 nanoparticles promoting the combustion of carbon particles in the cylinder wall [44]. Under both

322 loading conditions, the presence of Al2O3 nanoparticles in the alcohol/diesel blend can decrease THC
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323 emission by 19.5%-27.5%, with no significant difference in the alcohol/diesel blend type. Meantime,

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4122891
324 Al2O3 nanoparticles added to methanol/diesel and ethanol/diesel results in more HC emissions than

ed
325 that from pure diesel. This suggests that the addition of Al2O3 nanoparticles to M7 and E10 can mitigate,

326 but not eliminate, the increase in HC emission. However, the n-butanol/diesel mixture of Bu16 added

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327 with nanoparticles has lower HC emissions than pure diesel at both low and high load conditions.

328 3.2.3 NOx emissions

v
2200
D100

re
M7 M7Al25 M7Al100
E10 E10Al25 E10Al100
Bu16 Bu16Al25 Bu16Al100
NOX Emissions (ppm)

2000

1800
er
1200
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1100

1000
30 80
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329 Engine Load (%)

330 Fig. 9. NOX emissions for each fuel with different engine loads.
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331 Nitrogen oxides (NOX) are produced by chemical reactions between nitrogen and oxygen in the

332 air during the high-temperature combustion process, and the main conditions affecting their generation
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333 are the combustion temperature, oxygen content, and high-temperature duration [59]. Figure 9 depicts

334 NOX emissions from diesel fuel and other test fuels for different engine loads. It can be easily revealed
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335 that the NOX emission for each test fuel increases with engine load, because of the increased in-cylinder

336 temperature and combustion duration. As presented, the combustion of M7, E10, and Bu16 results in
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337 slightly lower NOX emissions, i.e. 7.2%, 5.9%, and 1.1% than that of D100 at low engine load. This

338 may be due to the higher latent heat of evaporation and lower LHV of alcohol fuel compared with pure

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4122891
339 diesel fuel, thus promoting the drop in the temperature in the cylinder [60, 61]. Moreover, the increased

ed
340 ignition delay (see Figure 3) facilitates more fuel burning in the premixed combustion phase to shorten

341 the diffused combustion process, during which more NOX emissions can be formed. While at high

iew
342 load, NOX emission for all alcohol/diesel mixtures are higher than that of D100, suggesting that the

343 cooling effect of the alcohol fuels could be weakened in a high-temperature environment. In addition,

344 the superior properties of alcohol fuels, such as low density, low viscosity, and intrinsic oxygen content,

v
345 make it a suitable fuel candidate for promoting optimal air/fuel mix to increase combustion rates [62].

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346 Among the three alcohol fuels, the blending of n-butanol in diesel fuel results in the most NOX emission,

347 followed by ethanol and butanol. The results may be explained by the shortest ignition delay for n-
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348 butanol/diesel may indicate more fuel combusted in the diffused combustion process than
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349 methanol/diesel and ethanol/diesel, leading to the increment in NOX emission. Furthermore, compared

350 to methanol and ethanol, the LHV of n-butanol has the largest LHV, which is most likely to increase

351 in-cylinder temperature, thus promoting NOX generation. As seen, the addition of Al2O3 nanoparticles
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352 in each alcohol fuel increases NOX emission, and the increment increases towards the higher dosage

of nanoparticles for both loading conditions. The addition of aluminum nanoparticles has been reported
tn

353

354 to reduce NOX emission because of its enhanced catalytic activity and scavenging capacity of nitric

355 oxide free radicals [38, 63]. As the results show, despite the oxygen absorption effect, the combined
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356 effect of additional oxygen release and increased contact area of fuel-air mixture may be more

357 significant, which promotes the completion of combustion and increases NOX generation and emission.
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358 In this study, the results show that compared to the alcohol/diesel mode, the maximum increase in NOX

359 emissions observed for M7Al100, E10Al100 and BuAl100 are 14.4%, 13.6%, and 6.9% at low load,
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360 respectively. However, under high load, the increase amplitude of NOX emission is relatively reduced,

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4122891
361 with the magnitude of 9.7%, 7.6%, and 6.8%, respectively. The results demonstrate that the increase

ed
362 in NOX is more significant under low load conditions, where the obvious reduction in HC and CO

363 emissions can be seen (Figures 7 and 8). Moreover, through comparative analysis, it is not hard to

iew
364 observe that, compared to ethanol/diesel and n-butanol/diesel mixture, the addition of Al2O3

365 nanoparticles in methanol/diesel mixture can bring more NOX emissions.

v
366 3.2.4 Smoke opacity emissions

re
40
D100
M7 M7Al25 M7Al100
35 E10 E10Al25 E10Al100
Bu16 Bu16Al25 Bu16Al100

30
er
Smoke (%)

25

20
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3

1
ot

0
30 80

367 Engine Load (%)

tn

368 Fig. 10. Soot emissions for each fuel with different engine loads.

369 Smoke opacity is the percentage of light absorbed into the smoke [64]. Fig. 10 represents the
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370 smoke opacity variations of the test fuels under both loading conditions. It is noted that smoke opacity

371 increases from the low to high engine load. This is due to the amount of fuel injection increasing as
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372 the load rises, resulting in an increase in anoxic regions to amplified smoke emission [65]. Both factors

373 can exacerbate the fuel incomplete combustion, which ultimately leads to an increase in smoke opacity
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374 emissions. As observed, the engine burning alcohol/diesel mixture emits lower smoke than it uses base

375 diesel fuel, which is probably due to the reduction in diesel-burning amount during the diffused

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4122891
376 combustion process [66]. In addition, the intrinsic oxygen property of alcohol fuel increases the

ed
377 diffusion combustion rate and promotes the post-flame oxidation of smoke in the later expansion and

378 exhaust process. Among the alcohol/diesel blends, the methanol/diesel produces the least smoke

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379 opacity emissions under both loading conditions, followed by ethanol/diesel and n-butanol/diesel.

380 There are three ways to explain this phenomenon. First of all, among the three alcohols, methanol has

381 the lowest viscosity, the best fuel atomization effect, and the smallest fuel droplet size, which are

v
382 conducive to reducing the opacity of exhaust gas. The second reason is that methanol has the highest

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383 oxygen content, which accelerates soot oxidation over the combustion process. Finally, methanol has

384 the lowest carbon content than ethanol and n-butanol, which is also supposed to reduce the opacity
er
385 level. As the data presented, under low/high engine load, the addition of methanol can reduce 30.6%
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386 /20.9% soot opacity emissions, followed by 19.4%/15.3% and 2.8%/10.9% reductions for ethanol and

387 n-butanol inclusion. After the addition of Al2O3 nanoparticles, the exhaust smoke emission for each

388 alcohol/diesel nanofuel was significantly reduced, especially for the high levels of Al2O3 nanoparticles
ot

389 addition. According to previous studies, Al2O3 nanoparticle additive has a strong catalytic effect in the

combustion process, which greatly enhances the fuel chemical reaction, thus inhibiting the engine–out
tn

390

391 smoke emission [67, 68]. Especially, under low load, smoke opacity shows a maximum reduction of

392 36.0%, 38.1%, and 37.4% with 100 ppm dosage of Al2O3 in methanol/diesel, ethanol/diesel, and n-
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393 butanol/diesel compared with M7, E10, and Bu16, respectively. While, at high load, less reduction

394 (less than 15%) in smoke opacity for these three alcohol/diesel blends with Al2O3 nanoparticles
ep

395 inclusion. From the experimental data, it can be observed that the addition of nanoparticles can reduce

396 smoke opacity more obviously at low load than the corresponding case at high load. This may be due
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397 to the low cylinder temperature under low load, where the addition of nanoparticles can better optimize

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4122891
398 the fuel evaporation and air-fuel mixing in the cylinder, thus shortening the combustion process and

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399 reducing soot production. This conclusion can be deduced from the results that the optimization of

400 ignition delay and combustion duration (Fig. 3 and Fig. 6) by nanoparticles under low load is more

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401 obvious with respect to the corresponding cases under high load.

402 4. Conclusions

403 In this study, three primary alcohol/diesel blends, i.e. methanol/diesel, ethanol/diesel, n-

v
404 butanol/diesel (keeping the same oxygen content), and their nanofuels with nano-Al2O3 nanoparticles

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405 additive (25 ppm and 100ppm), were employed to analyze the combustion and emission characteristics

406 of a DI diesel engine. According to the experimental results, the main conclusions are as follows:
er
407 (1) The addition of the primary alcohol fuel methanol, ethanol, or n-butanol to diesel arouses a
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408 longer ignition delay, an increase in HRRmax and CGPmax, and a shorter combustion duration.

409 Regardless of engine load, adding methanol to diesel fuel arouses the most apparent initiation delay

410 among these alcohol fuels. The promotion effects on HRRmax and CGPmax present the most obvious for
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411 n-butanol addition under low load and for methanol added at high load, respectively. While there is

little difference in the optimization effect on the combustion duration among the three alcohol additives.
tn

412

413 The addition of aluminum nanoparticles to the alcohol/diesel blend significantly improves the

414 combustion process, with the results of decreased ignition delay, increased CGPmax and HRRmax, and
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415 shortened combustion duration, especially for the cases in high nanoparticles dosage (with a few

416 exceptions). The results suggest that the addition of nano-alumina particles to the alcohol/diesel
ep

417 mixture can obtain a shorter combustion delay period than that of base diesel, and more significant

418 improvement occurs to the n-butanol/diesel blend under both loading conditions. The improvement in
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419 CGPmax and HRRmax under low load was more apparent than that under high load when nanoparticles

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420 and alcohol fuel are added together. Moreover, the addition of aluminum nanoparticles has a more

ed
421 significant effect on combustion process optimization under high load compared with the low load

422 condition.

iew
423 (2) When alcohol fuel is added to diesel, the engine emits less CO, higher HC, and lower smoke

424 opacity emissions under both tested loading conditions. While, NOX emission shows a slightly

425 decreasing trend under low load, but increases at high load. Under both loading conditions, the addition

v
426 of methanol leads to the least emissions of CO, NOX, and smoke opacity among the three alcohol fuels,

re
427 while HC emission shows just the opposite trends. With Al2O3 nanoparticles addition, the engine–out

428 CO, HC and smoke emissions are decreased significantly for all the alcohol/diesel nanofuels,
er
429 especially for the high levels of Al2O3 nanoparticles. Based on the results, aluminum nanoparticles
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430 used in methanol/diesel can more effectively reduce CO emission, followed by ethanol/diesel and n-

431 butanol/diesel. With the nanoparticle addition, HC emission reduces significantly (19.5%-27.5%)

432 regardless of engine loads and alcohol/diesel blend type. It can be observed that the addition of
ot

433 nanoparticles can reduce smoke opacity more obviously at low load than the corresponding case at

high load. Moreover, the addition of Al2O3 nanoparticles in the methanol/diesel mixture can bring
tn

434

435 more NOX emissions with respect to ethanol/diesel and n-butanol/diesel mixture.

436 Acknowledgments
rin

437 The work in this study was financially supported by the Fundamental Research Funds for the

438 Central Universities (Grant No. PA2021KCPY0033), the Science and Technology Major Project of
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439 Anhui Province (Grant No. 202003a05020023), and the Anhui Provincial Natural Science Foundation

440 (Grant No. 1908085ME137).

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441

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4122891
442

ed
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