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Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

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Renewable and Sustainable Energy Reviews


journal homepage: www.elsevier.com/locate/rser

Effect of alcohol blend and fumigation on regulated and unregulated


emissions of IC engines—A review
Meisam Ahmadi Ghadikolaei n
Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong

art ic l e i nf o a b s t r a c t

Article history: In recent years, the effect of alcohols as an alternative fuel on emissions of IC engines has been inves-
Received 9 August 2015 tigated in a lot of experimental works. However there is a lack of a comprehensive review study about
Received in revised form the definition and type of emissions (regulated and unregulated emissions) and alcohols and the
25 October 2015
influence of alcohols on unregulated emissions of IC engines. Therefore, this literature review study is
Accepted 17 December 2015
Available online 8 January 2016
presented. In the current literature review work, two sections are provided. A brief detail of the effect of
alcohols (methanol and ethanol) in blended and fumigation modes on regulated emissions in IC engines
Keywords: is presented in the first section. And the second section (main section of this work) is a comprehensive
IC engines review part of the literatures related to the effect of methanol and ethanol in blended and fumigation
Methanol modes on unregulated emissions in IC engines. In this literature review work, a wide type of IC engines,
Ethanol
such as SI and CI engines and motorcycles were collected with different operation conditions. Different
Blend
percentages of alcohol blend and fumigation were summarized to get informations about the effect of
Fumigation
Regulated and unregulated emissions
alcohol on regulated and unregulated emissions of IC engines. For regulated emissions, it was found that

Abbreviations: °C, degree celsius; mm, micrometer; 1-D, one dimension; AEA, Atomic Energy Authority; AFR, air/fuel ratio; Al, aluminum; ALD, aldehydes; ASTM D 2533,
Standard Test Method for Vapor–Liquid Ratio of Spark-Ignition Engine Fuels; ASTM D 4814, Standard Specification for Automotive Spark-Ignition Engine Fuel; ASTM D 5188,
Standard Test Method for Vapor–Liquid Ratio Temperature Determination of Fuels; B(a)P, benzo(a)pyrene; BALB/c, laboratory-bred strain of the house mouse; BDL, below the
detection limit; BTDC, before top dead center; BTEX, benzene, toluene, ethylbenzene and o-xylene, m/p-xylenes; BTX, benzene, toluene, xylene; Bu, butanol; C1  , chloride;
C10H8, naphthalene; C12H10, acenaphthene; C12H8, acenaphthylene; C13H10, fluorine; C14H10, phenanthrene; C14H30, diesel; C14Hl0, anthracene; C16H10, fluoranthene and
pyrene; C18H12, benzo[a]anthracene and chrysene; C20H12, benzo[j]fluoranthene, benzo[k] fluoranthene, henzo[a]pyrene and henzo[e]pyrene; C22H12, benzo[ghi]perylene
and indeno[1,2,3-c,d]pyrene; C22H14, dibenz[a,h]anthracene; C2H12, benzo[b]fluoranthene; C2H2, ethyne; C2H4, ethene; C2H5OH, ethanol; C2H6O, ethanol; C4H6, 1,3-buta-
diene; C6H6, benzene; C7H16, gasoline and N-heptane; C7H8, toluene; C8H10, xylene; Ca, calcium; CAD, Crankshaft angle degrees; CARB, California Air Resources Board's; CE-
CERT, Center for Environmental Research and Technology; CFR, Code of Federal Regulations; CH3CH2OH, ethanol; CH3OH, methanol; CH4, methane; CI, compression ignition;
CO, carbon monoxide; CO2, carbon dioxide; CR, compression ratio; Cu, copper; DC, direct current; DI, direct injection; DISI, direct injection spark ignition; DI, Drivability
Index; DMCC, diesel/methanol compound combustion system; DME, dimethylether; DMF, dimethylfuran; DNPH, di-nitro-phenyl-hydrazine; DOC, diesel oxidation catalyst;
DOE, Department of Energy; DOHC, double overhead camshafts; DPFs, diesel particulate filters; DPM, diesel particulate matter; E, ethanol; ED95, 95% ethanol and 5% ignition
enhancers; EGR, exhaust gas recirculation; EN228, EU fuel specifications for sulfur content (50 ppm); EPA, Environmental Protection Agency; ETH, ethanol; EtOH, ethanol;
EU, European Union; EUDC, extra-urban driving cycle; FAO, Food and Agriculture Organization; FBP, final boiling point; Fe, iron; FFV, flexible fuel vehicle; FID, flame
ionization detection; ft, foot; FTIR, Fourier transform infrared spectroscopy; FTP, Federal test procedure; g, gram; GC–MS, gas chromatography mass spectrometer; GDI,
gasoline direct injection; GDP, gross domestic product; h, hour; H2, hydrogen gas; HC, hydrocarbon; hp, horse power; HPLC, high performance liquid chromatograph; IARC,
International Agency for Research on Cancer; IBP, initial boiling point; IC, internal combustion; IDI, indirect injection; IEA, International Energy Agency; IHC, individual
hydrocarbons; ILUC, in-direct land use change; IMR, ion molecule reaction; ISAF, International Symposium on Alcohol Fuels; K, Kelvin; km, kilometer; KPa, kilo Pascal; KW,
kilowatt; L, liter; LabVIEW, Laboratory Virtual Instrument Engineering Workbench; lb, pound; LEV, low emission vehicle; LHV, lower heating value; LPG, natural gas and
motorgas/petroleum gas; M, methanol; MEK, methyl ethyl ketone (butanone); MeOH, methanol; MF, methlyfuran; Mg, magnesium; mL, milliliter; mm, millimeter; MMT,
million metric tons; MON, Motor Octane Number; MPa, mega Pascal; MTBE, methyl teriary buthyl ether; MTO, methanol to olefins; MTP, methanol to propylene; MY, model
year; N/D, no data; N2O, dinitrogen oxide; NA, naturally aspirated; Na, sodium; NDIR, Nondispersive Infrared Detection; NEDC, New European Driving Cycle; ng, nano gram;
NH4 þ , ammonium; Nitro, nitrogenate; nm, nanometer; N m, Newton meter; NMHC, non-methane hydrocarbons; NMOG, non-methane organic gases; NO, nitrogen oxide;
NO2  , nitrite; NO2, nitrogen dioxide; NO3,, nitrate; NOX, nitrogen oxides; O3, ozone; OECD, Organization for Economic Co-operation and Development; OEM, original
equipment manufacturer; Oxy, oxygenated; P, phosphorus; PACs, polycyclic aromatic compounds; PAHs, polycyclic aromatic hydrocarbons; PAN, peroxyacetyl nitrate; PDP-
CVS, positive displacement pump-constant volume sampling; PFI, port fuel injection; PM, particulate matter; ppm, parts per million; Psi, pounds per square inch; RFA,
Renewable Fuels Association; RON, research octane number; rpm, revolutions per minute; RVP, Reid vapor pressure; S, sulfur; SEPA, State Environmental Protection
Administration; SEPA, Swedish Environmental Protection Agency; SGC, summer grade commercial; SGDI, spray-guided direct-injection; Si, silicon; SI, spark ignition; SIDI,
spark ignition direct injection; SO2, sulfur dioxide; SO4  2, Sulfate; SOA, secondary organic aerosols; SOF, soluble organic fraction; SULEV, super-ultra-low emission vehicle;
TD, thermal desorbed; TDC, top dead center; THC, total hydrocarbons; TPM, total particulate matter; TWC, three-way catalyst; UDC, urban driving cycles; UK, United
Kingdom; ULP, unleaded petrol; ULSD, ultra-low-sulfur diesel; US, United States; USA, United States of America; USEPA, United States Environmental Protection Agency; V/L,
vapor/liquid; VERL, Vehicle Emissions Research Laboratory; VL, vapor lock; VOCs, volatile organic compounds; Vol%, volume percent; VT, variable temperature; VVT, variable
valve timing; WC, water cooled; Wt, weight; Zn, zinc
n
Tel.: þ 989355087335, þ 852 97193237.
E-mail address: meisam.ahmadi67@yahoo.com

http://dx.doi.org/10.1016/j.rser.2015.12.128
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1441

application of alcohols as alternative fuels in fumigation mode in IC engines led to reduction of NOX and
CO2 in most tests and PM in all cases. However, an increase of CO and HC was observed with using
alcohols in fumigation mode in most cases. It is noticeable that a diverse effect of alcohol application in
blended mode compared to fumigation mode on regulated emissions was recorded in considerable tests
except PM. For unregulated emissions, it was found a reduction of BTEX (benzene, toluene, ethylbenzene
and o-xylene, m/p-xylenes) in blended mode in most cases, polycyclic aromatic hydrocarbons (PAHs) in
blended mode in major experiments and 1,3-butadiene, ethyne and ethene in both modes in all tests
with using alcohols compared to fossil fuels. On the other hand, it was seen an increase of unburned
ethanol and methanol and total carbonyls in both modes in all tests. And, an increase of formaldehyde
and acetaldehyde which are the predominant carbonyls in the exhaust for vehicles was recorded in most
and major experiments, respectively for both modes. In addition, soluble organic fraction (SOF) had an
increase in both modes in major tests. And an increase of benzene, toluene, xylene (BTX) was observed in
fumigation mode in significant tests.
& 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1442
2. Alcohol as a supplementary fuel in IC engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1443
2.1. Physicochemical properties of alcohol as a fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1443
2.2. Fundamental aspects of alcohol chemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1444
2.2.1. Ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1444
2.2.2. Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1446
2.3. Differences of physicochemical characteristics of methanol with ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1449
2.4. Overview of fossil and alcohol fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1450
2.5. Alcohol productions and economics in the world . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1450
2.5.1. Ethanol productions and economics in the world . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1450
2.5.2. Methanol productions and economics in the world . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1450
3. Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1452
3.1. Regulated exhaust emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1452
3.1.1. Particulate matter (PM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1452
3.1.2. Carbon monoxide (CO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1452
3.1.3. Nitrogen oxides (NOX) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1453
3.1.4. Hydrocarbons (HC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1453
3.2. Unregulated exhaust emissions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1453
3.2.1. Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1453
3.2.2. Alkenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1453
3.2.3. Alkyl nitrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1453
3.2.4. Monoaromatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1454
3.2.5. Particulate emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1454
3.2.6. Peroxvacetyl nitrate (PAN). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1454
3.2.7. Polycyclic aromatic hydrocarbons (PAHs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1454
3.2.8. Nitro-PAHs and Oxy-PAHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1455
3.2.9. Carbonyl compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1455
3.2.10. Nitrogen dioxide, (NO2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1456
3.2.11. Quinones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1456
3.2.12. Sulfur dioxide (SO2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1456
3.2.13. Metal oxides and metallic PM. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1456
3.2.14. Nitrous oxide (N2O) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1456
3.2.15. Dioxins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1456
4. Results of regulated emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1462
5. Results of unregulated emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1462
5.1. G. Karavalakis and co-workers (2014) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1462
5.1.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1462
5.1.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1462
5.1.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1462
5.1.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1464
5.2. Ch. Wang (2014) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1464
5.2.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1464
5.2.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1465
5.2.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1466
5.2.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1466
5.3. Li and co-workers (2014) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1466
5.3.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1466
5.3.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1466
5.3.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1467
5.3.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1468
5.4. G. Karavalakis and co-workers (2012) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1468
5.4.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1468
1442 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

5.4.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1468


5.4.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1468
5.4.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1470
5.5. H.H. Yang and co-workers (2012) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1470
5.5.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1470
5.5.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1470
5.5.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1471
5.5.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1471
5.6. H. Zhao and co-workers (2011). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1471
5.6.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1471
5.6.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1472
5.6.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1472
5.6.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1472
5.7. Z.H. Zhang and co-workers (2010) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1473
5.7.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1473
5.7.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1473
5.7.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1474
5.7.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1475
5.8. Z.H. Zhang and co-workers (2010) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1475
5.8.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1475
5.8.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1475
5.8.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1476
5.8.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1477
5.9. C.S. Cheung and co-workers (2009) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1477
5.9.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1477
5.9.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1477
5.9.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1478
5.9.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1480
5.10. C.S. Cheung and co-workers (2008) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1480
5.10.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1480
5.10.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1480
5.10.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1480
5.10.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1481
5.11. M. Henke and co-workers (2005) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1482
5.11.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1482
5.11.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1482
5.11.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1482
5.11.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1483
5.12. P.M. Merritt and co-workers (2005) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1483
5.12.1. Test experimental setup and fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1483
5.12.2. Emissions testing and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1485
5.12.3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1485
5.12.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1487
5.13. Overview of researchers’ works since 2004 to 1983 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1487
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1491
6.1. Regulated emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1491
6.2. Unregulated emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1491
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1491
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1491

1. Introduction promising alternative fuels due to its storage facility, availability


and handling. High pressure is required to use biogas for auto-
The need for air quality improvements and the current cost of mobile. Again leakage from biogas may cause problem. Biodiesel
crude oil demands alternative fuels for automobiles/IC engines. from edible vegetable oil may cause the dearth situation to supply
The past and the present day civilization are closely interwoven of food for population. The use of non-edible oil as biodiesel
with energy and in future, our existence will be even more sources requires a large-scale cultivation that may cause decrease
dependent upon it [1]. Moreover, the sources of fossil fuel are in food crops [5]. The greatest task today is to exploit the non-
dwindling day by day. According to an estimate, the fossil fuel conventional energy resources for power generation. Alternative
reserves will continue until 41 years for oil, 63 years for natural gas fuels are also called non-conventional fuels. Alternative fuels can
and 218 years for coal [2–4]. The increasing industrialization and be used with the present day petrol/diesel internal combustion
motorization of the world has led to dearth situation in the field of engines with very little or no modification [1]. The development of
energy supply. Again the price of petroleum oil is becoming higher alternative fuels to reduce automotive emissions and provide
on daily basis. These pose a challenge to availability of fossil fuel. energy independence is becoming more important, especially
At these circumstances, demand of alternative biofuels is following the increased public attention on energy security and
increasing as a substitute of fossil fuel in transportation sector for environmental pollution [6]. Alcohols such as Ethanol and
energy security issues. Among the biofuels such as biogas, bioal- Methanol can be used as an alternative fuel in various gasoline
cohol and biodiesel, alcohol seems to be the most attractive and engines [7,8]. In Brazil, Ethanol has been accepted as an alternative
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1443

fuel for the last 35 years [9,10]. In 1970, Methanol was used as a processes are required to ensure the consistent production of
fuel during the oil crisis. In 1980 and 1990 the blending of diesel and gasoline from petroleum fuel [18]. Moreover in recent
Methanol with petrol was also used in different European coun- years concern about environmental pollution has been increased.
tries. Both alcohols (Ethanol and Methanol) will be used as alter- Therefore, alcohol fuels are attracting attention worldwide as
native fuels in pure form or in the form of blending with con- supplementary fuel [5].
ventional fuels in future to reduce the demand for conventional The use of alcohol blended gasoline and neat fuel alcohols as
fuels [11,12]. substitutes for neat gasoline have become matters of interest in
Alcohol fuels can also be used with diesel fuel in different duel many countries. The International Energy Agency (IEA), estab-
fuel operation techniques. The most used methods are blending lished in 1974, follows the development, and data and other
and fumigation. In blending method, alcohol fuels are mixed with experience from various trials have been presented and discussed
diesel fuel before injecting inside the cylinder. To stabilize the at symposia organized by the International Symposium on Alcohol
miscibility of blending alcohol with diesel fuel extra additives are Fuels (ISAF). The first ISAF-symposium was organized in Stock-
required. Hence there is a limitation on amount of alcohol which holm 1978 and since then a symposium has been organized every
can be used for blending operation. Alcohol fumigation has been 2–4 years [19].
defined simply as the introduction of alcohol fuel into the intake The number of models and types of alternative fuel vehicles
air upstream of the manifold either by spraying, carbureting or produced by manufacturers has varied considerably over the last
injecting. This method of introduction has the advantage of pro- 22 years (Fig. 1). In 1991, there were a total of 19 models available
viding a portion of the total fuel supply premixed with the intake that did not run on gasoline, 17 of which were diesel. In 2011 the
air thus improving air utilization. number of models began to surge, rising to 175 models by 2013
This method requires minor modification of engine which is and representing seven different fuel types. E85 (85% ethanol, 15%
done by adding low pressure fuel injector, separate fuel tank, lines gasoline) flex-fuel vehicles accounted for the majority of new
and controls [13,14] but allows a large percentage of alcohol fuels models available since 2010, although diesel and propane models
to be used in engine operation since no additives are required for contributed as well. But production of methanol vehicles was
stabilizing the miscibility of alcohol and diesel fuel [14,15]. As a stopped in 1997. In addition, Fig. 2 represents the Alternative Fuel
result, the efficiency of engine will be better in fumigation mode Vehicles in Use from 1995 to 2011.
[5].
This literature review study aims to investigate the definition
2.1. Physicochemical properties of alcohol as a fuel
and type of emissions (regulated and unregulated emissions) and
alcohols and the influence of alcohol on emissions of IC engines. In
Alcohol fuels such as ethanol and methanol are viable as
the current literature review, two sections are provided. A brief
alternative fuels for IC engines. The characteristics are:
detail of the effect of alcohols (methanol and ethanol) in blended
and fumigation modes on regulated emissions in IC engines is
presented at the first section. And the second section (which is
main section of this work) is a comprehensive review part of the
literatures related to the effect of methanol and ethanol in blended
and fumigation modes on unregulated emissions in IC engines. In
this literature review work, a wide type of IC engines, such as SI
and CI engines and motorcycles are collected with different
operation conditions. Different percentages of alcohol blend and
fumigation are summarized to get informations about the effect of
alcohols on regulated and unregulated emissions.

2. Alcohol as a supplementary fuel in IC engines

Alcohol is a form of renewable energy which can be produced


from carbon based agriculture feed stocks, local grown crops and
even waste products including waste paper, tree trimmings and
grass [16]. Sugarcane residue is another renewable energy source
of alcohol production [17]. In recent years, an increasing trend of
alcohol fuel production from renewable sources has been found
globally [5]. Alcohol is defined by the presence of a hydroxyl group Fig. 1. Number of vehicle models that run on fuels other than gasoline, 1991–2013
(–OH) attached to one of the carbon atoms. The use of alcohol fuels [20].
in internal combustion engine is not new. These fuels have been
used intermittently in internal combustion engine since their
invention. The first commercial use of ethanol as fuel started when
the automobile company Ford designed Henry Ford's Model T to
use corn alcohol, called ethanol in 1908. Ethanol became estab-
lished as an alternative fuel in 1970s due to oil crisis [13]. However,
fossil fuel has been the predominant transportation fuel since the
invention period of automotive engines due to the ease of opera-
tion for engine and availability of supply. But compared to alcohol
fuels, fossil fuels have some disadvantages as an automotive fuel.
Petroleum fuel has lower octane number and emits much more
toxic emission than alcohol fuels. Due to having much more
physical and chemical divers than alcohol, complex refining Fig. 2. Alternative fuel vehicles in use, 1995–2011 [20].
1444 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

 Alcohol has low viscosity than diesel fuel which makes the  Be used (and already is on a wide scale) as an oxygenate in
alcohol easily to be injected and atomized and mixed with air. gasoline.
 Due to having high oxygen content, high stoichiometric air–fuel  Create new jobs in the country related to its production [19].
ratio, high hydrogen–carbon ratio and low sulfur content,
alcohol emits less emission. At least five major reasons for blending ethanol in gasoline are
 Since alcohol has higher heat of vaporization, which results in discussed, including the following advantages of using ethanol as
cooling effect in the intake process and compression stroke. As a an alternative fuel:
result the volumetric efficiency of the engine is increased and
the required amount of the work input is reduced in the com-  Reduction of net carbon dioxide emissions, to mitigate global
pression stroke. warming.
 Alcohol has high laminar flame propagation speed, which may  The need to replace petroleum fuels with a renewable fuel.
complete the combustion process earlier. This improves engine  The need (especially in the US) to improve the air quality in
thermal efficiency [21,22]. non-attainment areas, i.e. areas of the country where air
pollution levels persistently exceed the national ambient air
Alcohol fuels such as ethanol and methanol have the same quality standards.
physical properties as that of petroleum fuels. The physical prop-  The need to reduce the dependence on imported fuels [19].
erties of alcohol fuels in comparison to gasoline and diesel fuels
are given in Table 1. Disadvantages of ethanol as a fuel are the following:

2.2. Fundamental aspects of alcohol chemistry  Ethanol has a lower heat of combustion (per mole, per unit of
volume, and per unit of mass) than petroleum.
2.2.1. Ethanol  Large amounts of arable land are required to produce the crops
Ethanol, in particular, is a biomass based renewable fuel (bio- required to obtain ethanol, leading to problems such as soil
ethanol), which can be produced, relatively easily and with low erosion, deforestation, fertilizer run-off and salinity.
cost, by alcoholic fermentation of sugar from vegetable materials,  Major environmental problems would arise out of the disposal
such as corn, sugar cane, sugar beets, barley, and from (non-food) of waste fermentation liquors.
agricultural residues such as straw, feedstock and waste woods  Typical current engines would require modification to use high
[18,27,28]. The first generation bio-ethanol is made from high end concentrations of ethanol [32].
stocks such as sugar cane, wheat, corn, etc., and is highly con-
troversial, because of its consumption of food supplies. The second 2.2.1.1. Usage of ethanol in blended and fumigation modes in IC
generation bio-ethanol is produced from low end stocks such as engines. Ethanol is considered primarily a good spark ignition
grass, wood chips, and agricultural wastes, therefore proving to be engine fuel, Because of its high octane number. Nonetheless, it has
less controversial [29]. been considered also a suitable fuel for compression ignition
Ethanol also is known as absolute alcohol, alcohol, cologne engines, mainly in the form of blends with diesel fuel [18,27,33–
spirit, drinking alcohol, ethane monoxide, ethylic alcohol, EtOH, 35], although investigations with pure ethanol (or methanol) have
ethyl alcohol, ethyl hydrate, ethyl hydroxide, ethylol, grain alcohol, been conducted too [36,37]. For the latter case, cetane improvers
hydroxyethane and methylcarbinol [30]. and/or glow plugs were implemented combined with an increase
Ethanol is isomeric with dimethylether (DME) and both etha- in the engine compression ratio to facilitate ignition, particularly
nol and DME can be expressed by the chemical formula C2H6O, during cold starting. Another successful method for using alcohols
C2H5OH or CH3CH2OH. Although that has the same physical for- in diesel engines is fumigation. In this technique, alcohol is ato-
mula, the thermodynamic behavior of ethanol differs significantly mized in the engine's intake air either by carburetion or injection.
from that of DME on account of its stronger molecular association Diesel fuel is directly injected into the cylinder and the combined
via hydrogen bonds [31]. air–alcohol/diesel mixture is auto-ignited, with diesel fuel con-
As a fuel, ethanol has advantages and disadvantages over fuels sumption being reduced by the energy of the alcohol in the intake
such as gasoline and diesel fuel. air. This procedure, however, requires separate fuel systems for the
The advantages of ethanol are that it can: diesel and ethanol fuel. Additionally, the amount of alcohol used is
practically limited by the amount that can be vaporized into the
 Provide a viable alternative to reduce the greenhouse effect. intake air. As a result, this approach seems more feasible as an
 Be produced domestically, thereby reducing dependence on engine retrofit, where total energy substitution is not the primary
imported petroleum. objective [18,38]. However, unlike gasoline or diesel fuel, the
 Be easily mixed with gasoline. vapors of ethanol above the liquid fuel in the fuel-tank are usually
combustible at ambient temperatures, posing a risk of an explo-
Table 1 sion particularly during refueling [31].
Comparison of various propetrties of primary alcohol fuels with gasoline and diesel The use of ethanol as substitute for gasoline gained consider-
[23–26]. able interest, mostly in the US (corn-based ethanol) and Brazil
Fuel Methanol Ethanol Gasoline Diesel
(sugar cane-based ethanol), following the global fuel crisis in the
1970s, although early applications originate from the 1930s
Formula CH3OH CH3CH2OH C7H16 C14H30 [18,27]. The initial investigations into the use of ethanol in diesel
Molecular weight (g/mol) 32.04 46.07 100.2 198.4 engines, on the other hand, were initiated in South Africa in the
Density (g/cm3) 0.792 0.785 0.737 0.856
1970s, and continued in Germany and the US during the 1980s.
Normal boiling point (°C) 64 78 38-204 125–400
LHV (kJ/cm3) 15.82 21.09 32.05 35.66 Most of these works related to the use of in-farm equipment
LHV (kJ/g) 19.99 26.87 43.47 41.66 (tractors and combines) (e.g. [39]) and employed an ethanol/diesel
Exergy (MJ/1) 17.8 23.1 32.84 33.32 fuel blend. The main benefit from the use of ethanol during
Exergy (MJ/kg) 22.36 29.4 47.46 46.94 (steady-state) diesel engine operation is the significant reduction
Carbon content (wt%) 37.5 52.2 85.5 87
Sulfur content (ppm) 0 0 200 250
of PM/smoke, due to the high oxygen content of the fuel blend
[18,27,40–47]. Carbon monoxide emissions have been reported
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1445

lower too, but NOX as well as unburned HC may increase. At the oxygen will vary if the blending volume is fixed to a certain
same time, the specific fuel consumption has been reported volume [19].
usually higher owing to the alcohol's lower calorific value, but at a 2.2.1.2.7. Water tolerance. It is well known that ethanol has
lower percentage compared to the decrease of the calorific value, affinity to water, so appropriate measures must be taken when
hence the brake thermal efficiency is (usually) slightly higher [18]. blending ethanol with gasoline and during the distribution of
Fig. 3 shows the atoms of ethanol in spatial arrangements. And ethanol–gasoline blends. According to the RFA the water tolerance
ethanol production way is shown in Fig. 4. of blended fuels is temperature dependent, i.e. the tolerance is
lower at low temperatures. A 10% ethanol blend in gasoline will
2.2.1.2. Impact of ethanol on the physicochemical properties of tolerate approximately 0.5% water (v/v) at temperatures of 15.5 °C
gasoline. In the US Renewable Fuels Association (RFA) paper the or more, while the water tolerance is 0.3% (v/v) water at
impact of adding ethanol to the base fuel on the physicochemical approximately  12 °C [49].
properties of the fuel was discussed [49]. The properties con- 2.2.1.2.8. Gasoline additives. Various additives may be used in
sidered are fuel volatility, vapor pressure, distillation properties, gasoline, such as detergent deposit additives. For ethanol-blended
calculated drivability index, and vapor lock protection index in six gasoline the RFA recommends that ethanol producing member
classes (according to ASTM D 4814), oxygen content, water toler- companies should "treat their ethanol with a corrosion inhibitor to
ance and gasoline additives. ensure that any final blend is properly treated for corrosion pro-
2.2.1.2.1. Fuel volatility. Adding ethanol to gasoline will increase tection”. The RFA has established recommendations for blending
the volatility, decrease the 50% distillation point (T50), and affect ethanol in gasoline, for storage tanks, for distribution, and at
both the drivability index and vapor lock protection [19]. customer delivery points, for protecting pumps and meters. Many
2.2.1.2.2. Vapor pressure. This is a measure of “front end” vola- of these recommendations are certainly known by suppliers of
tility, and a fuel with extremely high vapor pressure may cause ethanol blended fuels. However one of the recommendations is of
problems with hot start ability, hot drivability and vapor lock [19]. great importance for those filling cars with ethanol blended
2.2.1.2.3. Distillation properties. Ethanol in gasoline will reduce gasoline, namely that: “When first converting to an ethanol pro-
the T50 value of the fuel, which may cause problems with older gram it is advisable to recalibrate meters after 10–14 days to
vehicles in warm weather. It has been shown that later models of ensure that the change of product has not caused any meters to
fuel injected vehicles are less sensitive to a reduction in T50 than over dispense" [49].
older cars [19]. The effects of adding ethanol to gasoline on fuel properties
2.2.1.2.4. Drivability index. The drivability index is based on the have been discussed by Chandra Prakash in a report prepared for
relationship between the distillation temperature of the fuel and Environment Canada [51]. It was noted that inter alia, the advan-
the cold start and warming up parameters of the vehicle. The tage of using ethanol as an enhancer of the octane number of the
following formula can be used to calculate the drivability index blended fuel. As an example the author refers to a comparison
(DI): DI¼ 1.5T10 þ3.0T50 þ1.0T90 [19]. (summarized in Table 4) of ethanol blended gasoline with neat
2.2.1.2.5. Vapor lock protection index. ASTM D 4814 defines six gasoline.
classes of vapor lock production, as shown in Table 2. The author's essential message concerning the octane number
2.2.1.2.6. Oxygen content. The standard for the oxygenate con- was that the high octane rate of ethanol increased the value of the
tent in gasoline is set on a weight basis, as can be seen in Table 3. blended fuel. The author also pointed out that the higher octane
Since there are differences in the density of different grades of number of the blended fuel conferred advantages in terms of fuel
gasoline compared to the density of ethanol the final content of efficiency for later models of vehicles since they were commonly
equipped with knock sensors, which retarded the ignition timing

Table 2
ASTM D 4814 vapor lock protection class requirements [50].

Vapor lock protection class Vapor/Liquid (V/L)a,b

Test temperature (°C) V/L, max

Fig. 3. Atoms of ethanol in spatial arrangement [30]. 1 60 20


2 56 20
3 51 20
4 47 20
5 41 20
6 35 20

a
At 101.3 kPa pressure (760 mm Hg).
b
The mercury confining fluid procedure of test Method D 2533 shall be used
for gasoline–oxygenate blends. Test Method D 5188 may be used for all fuels. The
procedure for estimating temperature–V/L may only be used for gasoline (ASTM D
4814c).

Table 3
Ethanol content and oxygenate content in fuels [49].

Fuel ethanol content (vol%) Fuel oxygen content (wt%)

5.7 2.0
7.7 2.7
10 3.5
Fig. 4. Ethanol production way [48].
1446 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

in the event of knocking. In such cases the fuel would be more As a definitive conclusion from Table 5, it may be suggested
efficiently matched to the engine. The fact that ethanol had a that methanol can be used as a partial substitute of diesel such
lower heating value than gasoline may affect the performance of that its advantages can be well exploited and shortcomings to be
the vehicle, since the presence of an alcohol in gasoline would lean minimized. This is possible by operating diesel engines with dual
out the fuel, resulting in some loss of engine power. According to fuel mode (blend or fumigation) with methanol and diesel.
Prakash's work, this was somewhat offset by the fact that adding In energy deficit countries, Methanol can provide a sustainable
ethanol to gasoline results in a higher volume of combustion solution against petroleum crisis due to the following reasons.
gases, which increased the pressure in the cylinder and thus
increases the power efficiency by 1–2%.  Methanol can be manufactured from a variety of carbon-based
feedstock such as natural gas, coal, and biomass (e.g., wood).
2.2.2. Methanol  Use of methanol would diversify country's fuel supply and
Methanol, also known as Carbinol, Columbian spirits, Hydro- reduce its dependence on imported petroleum.
xymethane, Methyl alcohol, Methyl hydrate, Methyl hydroxide,  Methanol is much less flammable than gasoline and results in
Methylic alcohol, Methylol, Pyroligneous spirit, Wood alcohol, less severe fires when it does ignite. So for fire safety purpose it
Wood naphtha and Wood spirit, is a chemical with the formula is better than petroleum.
CH3OH (often abbreviated MeOH). It is the lowest alcohol with just  Methanol has a higher laminar flame propagation speed, which
one carbon atom, four hydrogen atoms and one oxygen atom. may make combustion process finish earlier and thus may
Fig. 5 shows the atoms of methanol in spatial arrangements. improve engine thermal efficiency [55].
Methanol is an oxygenated fuel. It provides a clean combustion  Methanol is a high-octane fuel that offers excellent acceleration
with negligible carbon footprints. In order to envisage methanol as and vehicle power. Though the latent heat of methanol is
a supplementary diesel engine fuel, it is essential that the physi- higher, measures are not necessary for the mixture preparation
due to lower fraction, while it may increase engine volumetric
cochemical properties of the fuel is to be determined and then
efficiency and thus increase engine power [56].
analyzed [52].
 With economies of scale, methanol could be produced, dis-
Methanol is usually synthesized from natural gas; as for
tributed, and sold to consumers at prices competitive with
hydrogen production, natural gas is ‘reformed’ to produce syngas
petroleum.
and the syngas catalytically converted into methanol. This process
has been in existence for over 40 years [35]. Methanol production
way is shown in Fig. 6.
Producing bio-methanol from biomass requires gasification
(Fig. 7), cleaning of the gas and adjusting the H2/CO/CO2 balance to
achieve a stoichiometric syngas. As the resulting syngas is CO2 rich
there is an opportunity for sequestration. Bio-methanol can be
produced using existing synthesis processes in large volumes. The
only technical limitation has been producing large volumes of high
quality syngas from biomass – now being resolved using advanced
gasification technologies such as CHOREN's Carbo-V process [53].
Fig. 6. Methanol production way [48].
2.2.2.1. Usage of methanol in blended and fumigation modes in IC
engines. Methanol has some advantage which causes to use it as a
supplementary fuel in blend or fumigation modes for IC engines.
Low cetane number, extremely low calorific value, and lower flash
point are its disadvantages for direct diesel engine application.
Table 5 provides a comparative assessment of methanol as a diesel
engine fuel [54].

Table 4
Ethanol and gasoline octane numbers [51].

Property Ethanol Gasoline

RON 102–130 90–100


MON 89–96 80–92
(RON–MON)/2 96–112 85–96
Blending RON 112–120 90–100 Fig. 7. Bio-methanol synthesis from biomass [53].
Blending MON 95–106 80–92

Table 5
Comparative study of methanol as a diesel engine fuel [54].

No. Methanol advantages Methanol shortcomings

1 High stoichiometric fuel air ratio Longer ignition delay


2 High oxygen content, high hydrogen to car- More corrosive
bon ratio and low sulfur content
3 High latent heat of vaporization Lower energy content
4 Reduced soot and smoke Lower flash point
5 Higher cooling, hence less compression Poor combustion
work characteristics
Fig. 5. Atoms of methanol in spatial arrangement [52].
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1447

Due to high octane rating and similarities with gasoline, Fig. 9 shows the effect methanol and other alcohols have on the
methanol has always considered as a good SI engine fuel. But bulk distillation curve of gasoline when added at the 15 wt% level.
of the transport fuel consumed worldwide is diesel. Above all the Methanol (labeled Cl in Fig. 9) shows the largest distillation curve
major contribution to pollution also comes from diesel engines. distortion which is caused by the methanol and its azeotropes
Therefore, substitution of diesel by potential fuels like methanol boiling off first. After about 60% of distilled, almost all the
by any method has more impact on economy and environment methanol is vaporized and the distillation curve reverts back to be
than substitution of gasoline by the same fuel [52]. nearly the same as for straight gasoline.
2.2.2.2.2. Water tolerance. While methanol is soluble in gaso-
2.2.2.2. Impact of methanol on the physicochemical properties of line, the presence of water may cause phase separation (water and
gasoline. Adding methanol to gasoline causes changes in both the methanol separate out of solution). Whether phase separation
physical and chemical properties, primarily an increase in vapor occurs depends on the amount of water and the temperature—
pressure and changed distillation and materials compatibility high water content and low temperatures favor phase separation.
characteristics. These changes in physical and chemical properties Methanol is the worst alcohol in regard to phase separation, which
can have adverse effects on vehicle operation and emissions [57]. is one of the reasons that higher molecular weight alcohols have
These changes and identifies some ways the changes can be been frequently recommended as co-solvents for methanol/gaso-
managed as follows. line blends. Co-solvents ameliorate phase separation, vapor pres-
2.2.2.2.1. Vapor pressure. While the Reid vapor pressure (RVP) sure increase, and materials compatibility problems. The EPA has
of methanol is only 4.6 psi (32 kPa), compared to gasoline that is required co-solvents for all methanol blend waivers for these three
typically in the range of 7–9 psi (48–63 kPa), adding methanol to reasons. For high methanol content fuels such as M85, phase
gasoline causes an increase in vapor pressure. This is because separation is not a problem because of the large capacity of
methanol combines with certain low molecular weight hydro- methanol to absorb water [57].
carbons to form azeotropes. Azeotropes have lower boiling points Fig. 10 shows the water tolerance of a gasoline with various
than the hydrocarbons from which they are made, resulting in an concentrations of methanol. This figure vividly illustrates how
increase in vapor generation at lower temperatures. Fig. 8 illus- methanol addition quickly causes the temperature at which phase
trates this phenomenon which has been documented widely by separation occurs to rise. For example, 10 wt% methanol will
several researchers [58,59]. separate when the blend is cooled to a temperature of only 15°F
Fig. 8 shows that the effect of methanol on gasoline vapor ( 9 °C). At 15 wt% methanol the phase separation temperature
pressure peaks with addition of around 10% methanol by volume, rises to just below freezing. Co-solvents can have a dramatic effect
and decreases with larger additions, decreasing in an almost linear on the water tolerance of gasoline blended with methanol.
fashion to 4.6 psi at 100% methanol. (However, the increase in Fig. 11 shows the impact that adding 5 wt% alcohol co-solvents
vapor pressure varies slightly with each blend of gasoline.) What is can have on the water tolerance of a 10 wt% blend of methanol in
particularly significant when adding methanol to gasoline is the gasoline. The higher alcohols of Fig. 11 significantly improve the
very rapid rise in RVP—the vast majority of the increase occurs by water tolerance of methanol blends.
the time 2–3% methanol is added. This large increase in RVP cre- 2.2.2.2.3. Materials compatibility. Automotive fuel systems con-
ates very large increases in vapor generated, which often over- tain a wide range of elastomeric and metallic components. The
whelm the fuel evaporative system and result in significantly elastomers are used primarily as seals and fuel lines but vehicle
increased evaporative emissions. manufacturers have recently been moving to fuel lines that are non-
Co-solvents can moderate the increase in vapor pressure metallic all the way from the fuel tank to the engine fuel system,
somewhat as illustrated in Fig. 8 for a 50/50 blend of methanol and which greatly increases the amount of wetted area between the
TBA, but the most effective remedy is to decrease the RVP of the
base gasoline. When used with co-solvents, the RVP peak occurs at
around 5% alcohol content.

Fig. 8. The effect of alcohol addition to gasoline RVP [59]. Fig. 9. The effect of alcohol addition to gasoline distillation [58].
1448 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

Fig. 12. Elastomer swell from exposure to gasoline, methanol, and a 10% methanol
blend [59].

Elastomers must not crack, leak, or become permeable to fuel;


if they do, vehicle safety is impaired and/or evaporative emissions
increases will occur. No elastomer is completely unaffected by
exposure to fuel, with changes occurring in volume (swell), tensile
strength, and elongation. The addition of methanol to gasoline
causes changes in elastomers that are difficult to predict. Fig. 12
illustrates testing done on various generic elastomers used in fuel
systems (measuring swell) using two gasoline, neat ethanol, and a
blend of the base gasoline and 10% methanol [59]. In general, neat
methanol caused less swelling of the elastomers than the blend of
10% methanol in gasoline, and in most cases, the 50% aromatic
gasoline caused more swelling than 10% methanol. Only the
fluorocarbon showed more swelling in methanol and the 10%
Fig. 10. The water tolerance of methanol added to gasoline [58].
blend than in either of the gasoline tested [57].
Figs. 13 and 14 show additional test data complementary to the
results in Fig. 12 for polyester urethane and fluorocarbon over the
entire range of methanol blends from 0% to 100% [60]. These data
show that elastomers change continuously with percent methanol
content, with the greatest change often occurring with an inter-
mediate blend. A field trial of 4% and 15% methanol in gasoline in
Norway reported swelling of some fuel lines, though the amount
was not quantified [61]. In a similar field trial of M15 in New
Zealand, problems with fuel lines were observed along with other
fuel system elastomers including carburetor needle valve seats,
fuel tank level floats, and fuel pump diaphragms [62]. The pro-
blems reported in the New Zealand fleet test were judged to be
relatively minor and were easily corrected by replacement with
new parts. Without a control fleet, it is not known whether these
problems represented a significant change or not [57].
These data suggest that the impact of methanol on elastomer
materials is relatively benign compared to high aromatic gasoline.
However, these tests were done using new elastomers and rela-
tively pure fuels. As elastomers age in service, they are less
amenable to change. There are several instances of field problems
caused by changes in fuel properties. For example, the change to
ultra-low sulfur diesel fuel caused numerous fuel system leaks
because the elastomers were adversely affected by a relatively
small change in fuel properties. New versions of the same elas-
tomers worked, illustrating the impact aging can have on fuel
system elastomers. Other confounding factors include
the shape of the elastomer and whether it is attached to a
metal that might be attacked by methanol. Complex-shaped
elastomers may react differently than the uniform elastomer
Fig. 11. The impact of co-solvents on the water tolerance of a 10 wt% blend of shapes used for testing. Methanol fuels of all types can be extre-
methanol in gasoline [58]. mely aggressive toward magnesium and, if they contain dissolved
or separated water, toward aluminum, also [63], Steel and other
elastomers and the fuel. Many fuel tanks are now non-metallic as ferrous metals are usually only slightly affected unless the blend
well for reasons of cost and ability to be molded into complex shapes has a separated water phase, in which case some pitting may
that maximize volume in tight vehicle confines [57]. occur. Additives have been found to be effective in reducing the
corrosive effects of methanol in gasoline (blends of up to 10%) on
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1449

Fig. 13. Polyester urethane compatibility with ethanol and methanol blends
Fig. 14. Fluorocarbon compatibility with ethanol and methanol blends (Gasoline A
(Gasoline A from Fig. 12) [60].
from Fig. 12) [60].

copper, cast iron, steel, and aluminum [64]. Corrosion inside engine adjustments optimized to methanol. In addition, an engine
4-stroke engines can be controlled through the use of properly optimized for high methanol blends can have higher specific power
formulated engine oils [65]. output, creating the opportunity to reduce engine displacement for a
2.2.2.2.4. Oxygen content. Gasoline and diesel fuels produced given application. With both an engine optimized for methanol and
from crude oil are composed entirely of compounds that are reduced engine displacement, significant increases in energy effi-
composed almost entirely of carbon and hydrogen with very small ciency are possible relative to gasoline engines [57].
amounts of nitrogen and sulfur. In contrast, methanol is 50% 2.2.2.2.5. Octane value. Methanol has good octane properties
oxygen with the remainder being carbon and hydrogen. As a compared to gasoline. With a research octane value of 108.6 and a
result, methanol needs less air for complete combustion since the modified motor octane value of 88.6, methanol has sufficient
oxygen in its composition displaces the need for oxygen in the air. octane to allow engines optimized for methanol to have high
The stoichiometric air/fuel ratio for methanol (weight basis) is 6.45 compression ratios with the attendant benefits of improved power
(mass air to mass methanol) compared to about 14.7 for gasoline. and efficiency. When used in blends, the high octane value of
Fig. 15 shows the impact this has on blends of gasoline and methanol can be used to reduce the refining severity of the
methanol. As methanol is added to gasoline, the oxygen content of associated gasoline blend stock, allowing increases in refinery
the blend goes up, but, since the oxygen does not contribute to
output and efficiency [57].
heating value, the volume of fuel needed to generate the same
power increases. (This discussion assumes that the efficiency of
the engine does not change with the amount of methanol, which is 2.3. Differences of physicochemical characteristics of methanol with
reasonable for fixed compression ratio engines.) Thus, a blend of ethanol
10% methanol in gasoline requires approximately 105% of the
volume of straight gasoline to make the same amount of power. If In the complete report [66], Chevron discussed the implications
an engine were capable of operating on 100% methanol, it would of the observation that “Methanol is not Ethanol” in that they had
require twice as much fuel volume compared to an engine running different physicochemical characteristics. According to Chevron:
on straight gasoline [57] Fig. 16.
The preceding discussion assumes the engine is designed for  Blends of gasoline with methanol are more corrosive towards
gasoline but is using methanol blends with gasoline. Engines opti- metals and cause more rapid deterioration of elastomers in the
mized for use of methanol blends where methanol is the pre- fuel system.
dominate component, such as 85% methanol (M85), can be made  Methanol–gasoline blends are not authorized by many manuals
more efficient through use of higher compression ratios and other for vehicle owners.
1450 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

oxygenated gasoline did not cause rusting or corrosion, but


water from the phase separation of gasoline oxygenated with
ethanol will, given time”.

2.4. Overview of fossil and alcohol fuels

Different fossil and alcohol fuels currently existing on the


market as well as fuels that are under development are presented
in Table 6.
Table 7 shows suitable fuels for different vehicle sizes, driving
patterns and combustion types.

2.5. Alcohol productions and economics in the world

2.5.1. Ethanol productions and economics in the world


Fig. 15. Oxygen content and fuel volume ratio for gasoline/methanol blends [57]. The U.S. is the world's largest fuel ethanol producer, accounting
for nearly 60% of global output in 2014. Brazil, which produced
roughly 6.2 billion gallons, was responsible for about 25% of world
production, while the European Union followed with 6%. China
and Canada were other leading producers [71]. Fig. 17, represents
the fuel ethanol production in different countries. There are many
benefits to the economy when building, producing and selling
ethanol in the word. For instance, the production of 14.3 billion
gallons of ethanol in the U.S. in 2014 had substantial economic
impacts, including:

 83,949 direct jobs


 295,265 indirect and induced jobs
 $53 billion contribution to gross domestic product
 $27 billion in household income
 $10 billion in tax revenues [71].

2.5.2. Methanol productions and economics in the world


In 2012, the world methanol capacity utilization rate was just
over 70%. The global methanol supply registered stable positive
growth from 2010 to 2012. In 2012, it stood at more than 62.9
Fig. 16. 2014 Global fuel ethanol production in different countries (country, million million tons. China was an unrivaled methanol manufacturer in
gallons, share of global production) [71].
2012, but the country used its production capacities only at
approximately 60% of their total potential. China is the largest
country of capacity (Fig. 17) and also demand for methanol. Cur-
 The vapor pressure of a methanol–gasoline blend is significantly rently, the major methanol producers are based in the developing
higher than that of a corresponding ethanol–gasoline blend. regions, like the Middle East and Asia-Pacific. Asia-Pacific
 Methanol is toxic. accounted for over half of the global methanol supply volume
In addition, the following performance-related issues have been in 2012.
highlighted by Chevron: Methanol is used to produce acetic acid, formaldehyde, and a
 Compared to neat gasoline, ethanol/gasoline blends need more number of other chemical intermediaries that are utilized to make
heat to evaporate, which can reduce drivability. countless products throughout the global economy—and by
 Blending ethanol in conventional gasoline, if it is not adjusted volume, methanol is one of the top 5 chemical commodities
for such blending may result in a fuel with too high volatility (in shipped around the world each year. The global methanol industry
this context the alcohol's previously mentioned effect on the generates $36 billion in economic activity each year, while creating
VL ¼20 temperature is relevant). over 100,000 jobs around the globe [73].
 Since ethanol increases the volatility of the fuel, adding it has The development of a methanol economy in China which is the
not been a viable option for summer reformulated gasoline. largest methanol producer and user has profound economic and
 Ethanol blended gasoline is not to be mixed with neat gasoline environmental implications. Coal-based methanol production
that has not been adjusted for such blending, since the resulting could provide China with a domestic alternative to imported oil
commingling will result in the RVP of the fuel in the tank and reduce conventional automotive emissions [74]. In addition,
exceeding standard limits. the U.S. economic impacts of methanol are the following:
 Conventional gasoline can dissolve up to 150 ppm water at
21 °C, depending on its aromatics content. An ethanol–gasoline  Domestic methanol plants and production of its derivative
blend with 10% ethanol can dissolve up to 6000–7000 ppm products (methanol fuel cells, building materials, plastics)
water at 21 °C. Phase separation may occur if ethanol blended already provide thousands of valuable high-skilled jobs to the U.
gasoline is transported in pipelines. S. economy.
 Some metal components in the engine fuel system will rust or  Renewable methanol fuel and derivative fuels such as biodiesel
corrode if water or acidic compounds are present in the fuel and dimethyl ether (DME) can help efficiently and economically
system. According to Chevron “additional water dissolved in achieve the U.S. Renewable Fuel Standard.
Table 6
Overview of fossil and alcohol fuels [67].

M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495


Renewable fuel Fuel, commer- Raw material(s) Highlighted emis- Is conversion of the Current limitations for increased Outlook for future use: Limited Current use
cially available sion components engine required in order usage amount of raw material
to use this fuel?

Fossil petrol Crude oil Increased demand from emerging Possibly less use in the future due to All over the world in SI appli-
markets. European legislation (EU Renewable cations; Potential to blend
Energy Directive [68]) to increase use of with different biofuels.
renewable fuels; Continued usage as
blending component in biofuels.
Fossil diesel Crude oil Aromats, PAH, Muta- Increased demand from emerging Possibly less use in the future due to All over the world in Cl
genic, NOX, particles markets. European legislation (EU Renewable applications; Potential to
Energy Directive [68]) to increase use of blend with different biofuels.
renewable fuels; Continued usage as
blending component in biofuels.
Ethanol ED95 E.g. crops/biomass Ultrafine particles, Yes. Minor adjustments Vehicle availability (ED95 only for Questions for Euro VI usage. Norway, Sweden, Finland,
with sugar and/or aldehydes (mainly dedicated vehicles). France, Holland, Poland, Spain,
starch content acetaldehyde) South Africa, Brazil, Thailand,
Australia
E85/E100 E.g. crops/biomass Aldehydes (mainly Yes. Minor adjustments Vehicle availability. Current EU ILUC proposal suggests max EU, USA, China and Brazil
with sugar and/or acetaldehyde) 5% of 1st generation ethanol. (E100) [69]
starch content
Low blends in fos- E.g. crops/biomass None for 0–10% [70] mix- Blending of 410% require vehicle Current EU ILUC proposal EU, USA, South America, Southeast Asia,
sil petrol with sugar and/or ture in petrol; Compatible if modifications. suggests max 5% of 1st gen- China
starch content complying with blending eration ethanol.
requirements in EN228.
Methanol M85/M100 Methane (natural Toxic when handling! Insufficient experience Highly toxic;v Corrosive properties; Major engine modifications required; Limited use (mainly in China),
gas, biogas) steam Aldehydes (mainly Production capacity for biometha- Investment in fueling equipment and blended in petrol and diesel;
reformed coal, formaldehyde) nol; Vehicle availability; up to 3% infrastructure; Safety and health Some provinces in China use
woody biomass methanol is allowed according to concerns. M15 and M85 (blends with
current EU standard (EN228). petrol).

1451
1452 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

Table 7 Table 8
Overview of fossil and alcohol fuels suitable for different vehicles [67]. Sensitivity of the flame ionization detector towards selected compounds relative to
that of the hydrocarbon n-heptane (C7H16), which is set to 1.00 [76].
Fuel Light vehi- Light vehi- Heavy vehi- Heavy vehi-
cles, Cl cles, SI cles, cles, urban Hydrocarbons Alcohols Organic acids
engines engines haulage
Methane 0.97 Methanol 0.23 Formic acid 0.01
Fossil diesel X – X X Ethane 0.97 Ethanol 0.46 Acetic acid 0.24
Fossil petrol – X – –
Ethanol, high blend – X – –
Ethanol, low blend – X – –
in fossil petrol Emission measurements must be carried out as part of the type
ED95 (95% ethanol – – X X
approval of the vehicle according to relevant legislation, for
and 5% ignition
enhancers) example the European regulations (current EU Directive 70/220
Methanol, low – X – – EEG with amendments). There is also a need for emission testing
blend in fossil to generate emission factors for use in emission inventories and air
petrol
quality studies. Characterization of emissions from vehicles is also
essential for research purposes. Emission tests are commonly
carried out according to standard procedures to enable data gen-
erated at different laboratories or during different projects to be
compared. There may also be a need to generate emission factors
for local traffic situations, in which case specific driving patterns
(driving cycles) may have to be followed when testing the vehicles,
depending on the regulations in force [19].
In both the US and Europe, a plethora of new diesel engine
emission control standards has led to an ever changing description
of DPM and its attendant gases and vapors [77]. Since 1992, there
has been a staged introduction of new regulations affecting the
emission of nitrogen oxides, hydrocarbons, and PM in on-road
diesel-powered vehicles. The values presented in Table 9 show
that the allowable emission of DPM has declined steadily in both
Fig. 17. Global methanol production by country, 2012 [72].
passenger cars and commercial vehicles. The emission of hydro-
carbons and nitrogen dioxide in diesel exhaust from passenger and
 In 2010, the U.S. consumed 5.3 million tons estimated to be a commercial vehicles was also projected to decline by more than 5-
$1.4 billion dollar industry. Extrapolated with the Commerce fold for the 12-year period beginning in 1992. The United States
Department's'ripple effect' multiplier for energy industries, the Environmental Protection Agency (USEPA) has developed a similar
total economic impact in the U.S. is $3.5 billion dollars annually set of emission limits that have been promulgated in two separate
at current consumption rates. phases lasting 5 years each. A third tier of regulations was initiated
 Expanded use of methanol as a clean-burning fuel source could in 2010 and is scheduled to end in 2016. The promulgation of these
provide tens of thousands more jobs at various skill levels and increasingly stringent regulations has required engine manu-
billions of dollars additionally in the clean energy economy [75]. facturers to make dramatic changes in the combustion character-
istics of new engines and introduce new pollution control mea-
sures, such as fuel reformulation, diesel particulate filters (DPFs),
3. Emissions and oxidation catalysts [78]. Since these technologies will continue
to be modified and improved to meet future restrictions on DPM
3.1. Regulated exhaust emissions and hydrocarbon emissions, the diesel emissions of today will
undergo further change with the types and quantities of each
The methods used to determine regulated pollutants have been pollutant shifting with time [79].
developed for application to conventional fossil based gasoline and Emissions that are regulated by law [80] are carbon monoxide
diesel fuels. These methods are: chemiluminescense detection for (CO), unburned fuel hydrocarbons (HC), nitrogen oxides (NOX) and,
NOX, nondispersive infrared detection (NDIR) for CO, gravimetric for diesel cars, particles [19]. And today in Europe, the U.S. and
analysis for particulates and flame ionization detection (FID) for Japan (the 3 major regions) there are currently regulated limits for:
HC. The chemical constituents of HC are, by definition, hydro- Particulate Matter (PM), Carbon Monoxide (CO), Nitrogen Oxi-
carbons which consist solely of carbon and hydrogen atoms. des (NOX) and Hydrocarbons (HC).
However, the chemical compounds emitted include compounds
other than pure hydrocarbons in relative abundances that vary 3.1.1. Particulate matter (PM)
depending on the fuel used, so the “HC” signal from the FID tends It can be referred to as diesel particulate matter (DPM) or
to be underestimated. This is because the hydrocarbons and par- total particulate matter (TPM). Diesel PM is a mixture of carbo-
tially oxygenated compounds have different response factors, as naceous soot, as well as other solid and liquid material [81].
widely reported in the scientific literature (Table 8). Consequently,
to make a valid comparison of HC emissions from gasoline and 3.1.2. Carbon monoxide (CO)
ethanol blended gasoline as fuels the comparison must be made Carbon monoxide (CO) is a poisonous, colorless, odorless, and
compound by compound to avoid over- or under-estimations. This tasteless gas. CO is a common industrial hazard resulting from the
requires the development of a method enabling the separate incomplete burning of natural gas and any other material con-
detection of hydrocarbons and alcohols (at least) in exhaust taining carbon such as gasoline, kerosene, oil, propane, coal, or
emissions [19]. wood. Forges, blast furnaces and coke ovens produce CO, but one
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1453

Table 9
European emission standards for nitrogen oxides, hydrocarbons, and PM in diesel exhaust [79].

Tier Date Passenger cars (g/km) Commercial vehicles o 1760 g (g/km) Commercial vehicles 41760 g (g/km)

NOX HCþ NOX DPM NOX HCþ NOX DPM NOX HC þNOX DPM

Euro I July 1992 – 0.97 0.14 – 0.97 0.14 – 1.7 0.25


Euro II Jan. 1996 – 0.7 0.08 – 0.7 0.08 – 1.2 0.17
Euro III Jan. 2000 0.50 0.56 0.05 0.50 0.56 0.05 0.78 0.86 0.10
Euro IV Jan. 2005 0.25 0.30 0.025 0.25 0.30 0.025 0.39 0.46 0.06
Euro V Sep. 2009 0.180 0.230 0.005 0.180 0.230 0.005 0.280 0.350 0.005
Euro VI Sep. 2014 0.080 0.170 0.005 0.080 0.170 0.005 0.125 0.215 0.005

of the most common sources of exposure in the workplace is the


internal combustion engine [82].

3.1.3. Nitrogen oxides (NOX)


Nitrogen oxides (NO and NO2) are formed by the oxidation of
nitrogen from the air in the combustion process. An important
parameter for the formation of nitrogen oxides is the combustion
temperature i.e. increased combustion temperature results in
increased nitrogen oxide emissions. It should be noted that
nitrogen oxides (NOX) are regulated pollutants that are deter-
mined jointly, as the sum of NO and NO2 contents rather than as
individual components [19].

3.1.4. Hydrocarbons (HC)


From a strictly chemical perspective, hydrocarbons consist
solely of the elements carbon and hydrogen. When using gasoline
as fuel in an Otto engine, the unburned fuel hydrocarbons (HC) in
the exhaust consist mainly of unburned gasoline which itself lar-
gely consists of hydrocarbons. However, when using gasoline/ Fig. 18. European emission standards for passenger cars [81].
ethanol blends as fuel the un-combusted fuel constituents include
both unburned gasoline (which consists mainly of hydrocarbons as
noted) and un-combusted ethanol. Thus, the HC emissions mea- to be updated and modified according to future findings is as
sured in the diluted exhaust consist of both hydrocarbons and follows.
ethanol (alcohol). From a legal perspective, HC emissions are
regulated by law, but not ethanol emissions. This means that 3.2.1. Alcohols
reported HC emissions from vehicles fueled with alcohol/gasoline When alcohols are used as blending components in fuel, un-
blends are overestimated, due to the contribution of the alcohol combusted alcohols from the fuel are emitted in the exhaust in
contents in the exhaust emitted from the vehicle, and the larger various amounts. These un-combusted alcohols in the exhaust
the alcohol contents present in the exhaust, the greater the error emissions should be measured since there is a risk that the “HC”
in estimated HC emissions [19]. signal from the FID will be overestimated, leading to estimates of
Fig. 18 details the trend which European emissions regulations
HC emissions from alcohol blended gasoline fuels being higher
have followed during the last 18 years and how they are projected
than they really are [19].
to be for Euro 6 in 2014. It should also be considered that since
Euro 5 there is an additional PM requirement, for a PM total
3.2.2. Alkenes
number limit at 6*1011 km  1 [81].
Alkenes such as ethene, propene and 1,3-butadiene can be
potentially metabolized by endogenous enzymes to reactive
3.2. Unregulated exhaust emissions
metabolites, which have the potential to initiate cancer. For
instance, the compound 1,3-butadiene is metabolized to ethylene
There are several additional unregulated pollutants that have
oxide in both animals and humans [84,85].
been found in Cl engine exhaust, which many of them are at much
According to Schuetzle et al. [86] significant sources of 1,3-
lower concentration levels than the regulated emissions. Indeed,
some represent a part of the complex PM emission whereas others butadiene are the olefins in the fuel. By blending gasoline with
are gas phase species. The US EPA has estimated that more than ethanol the “fuel olefin” content decreases, suggesting that emis-
20,000 individual chemical compounds are emitted from diesel sions of alkenes are reduced when it is used rather than neat
fueled vehicles [83], approximately 500 of which have been gasoline. However, this hypothesis needs to be experimentally
positively/tentatively identified in the scientific literature. This confirmed [19].
means that more than 97% of the estimated compounds emitted
from diesel vehicles are unknown (as are, therefore, their health 3.2.3. Alkyl nitrites
effects) [19]. However, a selection of unregulated exhaust con- Methyl and ethyl nitrite are mutagenic [87,88], hence they are
stituents is considered below that are considered to be important potential carcinogens. Alkyl nitrites are formed from un-combusted
and to have potential health effects on animals and humans, and alcohol reacting with nitrogen oxides (NOX) in exhaust plumes.
thus should be monitored and reduced in exhaust emissions from From vehicles fueled with methanol/gasoline blends and methanol/
automotive sources. The list of such compounds which is expected diesel blends methyl nitrite is formed [89]. Both methyl and ethyl
1454 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

nitrite are formed in exhaust plumes from vehicles fueled with which stated that acetaldehyde is particularly important since it
ethanol–gasoline blends [90]. reacted with NOX, forming PAN in the atmospheric photochemical
system.
3.2.4. Monoaromatics
Monoaromatic compounds emitted from vehicles include 3.2.7. Polycyclic aromatic hydrocarbons (PAHs)
benzene, toluene, ethyl benzene and xylene, which are often col- Polycyclic Aromatic Compounds (PACs) are a numerous group
lectively called BTEX. According to the California Air Resources of mutagenic carcinogenic compounds, of which a subgroup
Board [91] benzene is a known human carcinogen and may cause (Polycyclic Aromatic Hydrocarbons or PAHs), consists of mutagenic
leukemia through occupational exposure [92]. A source of BTEX carcinogenic hydrocarbons [93,94]. Each PAH has a relatively large
emissions from vehicles is the BTEX content of the fuel used,
number of hydrocarbons with two or more condensed aromatic
emitted in the un-combusted fuel constituents. However, BTEX
rings. However, in Sweden are the PAHs phenanthrene, fluor-
can also be pyrosynthesised in the combustion process from the
anthene, pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene,
fuel or lubricating oil constituents [19].
benzo(a)pyrene, indeno(l,2,3-cd)pyrene, dibenz(a,h)anthracene,
3.2.5. Particulate emissions dibenzo(a,l)pyrene, methyl anthracenes/phenanthrenes, retene
Participate emissions are measured on a weight basis i.e. and benzo(ghi)perylene recommended by the Swedish Environ-
through gravimetric determination using a dilution tunnel tech- mental Protection Agency (SEPA) for air monitoring programs in
nique at a diluted exhaust temperature below 52 °C. Exposure to 1999, which published in 2002 [104].
diesel exhausts clearly induces lung tumors in rats. These neo- Fig. 20 shows the priority listed PAHs. Some of compounds
plasms may be caused by the particle fraction of the exhaust shown in Fig. 20 are considered as 'probable human carcinogen'
[93–95]. Due to the findings that TiC2 and carbon black particles, (B2), while some are not listed as 'human carcinogens' (D) [105].
with no genotoxic compounds adsorbed on them (i.e. “clean” The toxicity of these PAH compound is highly dependent on their
particles) can also give rise to lung cancers in rats [96–98] interest molecular structure. Two isomers of PAHs with different structure
in particles per se has increased. Important particle parameters in show quite different toxicity. Therefore EPA has divided these PAH
general are their size, number, surface area and chemical compo-
compounds into different categories [106].
sition. Studies by Heinrich et al. [99] indicated that particle size
was a very important parameter. The Institute of Environmental
Medicine (Karolinska Institute, Sweden) had published a report
which concluded that it was not currently possible to tell if a non-
Naphthalene*
specific particle factor or a direct genotoxic effect of material Acenaphthylene (D) Acenaphthene
C10H8
adsorbed on the particles is responsible for causing lung cancer C12H8 C12H10
[95]. Therefore, the particles emitted should be chemically ana-
lyzed with respect to both their size and numbers [19].

Fluorine (D) Anthracene (D)


3.2.6. Peroxvacetyl nitrate (PAN) C14Hl0
Peroxyacetyl nitrate is a peroxyacyl nitrate. It is a secondary C13H10
Phenanthrene (D)
pollutant present in photochemical smog. It is thermally unstable C14H10
and decomposes into peroxyethanoyl radicals and nitrogen diox-
ide gas. It is a lachrymatory substance. Peroxyacetyl nitrate, or
PAN, is an oxidant more stable than ozone. Hence, it is better
capable of long-range transport than ozone. It serves as a carrier Benzo[a]anthracene
for oxides of nitrogen (NOX) into rural regions and causes ozone Fluoranthene (D) Pyrene (D)
C16H10 C16H10 (B2) C18H12
formation in the global troposphere. The formation of PAN on a
secondary scale becomes an issue when ethanol is used as an
automotive fuel. Fig. 19 shows the chemical structures of Perox-
yacetyl nitrate. In a study by Gaffney et al. [100] field measure-
ments taken in Albuquerque, New Mexico, were used to compare Chrysene (B2) Benzo[b]fluoranthene Benzo[k]
atmospheric levels of peroxyacetyl nitrate (PAN) associated with C18H12 (B2) C2H12 fluoranthene C20H12
the use of different fuels. Levels were measured before and after
introduction of a 10% ethanol gasoline fuel blend ( 499%) and the
cited authors detected increased levels of PAN and aldehydes
during the wintertime.
A study [101] which was more valid during summertime con-
ditions in Porto Alegre, Brazil, indicated that aromatics and alkenes Benzo[j]fluoranthe Henzo[a]pyrene (B2)
have a major role, and acetaldehyde and ethanol minor roles, as ne C20H12 C20H12 Henzo[e]pyrene
precursors to PAN in urban air-in contrast to a report prepared by C20H12
the Orbital Engine Company [102] for Environment Australia,

Indeno[1, 2,3-
c,d]pyrene (B2)
Dibenz[a,h]anthrac Benzo[ghi]perylene C22H12
ene (B2) (D)
C22H14 C22H12
Fig. 20. Priority list PAHs [105]. *—Not included in priority list; D—not listed as to
Fig. 19. Chemical structure of Peroxyacetyl nitrate (PAN) [103]. human carcinogens; B2—probable human carcinogen.
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1455

Table 10 (continued )

Compound Light-duty gasoline Heavy-duty diesel


emission factor (lg/L) emission factor (lg/L)

Gas Particle Gas Particle


Fig. 21. Carbonyl group, aldehyde and ketone [106].
phase phase phase phase

Table 10 4-Biphenylcarboxaldehyde 100


Emission factors for carbonyls in the gas and particle phases of diesel and gasoline
exhaust [126].
Aromatic ketones
Acetaphenone 4 1.2 230 1.8
Compound Light-duty gasoline Heavy-duty diesel
1-Indanone 5.7 75
emission factor (lg/L) emission factor (lg/L)
9-Fluorenone 2.9 0.3 190 24
Benzophenone 1.7 0.7 88 20
Gas Particle Gas Particle
Periiiaphthenone 38 43
phase phase phase phase
Xanthone 5
Aliphatics
Propanal 70 87 160 210 Aromatic dicarbonyl
Butanal 1900 27 8800 500 1,2-Acetylbenzene 1 49
Isobutanal 1.7 21 1,3-Acetylbenzene 7.9 130
Pentanal 770 7.6 2100 170 1,4-Acetylbenzene 2 28
Hexanal 420 3.6 7000 540 Naphthalic anhydride 130
Heptanal 18 13 690 160
Octanol 35 1.2 590 35
Nonanal 390 8.1 140 260
Decanal 110 2.3 860 140
Undecanal 18 380 Det
In recent decades, it is reported that PAHs presents in the diesel
Dodecanal 56 410 59 particulates are one of the main factor, which adversely affect
Tridecanal 17 380 human health. PAHs include various kinds of poly-aromatic com-
Tetradecanal 1600 pounds, which manifest different toxic properties. EPA has listed
16 PAHs as carcinogenic, probable carcinogenic and possible car-
Aliphatic ketones cinogenic and the molecular structure of these is shown in Fig. 20
2-Butanone 54 6 98 [105].
3-Pentanone 0.2 34 6.3
2-Pentanone 28 11
2-Hexanoiie 350 110 3.2.8. Nitro-PAHs and Oxy-PAHs
2-Heptanone 220 5.3 140 Nitro-PAHs are emitted in the atmosphere by primary sources
2-Octanone 3.9 180 [107] or formed by gas phase PAHs reacting with hydroxyl (OH)
2-Nonanone 2.4 740 radicals during the daytime and nitrate (NO3) radicals during the
nighttime, in the presence of NOX [108–110]. Nitro-PAH isomer
Unsaturated aliphatics patterns resent in direct emissions are significantly different from
Acrolein 4.3 0.4 22 140 those resulting from atmospheric reactions, reflecting thus their
Methacrolein 38
formation pathways. During incomplete combustion processes, 1-
Methyl vinyl ketone 2.1 210 310
Crotonaldehyde 2.5 1.5 29 41 nitropyrene (1-NP) and 3-nitrofluoranthene (3-NF), formed by
t-2-Methyl-2-butenal 0.5 electrophilic nitration, are the most abundant compounds found in
3-Methyl-2-butenal 7.5 0.5 83 37 diesel fuel particulate material [107]. Conversely, gas-phase reac-
t-2-Hexanal 3.6 tion pathways involve OH radical attack at the sites of highest
4-Hexen-3-one 1.2 0.3 14 5.7
5-Hexen-2-one 4.9
electron density, with subsequent NO2 addition followed by a loss
of water [107]. The most abundant nitroarenes produced by this
mechanism are 2-nitrofluoranthene (2-NF) and 2-nitropyrene (2-
Cyclic aliphatics
2-Methyl-2-cyclopentenone 0.7 0.1 27
NP) [107].
3-Methyl-2-cyclopentenone 1.6 89 16 Equivalent to the OH reaction, the attack of the NO3 radical
2-Cyclohexenone 2 Det 41 34 forms a fluoranthene–NO3 adduct, followed by the Ortho addition
of NO2 and subsequent loss of HNO3 [107]. This reaction is notably
Aliphatic dicarbonyls selective, forming only 2-NF. In the atmosphere, the gas-phase
Giyoxal 21 7.9 140 170 reactions of PAHs with OH and NO3 radicals form 2-NF, which is
Methyl giyoxal 550 46 4200 1400 the most abundant particle associated nitro-PAH [111,112].
2,3-Butanedione 0.4
Oxygenated PAH compounds (oxy-PAHs) such as aromatic
2,3(& 2,4)-Peixtaixedione Det 3 2.1
2,3-Hexanedione 55 32 3200 1200
ketones, aromatic aldheydes, quinones, and carboxylic acids have
2,5-Hexanedione 23 4.1 290 110 been identified in various environmental samples [113–115]. Oxy-
PAHs are mainly emitted from combustion processes; however,
Aromatic aldehydes
they are also produced by heterogeneous reactions of particulate
Benzaldehyde 9–7 9–5 660 130 associated PAHs with ozone [107,113,116].
o(& m)-Tolualdehyde 11 4.3 210 1.9
p-Tolualdehyde 26 4 180 2.8 3.2.9. Carbonyl compounds
t-Cinnamaldehyde 36
Diesel engines emit large number of different harmful com-
3,4,-Methyl-benzaldehyde 19 100
2-Ethyl-beiizaldehyde 130 pounds and many compounds are still unknown. The term car-
4-Ethyl-benzaldehyde 14 500 bonyl refers to the carbonyl functional group, which is a divalent
1-Naphthaldehyde 9.3 230 group consisting of a carbon atom double-bonded to oxygen.
2-Naphthaldehyde 10 380 Carbonyls are such compounds, which have significant presence in
1456 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

engine exhaust. Most studies have measured carbonyl emissions 3.2.12. Sulfur dioxide (SO2)
by derivatives of 2,4-di-nitro-phenyl-hydrazine (DNPH) [117–121], Sulfur dioxide from sulfur present in the fuel and the lube oil.
Carbonyl emissions lead to formation of secondary organic aero- Previously fuel sulfur levels were/are at high levels ( 4400 ppm).
sols (SOA) by forming oligomers [122], Contribution of carbonyls These levels may still exist in some developing markets. Sulfur
in diesel particles also enhances its responses physiologically dioxide is a precursor of acid rain and atmospheric particulate. The
[123]. Fig. 21 shows the basic structures of carbonyl group and problem of sulfur poisoning has seen much recent attention and
carbonyl compounds such as Aldehydes and Ketones. 17 carbonyl not just because of the direct pollution. Automotive catalysts can
compounds are listed in Table 11. be rendered ineffective (poisoned) by sulfur, as it deactivates the
Aldehydes are a part of the gaseous emission from Cl engines. catalytic sites of the catalyst. This has led to the reduction/elim-
Acetaldehyde and formaldehyde are probable carcinogens that ination of fuel and lube oil sulfur levels by the oil companies and
may also produce other health effects. Aldehydes can be identified legislative authorities [81].
by their O ¼CH at the end of a group R of indetermined length,
formaldehyde is the simplest (CH2O) [124]. 3.2.13. Metal oxides and metallic PM
Carbonyls are emitted in both the gas and particle phases [125]. Several fuel and engine oil additives include metallic com-
As shown in Table 10, the carbonyl levels in the gas phase are often pounds. This results in some metal oxide and elemental emissions,
many times higher than the levels found on PM, and that the mass including metals such as; iron, copper, zinc, cerium, calcium
recovered from diesel-generated particulates is substantially (added to the fuel for PM reduction) and phosphorus [131]. Metal
greater than the amount from gasoline [126]. oxide emissions and small nano-metallic particulate can be toxic
and carcinogenic (most especially nano-particulate) [132].
3.2.10. Nitrogen dioxide, (NO2)
Nitrogen dioxide constitutes a part of the NOX emission (it is 3.2.14. Nitrous oxide (N2O)
more toxic than NO and the other component of NOX) it could be Nitrous oxide (not included in NOX measurements) is a possible
anticipated that in the future NO2 may be regulated individually future concern as it is promoted in some after-treatment systems
[81]. Nitrogen dioxide (NO2) is a compound that plays a role in for use as an oxidant. As a pollutant it is a powerful greenhouse
respiratory diseases, especially those of asthmatics and children gas at 298 times the effect of CO2, though how long it would
[127]. remain as N2O is debatable as it reacts with oxygen to form NO
[133].
3.2.11. Quinones
Quinones are a group of organic compounds that consist of 3.2.15. Dioxins
diketones (carbonyls) which contain oxygen and are present in Dioxins (polychlorinated dibenzodioxins) have lipophilic (dis-
both diesel particles and ambient air [128]. Aromatic quinones solve in fats) properties, and are known teratogens (cause birth
have previously been identified and measured in gasoline parti- defects), mutagens, and suspected human carcinogens. This is a
culate exhaust extracts [128,129]. The origin of the aromatic qui- large area for research in environmental health thankfully emis-
nones is not fully understood if it is related to the gasoline fuel as sions are a problem only when chlorine is present during com-
un-combusted quinones (initially in the fuel) or if they are formed bustion. Consequently chlorine levels in diesel are now strictly
in the combustion process. A publication by Xia [130] showed that controlled. Potentially biodiesels can contain small levels of
a quinone-enriched polar fraction from a diesel particulate extract chlorine, if certain herbicides are used in production and this must
was more potent than PAH with respect to toxic effects in RAW be avoided [134].
264.7 cells macrophage-like cells derived from tumors induced in The numbers of unregulated emission compounds according to
male BALB/c mice by the Abelson murine leukemia virus. present literature review study are listed in Table 11.

Table 11
Numbers of unregulated emission compounds according to present literature review study.

Metal Inorganic ions Carbonyl compounds BTEX compounds PAH compounds Oxy-PAH compounds Nitro-PAH compounds
oxides

1 Al Nitrate (NO3  ) 1,3-Butadiene Ethylbenzene Benz[a]anthracene 9-Anthraldehyde 1 -Nitropyrene


2 Ca Nitrite (NO2  ) Acetaldehyde Toluene Benzo[a]pyrene Anthraquinone 2-Nitrofluorine
3 Cu Ammonium Acetone Benzene Benzo[b]fluoranthene Benz[a]anthracene-7,12- 7-Nitrobenz(a)anthracene
(NH4 þ ) dione
4 Fe Sulfate (SO4  2) Acrolein o-xylene Benzo[k]fluoranthene Anthrone 9-Nitroanthracene
5 Mg Chloride (C1  ) Benzaldehyde m/p-xylenes Chrysene Benzanthone 6-Nitrochrysene
6 Na Crotonaldehyde Dibenz[a,h]anthracene Xanthone 1-Nitronaphthalene
7 P Formaldehyde Indeno[1,2,3-c,d] 2-Nitrobiphenyl
pyrene
8 S Hexanaldehyde Acenaphthene 2-Nitronaphthalene
9 Si Isovaleraldehyde Acenaphthylene 3-Nitrobiphenyl
10 Zn m/p-Tolualdehyde Anthracene 3-Nitrofluoranthene
11 Methyl ethyl ketone Benzo[ghi]perylene 3-Nitrophenanthrene
12 O-Tolualdehyde Fluoranthene 4-Nitrobiphenyl
13 Propionaldehyde Fluorine 4-Nitrophenanthrene
14 Tolualdehyde Naphthalene 6-Nitrochrysene
15 Valeraldehyde Phenanthrene 9-Nitrophenanthrene
16 Methacrolein Pyrene 1,3-Dinitronaphthalene
17 Butyraldehyde 1,5-Dinitronaphthalene
18 1,8-Dinitronaphthalene
Table 12
NOX emission.

Author Used alcohol Reference fuel Engine tested Operation conditions Test results Year

Shahad [135] Ethanol Gasoline Single cylinder, WC, dual Different CR and speeds, 5%, 10%, Ethanol blending increased NOX concentrations in the exhaust gases by about 2015

M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495


fuel, SI engine and 15% of blending 16.18%.
Kak [136] Methanol Gasoline with hydrogen Single cylinder, air cooled SI Using E10 And M10 Blending NOX concentration was increased for both blends drastically. 2015
Ethanol enrichment engine
Iliev [137] Methanol Gasoline 1-D model of a 4-stroke SI Blending up to 30% A significant increase in NOX emissions when fuel blends percentage increased up 2015
Ethanol engine to 30% E30 (M30).
Li [138] Methanol Gasoline Motorcycles 15% methanol blends The concentration of NOX increased by 76.9–107.7% compared to gasoline. 2014
Ghazikhani [139] Ethanol Gasoline A two stroke gasoline engine Different speed and percentages of The most advantage of ethanol additives was NOX reduction which was reduced 2013
5%, 10% and 15% blending about 83% when it was used in high percentages of ethanol (15%) and averagely
38% for other cases.
Chauhan [140] Ethanol Diesel Diesel Engine Various fumigation ratio At overall engine load conditions, NOX decreased up to a certain level of fumi- 2011
gation then increased.
Zhang [141] Methanol Diesel Diesel engine with DOC 10%, 20% and 30% fumigation And Ethanol fumigation increased NOX emission compared to methanol. 2011
Ethanol various loads
Zhang [142] Methanol Diesel 4 cylinders DI engine 10%, 20% and 30% fumigation- All level of fumigation gave lower NOX emission than diesel fuel. NOX emission 2010
engine speed 1920 rpm increased with level of fumigation
Zhang [143] Methanol Euro V Diesel Diesel Engine with DOC 10%. 20% and 30% fumigation NOX emission decreased compared to Euro V diesel fuel with increasing fumi- 2009
gation concentration.
Cheng [144] Methanol ULSD 4-cylinder NA, DI diesel Various fumigation ratio 6.2% and 8.2% decreased in NOX emission using biodiesel with 10% fumigation 2008
engine ethanol compared to ULSD fuel.
Cheng [145] Methanol Diesel 4-cylinder NA, DI diesel Various fumigation ratio Methanol fumigation reduced NOX emission compared to baseline diesel fuel. 2008
engine
Ajav [146] Ethanol Diesel Single cylinder, NA, WC, DI Various fumigation ratio NOX emission increased 0.4% in case of ethanol vaporization (unheated) and 0.7% 1998
decreased in case of ethanol preheating compared with diesel fuel.
Hayes [147] Ethanol Diesel turbocharged diesel engine different proofs of alcohol fumiga- At a load of 0.8 MPa, NOX emission was greater than diesel fuel for higher level of 1988
tion and engine loads fumigation but NOX decreased within 150 proofs (75% (v/v) EtOH) of ethanol
fumigation.
Broukhiyam [148] Ethanol Diesel 5.7 I, v-8, light duty IDI diesel Various fumigation ratio NOX decreased with increase in fumigation levels. 1981
engine
Heisey [149] Methanol Diesel Single cylinder DI diesel Various fumigation ratio Methanol and ethanol had approximately same effect on NOX emission. Wet 1981
Ethanol engine methanol (160 proof) produced a significant reduction in NOX formation.
Houser [150] Methanol Diesel Oldsmobile 5.7 I, V-8 Diesel Various fumigation ratio NOX was observed to decrease for all rack settings and speeds as the amount of 1980
engine methanol fumigated was increased

1457
1458
Table 13
CO emission.

Author Used alcohol Reference fuel Engine tested Operation conditions Test results Year

Shahad [135] Ethanol Gasoline Single cylinder, WC, dual Different CR and speeds, 5%, 10%, and 15% of Ethanol blending reduced CO concentration in the exhaust gases by about 2015
fuel, SI engine blending 45%.
Kak [136] Methanol Gasoline with hydrogen Single cylinder, air cooled SI Using E10 And M10 Blending With hydrogen enrichment E10 was found to had lower CO specifically at 2015
Ethanol enrichment engine higher loads as compared to M10.
Iliev [137] Methanol Gasoline 1-D model of a 4-stroke SI Blending up to 30% When fuel blends percentage increased, the CO concentration decreased. 2015
Ethanol engine

M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495


Varol [151] Methanol Unleaded gasoline 4-cylinder, 4-strokes SI Blending by mass percent of 10% Compared with unleaded gasoline, blended fuels had a lower CO. 2014
Ethanol engine
Li [138] Methanol Gasoline motorcycles 15% methanol blends Compared with gasoline fuel, the concentration of CO with M15 2014
decreased by 63%–84%.
Ghazikhani [139] Ethanol Gasoline A two stroke gasoline Different speed and percentages of 5%, 10% and CO decreased approximately 71% when 15% ethanol added to gasoline. 2013
engine 15% blending Generally for different speeds and loads, CO decreased averagely 35%.
Surawski [152] Ethanol Diesel 4 cylinder diesel engine Engine speed 1700 rpm with 4 different engine CO emission increased at all loads except idle mode. At idle mode, 15% 2012
load conditions and 0%. 10%, 20% and 40% reduction was achieved by using 10% ethanol. CO emission increased
fumigation significantly in case of 40% fumigation ethanol at all loads.
Zhang [141] Methanol Diesel Diesel engine with DOC 10%, 20% and 30% fumigation And various loads Ethanol reduced CO emission in the same way like methanol but reduced 2011
Ethanol more CO emission than methanol compared to diesel fuel.
Chauhan [140] Ethanol Diesel Diesel Engine Various % of fumigation and loads At each load condition, CO emission decreased from initial level of 2011
fumigation to certain level, respectively, then increased with increasing
level of fumigation
Tsang [153] Ethanol Diesel 4-cylinder NA Diesel engine Various engine loads and fumigation ratio Increase in CO emission when they applied ethanol fumigation in diesel 2010
engine. They observed that CO emission increased by about 0.6 and
1.3 times with 10% and 20% ethanol fumigation at engine load 0.08 MPa
and at engine load 0.70 MPa the increase was about 1.8 times compared
to diesel engine.
Zhang [142] Methanol Diesel 4 cylinders DI engine Engine speed 1920 rpm with 5different engine Brake specific CO emission increased with increasing fumigation 2010
conditions methanol compared to diesel fuel.
Zhang [143] Methanol EuroV Diesel Diesel Engine withDOC 10%, 20% and 30% fumigation And various loads CO emission increase was 2.7 times. 3.8 times and 5.5 times of baseline 2009
value for three consecutive fumigation ratios.
Cheng [145] Methanol Diesel 4-cylinder NA, DI diesel Various fumigation ratio CO emission increased significantly with increasing level of fumigation 2008
engine methanol.
Cheng [144] Methanol ULSD 4-cylinder NA, DI diesel Various fumigation ratio The increase in CO emission was reported using 10% fumigation 2008
engine methanol.
Cheung [154] Methanol ULSD 4-cylinder NA, Diesel Constant speed of 1800 rpm for three engine CO emission increased at each engine load with increasing fumigation 2008
engine loads using fumigation ratio.
Abo- Qudais [155] Ethanol Diesel Single cylinder DI diesel Various engine speeds, blendind and fumiga- Fumigation gave better results than blends. In both cases CO emission 2000
engine tion ratio increased with increasing ethanol substitution.
Ajav [146] Ethanol Diesel Single cylinder, NA, WC, DI Ambient air temp. ¼ 20 °C and 50 °C before Ethanol vaporization increased CO emission. 1998
injection
Hayes [147] Ethanol Diesel Turbocharged diesel engine Different proofs of alcohol fumigation CO emission levels increased greatly as the ethanol flow rate was 1988
increased. This was most severe at low loads, Ethanol proof did not have
an effect on CO emissions
Heisey [149] Ethanol Diesel Single cylinder DI diesel Engine speed of 2400 and various loads, Var- Significant increase in CO emissions at low and medium load at 1981
Methanol engine ious fumigation ratio 2400 rpm. At full load condition, CO emissions showed only a slight
increased up to the point of 25% alcohol substitution.
Table 14
HC emission.

Author Used alcohol Reference fuel Engine tested Operation conditions Test results Year

Shahad [135] Ethanol Gasoline Single cylinder, WC, dual fuel, Different CR and speeds, 5%, 10%, Ethanol blending reduced UHC concentration in the exhaust gases by 2015
SI engine and 15% of blending about40.15%.
Kak [136] Methanol Gasoline with hydrogen Single cylinder, air cooled SI Using E10 And M10 Blending With hydrogen enrichment E10 was found to have lower UHC specifically at 2015

M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495


Ethanol enrichment engine higher loads as compared to M10.
Iliev [137] Methanol Gasoline 1-D model of a 4-stroke SI Blending up to 30% When fuel blends percentage increased, HC concentration decreased. 2015
Ethanol engine
Li [138] Methanol Gasoline motorcycles 15% methanol blends Compared with gasoline fuel, the concentration of total hydrocarbons (THC) with 2014
M15 decreased by 11–34.5%.
Varol [151] Methanol Unleaded gasoline 4-cylinder, 4-strokes SI engine Blending by mass percent of 10% Compared with unleaded gasoline, blended fuels containing different alcohols 2014
Ethanol appeared to have a lower HC
Ghazikhani [139] Ethanol Gasoline A two stroke gasoline engine Different speed and percentages of Using ethanol reduced HC level in all cases and for each 5% ethanol, HC 2013
5%, 10% and 15% blending approximately 6% decreased.
Surawski [152] Ethanol Diesel 4-cylinder engine Different loads and fumigation ratio HC emission increased 30% by 20% ethanol substitution at 25% (quarter load) of 2012
maximum load. At half load condition, HC emission increased more than double
using 40% ethanol substitution.
Zhang [141] Methanol Diesel Diesel Engine with DOC 10%, 20% and 30% fumigation And In case of ethanol fumigation, the reduction of HC emission was more than 2011
Ethanol various loads methanol since ethanol has lower latent heat of vaporization than methanol
Zhang [142] Methanol Diesel 4 cylinders DI engine Engine speed 1920 rpm, Various Methanol fumigation increased the HC emission compared to diesel fuel. 2010
fumigation ratio
Tsang [153] Ethanol Euro V Diesel 4-cylinder NA, Diesel engine Different loads and fumigation ratio An increase of about 1.6 and 3.3 times in BSHC with 10% and 20% fumigation at 2010
engine load 0.08 MPa compared to Euro V diesel fuel while the corresponding
increased at 0.70 MPa are 1.1 and 2.4 times compared to diesel fuel.
Zhang [143] Methanol EuroV Diesel Diesel Engine with DOC different and fumigation ratio Increase of BSHC emission with level of fumigation was higher at low engine load 2009
and lower at high engine load. They found highest increase in BSHC about
7 times at 0.08 MPa and the max reduction was about 3 times at 0.7 MPa com-
pared to diesel fuel.
Cheng [145] Methanol Diesel 4-cylinder, NA, DI diesel 10%, 20% and 30% of fumigation HC emission increased with level of methanol fumigation. 2008
engine
Abo-Qudais [155] Ethanol Diesel Single cylinder DI diesel various engine speeds, blend and Due to ethanol addition to diesel fuel, HC emission increased with increasing 2000
engine fumigation ratio engine speed in fumigation and blend methods. Increase in fumigation method
was lower than blend method.
Hayes [147] Ethanol Diesel Turbocharged diesel engine Various fumigations HC emissions increased greatly compared to diesel fuel. HC emission increased 1988
7.2 times from the diesel levels at low load, 6 times at medium load and 3.8 times
at high load.
Schroeder [156] Methanol Diesel Multi-cylinder, turbocharged Changing the diesel injection timing Advancing the injection timing decreased HC levels in the exhaust gas. 1988
diesel engine

1459
1460
Table 15
CO2 emission.

M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495


Author Used alcohol Reference fuel Engine tested Operation conditions Test results Year

Shahad [135] Ethanol Gasoline Single cylinder, WC, dual Different CR and speeds, 5%, 10%, and Ethanol blending increased CO2 concentrations in the exhaust gases by about 7.5%. 2015
fuel, SI engine 15% of blending
Varol [151] Methanol Unleaded 4-cylinder, 4-strokes SI Blending by mass percent of 10% Compared with unleaded gasoline, blended fuels containing different alcohols 2014
Ethanol gasoline engine appeared to have a higher rate CO2
Ghazikhani [139] Ethanol Gasoline a two stroke gasoline Different speed, 5%, 10% and 15% By each 5% increasing the ethanol to the fuel, CO2 decreased about 6.3%. 2013
engine blending
Pannirselvam [157] Ethanol Diesel Single cylinder, WC various loads– various fumigation ratio Lower CO2 emission using ethanol fumigation compared to base line diesel fuel. 2012
Hebbar [158] Ethanol Diesel DI diesel engine with EGR Various fumigation ratio using EGR CO2 emission increased with increasing percentage of EGR. They did not find any 2012
considerable change at hot EGR with and without fumigation.
Chauhan [140] Ethanol Diesel Diesel engine Various loads–various fumigation ratio At no load condition, CO2 percentage remains almost constant throughout the level of 2011
fumigation but 20% and 45% load condition, CO2 percentage decreased as ethanol
substitution was increased. At full load condition, CO2 percentage decreased up to 15%
of fumigation level then increased. They found 15% ethanol fumigation as optimum
level of fumigation.
Ciniviz [54] Methanol Diesel 4-cylinder, 4 l CI diesel Different engine speed and blending The amount of CO2 increased when the methanol amount was increased in the fuel 2011
engine mixture,
Zhang [143] Methanol Euro V Diesel Diesel engine with DOC 10%. 20% and 30% loads BSCO2 decreased at over all load conditions. At low to medium engine load, the 2009
average reduction had been found up to 4.3% for all percentage of fumigation whereas
up to 7.2% reduction had been found with 30% fumigation methanol at high engine
load.
Cheng [144] Methanol Diesel 4-cylinder NA, DI diesel Various fumigation ratio CO2 emission dropped to 2.5% compared to diesel. 2008
Engine
Cheung [154] Methanol ULSD 4-cylinder NA, diesel Constant speed of 1800 rpm and var- As the fumigation ratio increased from zero to 0.55, CO2 concentration decreased from 2008
engine ious loads and fumigation ratio 3.47% to 3.21% at 0.19 MPa. When the fumigation ratio increased to 0.6, CO2 emission
decreased from 5.55% to 4.99% at 0.38 MPa. At 0.56 MPa, it decreased from 7.96% to
7.59% as the fumigation ratio increases to 0.4.
Table 16
PM and Smoke emissions.

Author Used alcohol Reference fuel Engine tested Operation conditions Test results Year

Karavalakis [159] Ethanol Gasoline Two 2012 MY vehicles of SI DI E10, E15, and E20 blends PM mass emissions exhibited decreases as the oxygen content in the fuel 2014
engines increased. In most cases the reductions in PM mass emissions for both
vehicles were statistically significant.
Wang [29] Ethanol Gasoline A single-cylinder DISI engine Deferent speeds, blends and IMEP PM emissions from ethanol were lower than those from gasoline. 2014
Zhang [141] Methanol Diesel diesel engine with DOC 10%, 20% and 30% fumigation and various Methanol fumigation caused lower PM emission than ethanol fumigation 2011
ethanol loads and reduction was 15–32% and 20–41% for 10% and 20% fumigation

M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495


methanol and 9–19% and 7–26% for 10% and 20% fumigation ethanol. They
also observed that PM decreased with increasing ethanol fumigation like
methanol.
Chauhan [140] Ethanol Diesel Diesel engine Various fumigation ratio and loads Smoke opacity decreased as ethanol fumigation increased. At higher load of 2011
70% and 100%, smoke opacity decreased very quickly up to 14% ethanol
fumigation then reduction was lightly.
Zhang [142] Methanol Diesel 4 cylinders DI engine 10%,20% and 30% fumigation at the engine For all fumigation ratios, PM emission decreased compared to diesel fuel. 2010
speed of 1920 rpm with five steady conditions They observed that reduction was more significant at medium load with all
percentage of fumigation. About 14–31% reduction was measured with 10%
fumigation methanol when reduction was about 27–57% with 30% fumiga-
tion ethanol.
Tsang [153] Ethanol Diesel 4-cylinder NA, diesel engine Various loads and fumigation ratio Fumigation reduced smoke opacity and PM emission compared to diesel 2010
fuel. Smoke opacity increased with increasing engine load with all levels of
fumigation but no significant change was found at low engine load. At
medium and high loads, significant change in smoke opacity reduction was
achieved with all levels of fumigation.
Surawski [160] Ethanol Diesel 4-cylinder engine At 2000 rpm with full load and at inter- In both cases neat diesel used having 10 ppm sulfur and ethanol having 2009
mediate speed 1700 rpm with 4 different 0.55% moisture denatured with 1% unleaded petrol. Their results showed
loads that ethanol fumigation significantly reduced PM emission especially at full-
load operation during the E40 test. At half or quarter load. PM reduction was
not satisfying compared to full-load.
Zhang [143] Methanol Euro V diesel Diesel engine with DOC 10%, 20% and 30% fumigation and various No significant change was found in smoke opacity and PM concentration at 2009
loads low loads but at medium and high engine load condition, remarkable
reduction was found compared to diesel fuel. Maximum 58% smoke
reduction was found with 30% fumigation methanol at the engine load of
0.58 MPa.
Cheng [145] Methanol Diesel 4-cylinder NA, DI diesel engine Various fumigation ratio Methanol fumigation reduced smoke opacity and PM emission in compar- 2008
ison with diesel fuel. They found average reduction in particulate mass
concentration is about 25% for 10% fumigation methanol. But maximum
reduction was 49% at higher level of fumigation.
Lapuerta [46] Ethanol Diesel 4-cylinder, 4-stroke, turbo-charged, 0% and10% ethanol percentage of blending The amount of PM and smoke decreased with using ethanol compared to 2008
intercooled, DI diesel engine diesel.
Abo- Qudais [155] Ethanol Diesel Single cylinder DI diesel engine Various speeds and fumigation ratio They measured maximum decrease in smoke opacity and soot mass con- 2000
centration of 48% and 51% for 20% ethanol fumigation whereas for ethanol–
diesel blend the maximum reduction was measured as 33.3% and 32.5% at
15% ethanol blend.

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4. Results of regulated emissions 5.1.2. Emissions testing and analysis


All tests were conducted in CE-CERT's Vehicle Emissions
NOX, CO, HC, CO2, PM and smoke are the regulated emissions Research Laboratory (VERL), which was equipped with a Burke E.
which are listed in present literature review work. The results of Porter 48-inch single-roll electric dynamometer. A Pierburg Posi-
different studies about regulated emissions are summarized in tive Displacement Pump-Constant Volume Sampling (PDP-CVS)
Tables 12–16. It can be found from Tables 12–16 that application of system was used to obtain certification-quality emissions mea-
alcohol as an alternative fuel in fumigation mode in IC engines surements. For all tests, standard bag samples for carbonyl analysis
lead to reduction of NOX and CO2 in most tests and PM in all cases. were collected through a heated line onto 2,4-dinitrophenylhy-
However, an increase of CO and HC is observed with using alcohol drazine (DNPH) coated silica cartridges (Waters Corp., Milford,
in fumigation mode in most cases. It is noticeable that a diverse MA). Sampled cartridges were extracted using 5 mL of acetonitrile
effect of alcohol application in blended mode compared to fumi- and injected into an Agilent 1200 series high performance liquid
gation mode on regulated emissions except PM is recorded in chromatograph (HPLC) equipped with a variable wavelength
considerable tests. detector. The column used was a 5 pm Deltabond AK resolution
(200 cm*4.6 mm ID) with upstream guard column. They reported
that the HPLC sample injection and operating conditions were set
up according to the specifications of the SAE 930142HP protocol
5. Results of unregulated emissions [161].
Samples for 1,3 butadiene, benzene, toluene, ethylbenzene, and
In the part of the effect of alcohols on unregulated emissions of
xylenes were collected using Carbotrap adsorption tubes consist-
IC engines, 19 experimental works which had done by different ing of multi-beds, including a molecular sieve, activated charcoal,
researchers since 1983–2014 are selected to analyze for this lit- and carbotrap resin. An Agilent 6890 GC with a FID maintained at
erature review study. The test engine and fuel, emissions testing 300 °C was used to measure volatile organic compounds. A Gerstel
and analysis, results and summary of different works are the TDS thermal adsorption unit was used for sample injection. This
following: unit ramps the temperature from 30 °C to 380 °C at a rate of 6 °C
per minute to desorb the sample from the tubes. A 60 m * 0.32 mm
5.1. G. Karavalakis and co-workers (2014) HP-1 column was used. For these analyses, the GC column and
operating conditions were set up according to the specifications of
The goal of the Karavalakis's study et al. [159] was to examine SAE 930142HP Method-2 for C4–C12 hydrocarbons.
how ethanol/gasoline blends and iso-butanol gasoline blends
impact the criteria emissions, gaseous air toxic pollutants, and PM 5.1.3. Results and discussion
emissions from two modern technology light-duty gasoline vehi- The study's aim was to identify and quantify 13 aldehydes and
cles fitted with DI stoichiometric engines. However, the influence ketones in the exhaust of both vehicles when operated with
of different ethanol/gasoline blends on unregulated emissions is alcohol formulations. Figs. 22 and 23 show the carbonyl emissions
only mentioned in the present literature review study. for the Kia Optima and Chevrolet Impala, respectively, expressed
in mg/mile. For both SI DI vehicles, formaldehyde and acet-
5.1.1. Test experimental setup and fuels aldehyde were the most abundant compounds in the tailpipe
The test matrix included two 2012 model year (MY) passenger followed by butyraldehyde, benzaldehyde, crotonaldehyde,
cars equipped with wall-guided direct injection fueling with methacrolein, and propionaldehyde. Other carbonyl compounds
stoichiometric combustion. Both vehicles were also fitted with a were also present in the exhaust but in lesser amounts, including
three-way catalyst (TWC). The first vehicle (Kia Optima) was a those of methyl ethyl ketone (MEK), valeraldehyde, and hex-
2.4 L, 4 cylinders DI engine, having a rated horsepower of 200 hp analdehyde. Hexanaldehyde was detected in small concentrations
at 6300 rpm. The second vehicle (Chevrolet Impala) was a 3.6 L,
6 cylinders DI engine, having a rated horsepower of 300 hp at
6500 rpm. The Kia Optima and the Chevrolet Impala had 11,824
and 25,372 miles, respectively, at the start of the test campaign.
The Kia Optima was certified to the Federal Tier 2, Bin 2 emission
standards, while the Chevrolet Impala was certified to California
LEV II, SULEV emission standards. It should be noted that not every
vehicle was tested on all fuels. Only the 2012 Kia Optima was
tested on the E10/Bu8 mixture.
A total of seven fuels were employed in the authors’ work. The
fuel test matrix included an E10 fuel (10% ethanol and 90% gaso-
line), which served as the baseline fuel for their study, and two
more ethanol blends, namely E15 and E20. For their study, iso-
butanol was blended with gasoline at proportions of 16 (Bu16), 24
(Bu24), and 32% (Bu32) by volume, which were the equivalent of
E10, E15, and E20, respectively, based on the oxygen content. In
addition, an alcohol mixture consisting of 10% ethanol and 8% iso-
butanol (E10/Bu8) was used. This mixed alcohol formulation was
equivalent to E15 based on the oxygen content. All fuels were
custom blended to match the oxygen contents, maintain the Reid
vapor pressure (RVP) within certain limits (6.4–7.2 psi), and match
Fig. 22. Individual carbonyl compounds for the Kia Optima over the FTP cycle.
the fuel volatility properties, except the E10/Bu8 fuel that was a Errors bars represent7 one standard deviation around the average value for each
50/50 splash blend of the E20 and Bu16 fuels. fuel [159].
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1463

Fig. 24. 1,3-Butadiene and BTEX emissions for the Kia Optima over the FTP cycle.
Errors bars represent 7one standard deviation around the average value for each
fuel [159].
Fig. 23. Individual carbonyl compounds for the Chevrolet Impala over the FTP
cycle. Errors bars represent 7one standard deviation around the average value for
each fuel [159].

for some fuel blends and its mainly decreased by the addition of
oxygenates in gasoline. Tolualdehyde was undetectable for all fuel
blends and for both test vehicles.
Acetaldehyde is classified as probably carcinogenic whereas
formaldehyde is classified as human carcinogen by the U.S.
Department of Health and Human Services. For both vehicles, a
clear reduction in formaldehyde and acetaldehyde emissions was
observed with E15 relative to E10. For the Chevrolet Impala, an
increase in both formaldehyde and acetaldehyde emissions was
seen for E20 relative to E10 blend but not at a statistically sig-
nificant level. On the contrary, for the Kia Optima, E15 and E20
blends showed marked and statistically significant reductions in
both formaldehyde and acetaldehyde emissions relative to E10. For
formaldehyde, these reductions were 74% and 88% for E15 and
E20, respectively, while for acetaldehyde the reductions were 72%
and 82% for E15 and E20, respectively.
Generally, gasoline fuels do not contain carbonyl compounds,
with the emissions of aldehydes and ketones being a result of Fig. 25. 1,3-Butadiene and BTEX emissions for the Chevrolet Impala over the FTP
cycle. Errors bars represent 7one standard deviation around the average value for
partial oxidation of the fuel components during combustion. The
each fuel [159].
authors compared their results with previous studies which had
shown that the addition of ethanol fuels can produce higher for-
were measured cumulatively over the entire cycle and were not
maldehyde and acetaldehyde emissions [162–164]. According to weighted like the traditional regulated gaseous emissions. They
their results, the butanol blends and the alcohol mixture (E10/Bu8) reported that the aromatic hydrocarbons of benzene, ethylben-
showed higher butyraldehyde emissions than the ethanol blends zene, toluene, m/p-xylene, and o-xylene were usually termed as
for both vehicles. BTEX. The most reactive volatile organic compounds (VOCs) from
It was reported that, benzaldehyde, which is primarily pro- internal combustion engines are BTEX compounds, since they
duced from fuel aromatic hydrocarbons, showed mixed trends contain a C¼ C bond, that can add free radicals. In general, BTEX
with the alcohol fuels for both vehicles. For the Kia Optima, ben- emissions for the Kia Optima were found significantly higher than
zaldehyde emissions for E15 were higher relative to E10, while E20 those for the Chevrolet Impala, following similar trends with the
was lower. The alcohol mixture was at about the same levels with THC emissions for these vehicles.
those of E15. For the Chevrolet Impala, both higher ethanol blends Overall, They found that 1,3-butadiene and BTEX emissions did
trended lower in benzeldehyde emissions compared to E10. Their not follow a uniform trend for both vehicles and showed both
results were in agreement with those showing that the addition of increases and decreases with the use of oxygenated fuels. For the
oxygenates decreased benzaldehyde emissions [165,166,163], but Kia Optima, E15 and E20 increased 1,3-butadiene emissions by 53%
consistent with other studies showing some increase in benzal- and 199%, respectively, relative to E10 blend, with the increase for
dehyde emissions probably because of the enhancement of aro- E20 being statistically significant. This is an important finding
matics oxidation [167,168]. since 1,3-butadiene is one of the air toxics of interest and a
Authors analyzed their data in Figs. 24 and 25 which indicate recognized human carcinogen. In contrast to the results observed
the cumulative 1,3-butadiene, benzene, ethylbenzene, toluene, m, for the Kia Optima, for the Chevrolet Impala 1,3-butadiene emis-
p-xylene, and o-xylene emissions over the FTP cycle for the Kia sions trended lower for E15 and E20 relative to E10 but not at a
Optima and the Chevrolet Impala, respectively. These emissions statistically significant level.
1464 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

Benzene is one of the major toxic species emitted in tailpipe iso-butanol (E10/Bu8). The two 2012 MY vehicles tested over the
emissions and a suspected carcinogen. The authors mentioned FTP cycle on a light-duty chassis dynamometer were equipped
that some increases were seen in their results for both vehicles in with stoichiometric, wall-guided SI Dl engines with TWCs. The
benzene emissions with the use of higher ethanol blends. This conclusions drawn from that study are the following points:
phenomenon was more pronounced for the Kia Optima where the
increase in benzene emissions for E15 and E20 relative to E10 were  Formaldehyde and acetaldehyde were the predominant
47% and 112%, respectively, and also statistically significant. For the carbonyls in the exhaust for both vehicles followed by butyr-
Chevrolet Impala, there was a statistically significant 69% increase aldehyde, benzaldehyde, crotonaldehyde, methacrolein, and
in benzene emissions for E15 compared to E10, whereas E20 propionaldehyde.
produced similar levels of benzene emissions with E10 blend.  Formaldehyde and acetaldehyde increased and decreased with
Ethylbenzene was the highest emission among the target air the higher ethanol blend relative to E10.
toxics for all vehicles/fuel combinations. For the Kia Optima,  Emissions of 1,3-butadiene did not follow a global trend
ethylbenzene emissions showed a marked increase for E15 (148%) between the test fuels for both vehicles, showing statistically
and E20 (136%) blends compared to E10 at a statistically significant increases for the higher ethanol blends relative to
significant level. E10 for the Kia Optima.
Toluene emission exhibited some increases with E15 (117%) and  Benzene emissions showed elevated emissions for the higher
E20 (224%) compared to E10 for the Kia Optima. The increase in ethanol blends.
toluene emissions for E20 relative to E10 was statistically sig-  For the Kia Optima, E15 and E20 blends led to higher ethyl-
nificant level. As they expected, toluene emission levels for E15 benzene, toluene, and xylenes emissions compared to E10.
and E10/Bu8 were about the same for the Kia Optima. For the  For the Chevrolet Impala, the higher ethanol resulted in mini-
Chevrolet Impala, the higher ethanol blends did not show any mal differences in ethylbenzene, toluene, and xylenes emissions
strong trends in toluene emissions. It was expected that a reduc- compared to E10.
tion in toluene emissions would have occurred with increasing
oxygen content and with the reduction in aromatics content in the 5.2. Ch. Wang (2014)
fuel. The results of that study indicated that toluene may have a
different production pathway in SIDI engines other than through Wang et al. [29] investigated the combustion characteristics
the aromatics in the fuel. and emissions of ethanol and two other novel biofuel candidates,
Tests results indicated that xylene emissions followed similar 2-methlyfuran (MF) and 2,5-dimethylfuran (DMF) in a spray-
patterns with toluene emissions for both vehicles. For the Kia guided GDI engine. However, the effect of ethanol on unregu-
Optima, E15 and E20 trended higher than E10, with E20 showing a lated emissions is only presented in this literature review study.
statistically significant increase in m/p/o-xylenes emissions.
Higher xylene emissions were also seen for the E10/Bu8 blend 5.2.1. Test experimental setup and fuels
relative to E10 at a statistically significant level with E10/Bu8 In author's experiment thesis, the engine and instrumentation
having about the same emission levels as E15. For the Chevrolet setup (Fig. 26) consisted of a direct current (DC) dynamometer,
Impala, the ethanol blends did not present any significant fuel single cylinder spray guided DISI research engine, control, data
trends. acquisition and recording system as shown in Fig. 26.
He conducted the experiment on an engine which was coupled
5.1.4. Summary to a DC dynamometer that was capable of maintaining engine at a
Karavalakis and co-workers examined the effect of fuel for- fixed speed (resolution: 71 rpm) regardless of the engine power
mulation on the criteria emissions, gaseous air toxic pollutants, output. The dynamometer was used as an engine starter when the
and particle emissions from two modern technology gasoline engine starts and as a load absorber when the engine was fired. A
passenger cars equipped with direct injection fueling. A total of 100 L intake buffer box made of steel was used to reduce intake
seven alcohol fuel formulations were utilized, including ethanol flow oscillation introduced by the single cylinder engine, which
blends (E10, E15, and E20), iso-butanol blends (Bu16, Bu24, and improved the volumetric efficiency and the accuracy of air flow
Bu32), and an alcohol mixture comprised of 10% ethanol and 8% rate measurement. The engine was operated via a Lab VIEW

Fig. 26. Schematic of engine and instrumentation setup [29].


M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1465

program. The controllable parameters included injection timing used for aldehyde emissions measurement. The specifications of
and pulse width, injection mode (DI or PFI, or dual-injection HPLC is shown in Table 18.
mode), ignition timing and ignition energy, intake and exhaust In that study, carbonyls also were analyzed by using HPLC. The
valve timing. The throttle was manually controlled via a cable. raw exhaust sample was bobbling into a glass (20 mL DNPH
The 4-valve, 4-stroke single-cylinder close-space concept solution) immersed in an ice bath (Fig. 28). The aldehyde com-
(spray-guided) DISI research engine is shown in Fig. 27. ponents in the exhaust reacted with DNPH (Fig. 29) and the DNPH-
The technical data and engine specification are listed in derivative products were retained in the solvent. The solvent then
Table 17. The engine had a geometric compression ratio (CR) of was analyzed by HPLC.
11.5, which could be changed by adjusting the number and the size The engine was firstly run for at least 20 min, using the PFI
injection system. When the coolant and oil temperatures stabi-
of metal blocks between the crankcase and cylinder block. How-
lized at 358 K, the engine was considered to be warm and then
ever the increase of CR was limited due to the risk of intake valves
GDI injection system was switched on to replace the PFI injection
hitting the piston crown. The engine featured a modem spray-
system. For all of the tests, the exhaust temperature was mon-
guided direct-injection (SGDI) cylinder head as a single cylinder
itored as an important indicator of stable test conditions. All of the
version of Jaguar AJ133 (V8) engines. The engine had compact tests were carried out at ambient air intake conditions (2987 1 K),
double overhead camshafts (DOHC) and equipped with variable at the engine speed of 1500 rpm and stoichiometric air/fuel ratio
valve timing (VVT) systems in both intake and exhaust sides
enabling a 50 CAD valve timing adjusting window. The engine was Table 18
equipped with both DI (150 bar) and PFI (3 bar) injection systems. Specifications of HPLC [29].
The author conducted his experiment base on Gasoline, etha-
Separation Shimadzu LC20
nol, 2-Methylfuran (MF) and 2,5-Dimeihylfuran (DMF). Gasoline Detection Shimadzu SPD-M20A
and ethanol were supplied by the Shell Global Solutions, UK. MF Column Luna: 250 4.6 mm  5 mm
was supplied by the Fisher Scientific, UK. DMF was supplied by the Sample DNPH (20 mL)
Injection size 25 mL
Shijiazhuang Lida Chemical Co. Ltd. and the Beijing LYS Chemicals Flow rate lmL/min
Co. Ltd. with a purity of 99%. But ethanol is chosen to investigate Test conditions 10:90–70:30 v/v; MeCN/water, 120 min; UV λ ¼ 360 nm
for this literature review study. Test duration 130 min

5.2.2. Emissions testing and analysis


The emissions which were measured in the thesis were gas-
eous emissions, PM emissions, and aldehyde emissions. HPLC was

Fig. 27. Single cylinder GDI engine [29]. Fig. 28. Sample collection set up [29].

Table 17
Engine specification [29].

Engine type 4-Stroke, 4-valve


Combustion system Spray guided DISI/PFI
Swept volume 565.6 cm3
Bore  stroke 90  88.9 mm2
Connecting rod length 160 mm
Geometric CR. 11.5:1
Injection system Dl (150 bar) and PFI (3 bar)
Intake valve opening  25° to 25° aTDC
Exhaust valve closing 0–50° aTDC
Fig. 29. Reaction scheme [29].
1466 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

(AFR). The test conditions for Carbonyls emissions are listed in  Acetaldehyde emissions of ethanol were more than gasoline.
Table 19.  Formaldehyde emission of ethanol was lower than that of
Aldehydes were measured using a HPLC (model: Shimadzu gasoline but higher than MF and DMF.
LC20). The aldehydes were measured including formalde-  Acetaldehyde emission of ethanol was higher than gasoline, MF
hyde, acetaldehyde, acrolein, propionaldehyde, methacrolein, and DMF.
benzaldehyde, valeradehyde, m-tolualdehyde and hexaldehyde.  Overall aldehyde emissions of ethanol were considerably higher
The samples were bubbled at 1 L/min for 20 min in an acidified than those of gasoline, MF and DMF.
2,4-dinitrophenylhydrazine (DNPH) reagent (20 mL). The reaction
of carbonyls with the DNPH reagent forms DNPH-carbonyl deri- 5.3. Li and co-workers (2014)
vatives, which was analyzed then by HPLC.
The emission characteristics of motorcycles using gasoline and
5.2.3. Results and discussion M15 (consisting of 85% gasoline and 15% methanol by volume)
It can be seen from Fig. 30 that formaldehyde and C3–C6 were investigated in an article [138]. Exhaust and evaporative
aldehyde emissions of ethanol were recorded less than gasoline. emissions, including regulated and unregulated emissions, of three
But acetaldehyde emissions of ethanol was observed more than motorcycles were presented in that paper. But, the impact of
gasoline. The author showed the aldehyde emissions of MF, DMF, methanol blends on unregulated emissions compared to gasoline
gasoline, and ethanol at 6.5 bar IMEP in Fig. 30. He observed that is only summarized in present literature review study.
formaldehyde emission of ethanol was lower than that of gasoline
but higher than MF and DMF. Acetaldehyde emission of ethanol 5.3.1. Test experimental setup and fuels
was higher than gasoline, MF and DMF. The concentrations of Their experiments were performed on three motorcycles in a
aldehydes ranging from C3 to C6 were relatively lower compared national emission certification laboratory with excellent quality
with formaldehyde and acetaldehyde. The overall aldehyde emis- control and sample management system. Because the actual
sions of MF (89 ppm) and DMF (104 ppm) were considerably emissions of in-use motorcycles are affected by many factors (such
lower than those of gasoline (258 ppm) and ethanol (462 ppm). as age, mileage, and maintain and inspection), the motorcycles
The total aldehyde emissions accounted for 4.6%, 4.7%, 9.2% and studied in their paper were selected from the enterprises' certifi-
25.1% of total HC emissions for MF, DMF, gasoline and ethanol, cation test products. The selected motorcycles were produced by
typical enterprises and enjoyed the most sales in China. They were
respectively.
also in good shape with good emission stability and repeatability
5.2.4. Summary and could meet the experiment requirements for emission con-
The tests were performed on a 4-valve, 4-stroke single-cylinder trast between different fuels.
close-space concept (spray-guided) DISI research engine with a Technical data of the three motorcycles are shown in Table 20.
Two fuels were used: commercial 93# (research octane number)
fixed compression ratio of 11.5:1. The author conducted his
gasoline and M15 methanol gasoline. The commercial 93# gaso-
experiment base on Gasoline, ethanol, 2-Methylfuran (MF) and
line complied with China fourth-stage fuel standard which equal
2,5-Dimeihylfuran (DMF). The main summaries are the following:
to Euro 4. M15 methanol gasoline was made by mixing the com-
 Formaldehyde and C3–C6 aldehyde emissions of ethanol were mercial 93# gasoline with industrial grade methanol in fraction of
less than gasoline. 15% by volume.

Table 19
5.3.2. Emissions testing and analysis
Engine test conditions and test equipment [29]. Fig. 31 shows the schematic diagram of the measurement
system for motorcycle exhaust emissions. The exhaust gas was
Emissions Tested IMEP Spark timing Emission measurement diluted with indoor air by the CVS system (CVS-7100, Horiba,
fuels (bar) (°bTDC) equipment
Japan) and collected to the sampling bags. According to U.S.
Carbonyls MF,DMF, 6.5 KLSA/MBT HPLC Environmental Protection Agency (EPA) technical standard TO-11A
ULG,ETH (EPA/625/R-96/010b), carbonyls were collected by air sampling
pump using tubes coated with 2, 4-dintrophenylhydrazine (DNPH)
(Supelco, USA). In order to ensure that the carbonyls could fully

Table 20
Specifications of the test motorcycles [138].

Items Value

A B C

Engine type Single-cylinder, 4-stroke, water-cooling, 2 valves


per cylinder
Tank volume (L) 4 12 12
Displacement (mL) 110 125 150
Borexstroke (mm  mm) 52.4  49.5 54  54 62  49.5
Rated power at engine 5.3/7500 7.1/7800 8.3/8000
speed (kW/rpm)
Maximum torque at 8.0/4500 8.0/6000 11.4/6000
engine speed (N m/
rpm)
Odometer (km) 1253 1570 1405
After-treatment TWC TWC TWC
Fig. 30. Formaldehyde and acetaldehyde and total C3–C6 aldehyde emissions for Engine fuel system Carburetor Carburetor Carburetor
MF and other tested fuels at 6.5 bar IMEP [29].
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1467

Fig. 31. Schematic diagram of the measurement for motorcycle exhaust emissions [138].

react with 2-4 DNPH, sampling flow and time were set for Table 21
1000 mL/min and 20 min, respectively. After extracted by acet- The carbonyls from exhaust emissions (unit: mg/km) [138].
onitrile, 14 kinds of carbonyls in the sample were measured by
A B C
high performance liquid chromatography (HPLC) (HPLC1200,
Agilent, USA), namely, formaldehyde, acetaldehyde, acrolein, Gasoline M15 Gasoline M15 Gasoline M15
acetone, propionaldehyde, crotonaldehyde, methyl ethyl ketone,
methacrolein, butyraldehyde, benzaldehyde, valeraldehyde, Formaldehyde 0.226 0.347 0.483 0.562 0.364 0.604
Acetaldehyde n.a. 1.130 n.a. 0.875 n.a. 1.216
tolualdehyde, cyclohexanone and hexanaldehyde.
Acrolein þacetone 0.299 0.313 0.203 0.270 0.266 0.362
VOCs are defined as the general term for all the organic com- Propionaldehyde n.a. 0.179 n.a. 0.139 0.137 n.a
pounds whose boiling points were between 323 K and 633 K Crotonaldehyde n.a. n.a n.a. n.a. n.a. 0.063
under the normal pressure. In their paper, the targets VOCs con- Methyl ethyl ketone 0.608 0.842 0.464 0.710 0.547 0.870
Benzaldehyde n.a. 0.630 n.a. 0.736 n.a. 0.814
tained benzene, toluene, ethylbenzene, m-xylene, p-xylene,
Carbonyls 1.133 3.441 1.150 3.292 1.314 3.929
o-xylene, styrene, n-butylacetate, and n-undecane. According to
the US Environmental Protection Agency (EPA) technical standard n.a. means that the pollutants have not been detected.
TO-17 (EPA/ 625/R-96/010b), VOCs were collected by air sampling
pump using stainless steel sorbent tubes coated with Tenax TA Table 22
(Markes, UK). In order to ensure that the VOCs can fully absorbed VOCs from exhaust emissions (unit: mg/km) [138].
by Tenax TA, sampling flow and time were set for 500 mL/min and
20 min respectively. After thermal desorbed (TD), nine kinds of A B C

VOCs were measured by gas chromatography mass spectrometer Gasoline M15 Gasoline M15 Gasoline M15
(GC–MS)(GC–MS, Agilent, USA).
Both of carbonyls and VOCs were identified by matching Benzene 15.185 10.725 11.167 8.091 8.158 3.326
retention time with those of commercial standard mixtures Toluene 94.322 58.002 93.078 63.875 42.101 23.077
n-Butylacetate 0.022 0.071 0.033 0.040 0.019 0.009
(Supelco, USA) and quantified by using five-point external stan-
Ethylbenzene 10.776 19.218 10.803 19.784 14.686 5.650
dard methods in their work. During each test, the unregulated p,m-Xylene 11.883 23.334 26.276 14.849 12.878 4.837
emissions in the diluted air were sampled and analyzed as the Styrene 15.113 9.588 10.625 6.721 6.341 0.726
blank values, which were subtracted from samples. o-Xylene 40.360 31.860 24.539 15.668 12.286 2.268
n-Undecane 0.167 4.279 3.075 1.453 1.101 0.033
VOCs 187.828 157.076 179.595 130.481 97.570 39.925
5.3.3. Results and discussion
The unregulated emission results indicated that the amounts of
the emitted methanol were quite few when comparing with car- both of the formaldehyde for M15 and gasoline were far lower
bonyls and VOCs. Most of methanol can be completely burnt in the than the formaldehyde limit value of 15 mg/mile in the EPA
cylinders for its higher oxygen content and faster flame propaga- exhaust emission standard. The total carbonyls increased by three
tion velocity. Thus they paid more attentions to carbonyls and times when compared with gasoline fueling motorcycles, because
VOCs in the exhaust emission. the additives in M15 contain other polymeric alcohol to ensure the
Eight kinds of carbonyls detected and the total carbonyls from mutual solubility of methanol and gasoline, which may produce
exhaust emissions are listed in Table 21. It is obvious that the acetaldehyde in the process of combustion or in the catalyst.
amounts of formaldehyde and acetaldehyde are the dominant Nine kinds of VOCs from exhaust emissions were analyzed by
among carbonyls analyzed by HPLC. Formaldehyde can cause GC–MS and the results are listed in Table 22. They reported that
respiratory dysfunction, hepatic toxic lesions and carcinogenicity, due to the difficulties in resolving the chromatography peaks, the
so their paper focused on the results of formaldehyde and total results for m-xylene and p-xylene were represented as a sum.
carbonyls from exhaust emissions. Since it was much easier for BTEX (benzene, toluene, ethylbenzene, p,m,o-xylene) dominating
methanol to generate formaldehyde than gasoline did, motorcycle VOCs accounted for more than 90%, especially the toluene
fueled with M15 emitted 16.4–52.5% more formaldehyde than that accounting for approximately 50% of VOCs whatever the motor-
motorcycle fueled with gasoline did. However, they found that cycle was fueled with, gasoline or M15. BTEX from motorcycles
1468 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

fueled with M15 decreased by 16–60% compared with that from resin. For BTEX and 1.3-butadiene, the GC sample injection, col-
gasoline fueling motorcycles, because the higher levels of unsa- umn, and operating conditions were set up according to the spe-
turated hydrocarbons (including olefins, aromatics and benzene in cifications of SAE 930142HP Method-2 for C4–C12 hydrocarbons.
gasoline) made it easier to perform nucleation, condensation An HP 5890 Series II GC with a flame ionization detector
reaction, which contributed to the formation of VOCs. (FID) maintained at 300 °C was used to measure BTEX and 1,3
butadiene. A 2 m*0.32 mm deactivated fused silica BTEX and
5.3.4. Summary 1,3-butadiene. A 2 m*0.32 mm deactivated fused silica pre-column
An experiment was performed on three motorcycles in a and a 60 m*0.32 mm HP-1 column were used. Samples for car-
national emission certification laboratory with excellent quality bonyl analysis were collected through a heated line onto 2,4-
control and sample management system. Two fuels were used; dinitrophenylhydrazine (DNPH) coated silica cartridges (Waters
commercial 93# (research octane number) gasoline and M15 Corp., Milford, MA).
methanol gasoline. The conclusions drawn from that study are the
following points: 5.4.3. Results and discussion
Carbonyl emissions (aldehydes and ketones) were obtained from
 Formaldehyde was the main pollutant among the total carbo- two of the seven vehicles. A total of 13 carbonyls were identified
nyls emitted from vehicles both fueled with gasoline and M15. and quantified in the exhaust. Fig. 5a and b show the carbonyl
 The carbonyls from exhaust emissions of M15 were more than compounds emitted from the 1996 Honda Accord (a) and the
gasoline. 2007 FFV Chevrolet Silverado (b). They reported that consistent
 Motorcycles fueled with M15 emitted 16.4–52.5% more for- with previous findings [120,164,169,170], formaldehyde, acet-
maldehyde than gasoline fueling motorcycles. aldehyde, and acetone were the most prominent carbonyl com-
 The totality of BTEX decreased by 16–60% with using M15. pounds for both vehicles. High molecular weight carbonyl com-
 Controlling the concentration of formaldehyde in the exhaust pounds were also presented, but in significantly lower amounts. For
emissions can make methanol more popular as a kind of the 1996 Honda Accord, emission levels of acrolein, propionalde-
alternative fuel. hyde, valeraldehyde, tolualdehyde, and hexanaldehyde were below
the detection limits of the method for all test fuels. For the FFV, in
5.4. G. Karavalakis and co-workers (2012) addition to the above compounds, crotonaldehyde, MEK, and
methacrolein were almost undetectable. However, only tolualde-
The impact of ethanol blends on criteria emissions (THC, NMHC, hyde was found in detective levels for the E85 fuel.
CO, NOX), greenhouse gas (CO2), and a suite of unregulated pollu- For toxic emissions, acetaldehyde showed the most consistent
tants in a fleet of gasoline-powered light-duty vehicles was inves- trend, increasing with ethanol content for both vehicles. For the
tigated in [166]. But, the influence of ethanol on unregulated pol- 1996 Honda Accord, acetaldehyde emissions increased for the E10
lutants is only summarized in the present literature review work. blend by 71% and 98%, while E20 increased 202% and 251%,
compared with CARB 2 and CARB 3. For the 2007 Chevy Silverado,
5.4.1. Test experimental setup and fuels significant increases in acetaldehyde were only seen with the use
A total of six fuels were employed in their experimental work. of the E85 fuel, with increasing on the order of 1097% (compared
The fuel test matrix included a CARB phase 2 certification fuel with to CARB 2) and 1430% (compared with CARB3). Acetaldehyde
11% MTBE (CARB 2) and a CARB phase 3 certification fuel with 5.7% emissions for E10 were  39% and  23% lower than CARB 2 and
ethanol (CARB 3). CARB 2 served as the base fuel for comparisons, CARB 3. The changes in acetaldehyde emissions for E20 and E50
as it was the fuel currently used for certification. CARB 3, with 5.7% were within the experimental variability. Their results were in
ethanol, was used as the base fuel for creating blends with ethanol agreement with other studies. For instance previous studies had
at proportions of 10 (E10), 20 (E20), 50 (E50), and 85% (E85) by generally shown consistent increased in acetaldehyde emissions
volume. The test matrix included seven vehicles, selected from with increasing ethanol content [171–177], as ethanol was the
three categories, based on their technology. Two vehicles (1984 main precursor of acetaldehyde in vehicular emissions.
Toyota pickup and 1985 Nissan 720 pickup) were from the Tech For the 2007 Chevrolet Silverado, the blends of E10, E20, and
3 category (1981–1985), having early three-way catalysts (TWC) E50 resulted in reductions in formaldehyde emissions, when
with closed loop fuel control. Two vehicles (1991 Ford Explorer compared to CARB 2. The reductions were  44% for E10,  36% for
and 1993 Ford Festiva) were from the Tech 4 category (1986– E20, and  27% for E50. Compared to CARB 3, only E10 resulted in
1995), while three vehicles (1996 Honda Accord, 2000 Toyota limited reductions ( 5%) of formaldehyde emissions, while E20
Camry, and 2007 Chevy Silverado) were from the Tech 5 (1996– and E50 increased emissions by 8–23%, respectively. The use of
2010) category. In the Tech 5 category, one of the vehicles (2007 E85 resulted in significant increases in formaldehyde emissions
Chevy Silverado) was a Flexible Fuel Vehicle (FFV), which could be 88% increase when compared to CARB 2 and 216% increase when
operated on fuels containing 85% ethanol by volume. The chosen compared with CARB 3. They indicated that the increase for-
vehicles were representative of the vehicle fleet in the State of maldehyde emissions for E85 might be attributed to the presence
California. The Tech 3 and Tech 4 vehicles were tested on a four of ethanol, and the higher oxygen content in the fuel, as well as
fuel test matrix including the CARB Phase 2 certification fuel, the decreases in fuel aromatics, because these compounds do not
CARB Phase 3 certification fuel, E10 and E20. The FFV was tested participate in formaldehyde formation [167]. For the 1996 Honda
on a six fuel test matrix including E50 and E85 ethanol blends in Accord, the use of CARB 3 resulted in 14% decrease in for-
addition to CARB 2, CARB 3, E10 and E20. maldehyde emissions, when compared with CARB 2, with E10
following closely behind showing 10% reduction, though the
5.4.2. Emissions testing and analysis reductions were not statistically significant. E20 showed no
Emissions of carbonyl compounds, 1,3-butadiene, and BTEX changes in formaldehyde emissions. Their observation followed
were performed in accordance with protocols developed as part of same behaviors as other works. Previous studies also reported no
the Auto/Oil Air Quality Improvement Research Program [161], or inconsistent changes in formaldehyde emissions as a function of
with enhancements. Samples for BTEX and 1,3-butadiene were ethanol content [171–174].
collected using Carbotrap adsorption tubes consisting of multi- Acetone emission reductions were seen in both the 1996 Honda
beds including a molecular sieve, activated charcoal, and carbotrap and the 2007 Chevy Silverado. The 1996 Honda showed reductions
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1469

Fig. 32. (a) and (b) Individual carbonyl compound emissions for the 96 Honda Fig. 33. (a) and (b) 1,3-Butadiene and BTEX emissions for the 96 Honda Accord
Accord (a) and the 07 FFV Chevrolet Silverado (b) over FTP operation [166]. (a) and the FFV Chevrolet Silverado (b) over FTP operation [166].

in acetone emissions of 39–56%, with higher ethanol levels related formed during combustion of other aromatic and non-aromatic
to the greater reductions. For the 2007 Chevrolet Silverado, the compounds found in gasoline [178]. The authors compared their
highest acetone reductions were achieved with E10, with reduc- observation with other works. Previous studies had shown that
tions of 63% (compared to CARB 2) and 60% (compared to CARB 3). benzene generally decreased with increasing levels of ethanol,
Higher molecular weight carbonyls were found at fairly low levels with this trend primarily be attributable to benzene levels in the
for the 1996 Honda Accord and none of the emission changes were fuel [164,172–174,179,180]. The higher BTEX emissions for CARB
statistically significant. Ethanol blended fuels all had higher cro- 2 did not appear to be directly attributable to fuel aromatic levels
tonaldehyde emissions than CARB 2 for the 1996 Honda, as well. In or oxygen content. Although the CARB 2 fuel had the highest levels
fact, the use of CARB 3, E10, and E20 resulted in increases in cro- of benzene, ethylbenzene and m/p xylenes, the CARB 3 and E10
tonaldehyde emissions of 486%, 510%, and 327%, when compared fuels had either higher or comparable levels of toluene, o-xylene
to CARB 2. Fig. 32(a) and (b) represents the individual carbonyl and total aromatics.
compound emissions for the 96 Honda Accord (a) and the 07 FFV Similar conclusions about fuel aromatic levels cannot be drawn
Chevrolet Silverado (b) over FTP operation. about 1,3-butadiene (which is characterized as a human carcino-
Fig. 33(a) and (b) represents the BTEX and 1,3-butadiene gen and as precursor for secondary formation of formaldehyde and
emissions over the FTP for the 1996 Honda Accord (a) and 2007 acrolein), because it is a product of fuel fragmentation and is not
Chevrolet Silverado (b). The author noted that ethylbenzene was presented originally in the fuel [181,182]. Their observation fol-
almost undetectable for all fuels and both vehicles. For the 1996 lowed same behaviors as other works. Previous studies had not
Honda Accord, BTLX and 1,3-butadiene emissions were sig- shown consistent trends for 1,3-butadiene, either
nificantly higher for CARB 2 than the other fuels. They noted a [171,172,174,176]. In their study, the 2007 FFV Chevrolet Silverado,
previous study [172], which had shown that benzene decreased showed a consistent decreasing trend in 1,3-butadiene, with
with increasing ethanol levels, the current study showed that E20 emissions decreasing as ethanol level increased. Emissions of 1,3-
had lower benzene, as well as toluene and xylene emissions than butadiene were undetectable for E85 and E50 showed a reduction
either CARB 3 or E10. of 78% compared to CARB 2. Benzene levels for the 2007 Chevrolet
Their results presented that benzene levels for the 2007 Silverado did not show consistent trends with increasing ethanol
Chevrolet Silverado did not show consistent trend benzene levels levels. Benzene levels were undetectable for E85 and were lower
were undetectable for E85 and were lower for CARB 3 and E50 for CARB 3 and E50 compared to CARB 2, while benzene levels for
(compared to CARB 2), while benzene levels for E10 and E20 were E10 and E20 were similar to those for CARB 2. They mentioned the
similar to those of CARB 2. The lower emissions of BTEX species for latter phenomenon might be due to the fact that the addition of
the E20 blend might be due to lower levels of total aromatics in oxygenated compounds such as ethanol inhibits the oxidation of
the fuel. The benzene emissions also followed a trend that was benzene. It was therefore possible that an increase in soot volume
roughly consistent with the benzene level in the fuel. Benzene was fraction might result in some increases for benzene emissions
formed from either unburned fuel-borne benzene or benzene [183].
1470 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

For other BTEX compounds, toluene, and m-, p- and o-xylene, and gasoline were the main objective of Yang's work [184]. But, the
the highest emissions were found for CARB 2, while E20 and E50 emission characteristics of carbonyls are presented in this litera-
showed higher emissions of these species than the other ethanol ture review study.
blends, i.e., CARB 3, E10 and E85. The substantially lower BTEX
emissions for E85 relative to the other blends was presumably due 5.5.1. Test experimental setup and fuels
to the higher oxygen content and the lower amount of aromatic Both unleaded gasoline (E0) and an unleaded blend with 3%
compounds in the fuel, although the other fuels did not generally ethanol (E3) were tested. Nine motorcycles manufactured by three
follow this trend. For both the 1996 Honda and the 2007 Chevy, companies in Taiwan with the most overall sales were tested in
emissions of BTEX and 1,3-butadiene were mostly produced dur- that study. All nine were four-stroke motorcycles. The fuel systems
ing the cold-start of FTP, while their concentration levels during for the nine tested motorcycles were all carburetor systems since
the second and third hot-start phases were negligible. most motorcycles used carburetor, whether in Taiwan or other
countries. The displacement volumes were from 100 cm3 to
5.4.4. Summary 150 cm3 and all were manufactured after 2005 with pre-testing
The study of regulated and unregulated emissions profiles of mileages between 733 and 15,800 km. Since E3 was designed for
gasoline-powered light-duty vehicles included models ranging in using in vehicles needing not modification, the test motorcycles
years from 1984 to 2007. Test fuels included a CARB phase 2 cer- were not modified and all motorcycles had the same after-
tification fuel with an 11% MTBE content, a CARB phase 3 certifi- treatment device—a two-way catalytic converter. The motor-
cation fuel with a 5.7% ethanol content, E10, E20, E50, and E85. cycles were tested with E3 and E0 separately. Before each test, the
Regulated and unregulated emission and fuel consumption mea- fuel tank was drained and the vehicle run with test fuel for at least
surements were analyzed over the FTP using a chassis dynam- 1 h to avoid the shadow effect of the old residual fuel. In addition
ometer in at least duplicate for each vehicle/fuel test combination. to these nine motorcycles, two brand-new motorcycles of the
The results of unregulated emissions lead to the following same manufacturer and model were durability tested with E3 and
conclusions: E0, respectively.
The driving modes were comprised of idling, acceleration,
 In general, carbonyl emissions were lower for the ethanol cruise and deceleration to simulate real-world deterioration
blends than those of CARB 2 and CARB 3 fuels, with the within a short period of time. The running mileage was about
exception of the E85 fuel.
500 km every day until they accumulated 15,000 km. Air-pollutant
 Carbonyl emission levels were higher for the 1996 Honda
emissions were measured every 2500 km up to 15,000 km. The
Accord than those of the 2007 FFV Chevrolet Silverado.
motorcycles were inspected and maintained fallowing the manu-
 The most consistent trend for carbonyl emissions was an
facturer's instructions. Air-pollutant emissions were measured at
increase in acetaldehyde emissions with increasing ethanol.
5000 and 10,000 km both before and after maintenance. Fig. 34
 Using of E85 resulted in significantly higher formaldehyde and
illustrates the motorcycle emission sampling system.
acetaldehyde emissions than for the CARB fuels and the other
ethanol blends.
5.5.2. Emissions testing and analysis
 1,3-butadiene and BTEX emissions were found in lower levels
After sample collection, they drew the diluted exhaust from the
for the 2007 Chevrolet Silverado than the 1996 Honda Accord.
Tedlar bag into a pre-coated dinitro-phenyl-hydrazine (DNPH)
 In general, the addition of ethanol resulted in lower toxic
cartridge (LpDNPH SIO Cartridge, Supelco Inc.) at a sampling rate
emissions for the Honda Accord, compared to the CARB 2 fuel,
of 1 L/min for 20 min. The cartridges were then capped and stored
with E20 having the lowest BTEX emissions.
 until analysis. Before analysis, each cartridge was extracted with
For the Chevrolet Silverado, 1,3-butadiene showed the most
consistent trends, with CARB 2 having the highest emissions 5 mL of acetonitrile. Then the extract was passed through a 0.45
and emissions decreasing as a function of ethanol level. 1 m filter to remove particles during the extraction. Analysis was
 For toluene, and m-, p- and o-xylene, for the 2007 Chevrolet performed by a high-performance liquid chromatography/ultra-
Silverado, the highest emissions were found for the CARB 2 fuel, violet detector (HPLC/UV, Hitachi L-2400). Extracts were analyzed
while the E20 and E50 fuels interestingly showed higher with a 250 mm (length) 4.6 mm (diameter) Mightysil RP-18 GP
emissions of these species than the other ethanol blends, i.e., column at a flow rate of 1 mL/min and detected at a wavelength of
CARB 3, E10, and E85. 360 nm. The gradient elution program was applied, beginning
 The unregulated emissions showed some trends with decreas- with a mixture of mobile-phase, methanol/water/acetonitrile
ing BTEX emissions with increasing ethanol for the 1996 Honda
Accord and very low levels of toxic aromatics for the E85 fuel for
the 2007 Chevrolet Silverado, but the BTEX emissions did not
appear to be directly correlated to fuel aromatic levels, although
the CARB 2 fuel did have the highest level of benzene, ethyl-
benzene, and p/m xylenes.
 Overall, the impact of ethanol on emissions for the in-use
gasoline vehicle fleet can depend on a number of factors,
including the mix of vehicle technologies and the ability of
these vehicles to adjust to the level of ethanol in the fuel, the
sensitivities of different vehicles to changes in ethanol content,
interactions with other fuel properties, such as volatility, as well
as other potential factors.

5.5. H.H. Yang and co-workers (2012)

The emission characteristics of regulated air pollutants and


carbonyls from motorcycles using gasoline blended with ethanol Fig. 34. Illustration of the motorcycle emission sampling system [184].
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1471

(0/80/20) for the first 5 min; then methanol/water/acetonitrile 5.5.4. Summary


(30/20/50) for 35 min. The total run time was 40 min. That study investigated the emissions of CO, THC, NOX, CO2 and
Fifteen carbonyls were analyzed in their study: formaldehyde, carbonyls for motorcycles using E0 and E3 gasoline/ethanol blen-
acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, ded fuels. Nine motorcycles manufactured by three companies in
butyraldehyde, benzaldehyde, isovaleraldehyde, valeraldehyde, Taiwan with the most overall sales were tested. All nine were four-
m-tolualdehyde, o-tolualdehyde, p-tolualdehyde, hexaldehyde stroke motorcycles. The main summaries of the paper are the
and 2,5-dimethylbenzaldehyde. A commercial aldehyde-DNPH following.
standard (TO-11 Mix, Supelco Inc.) was used for calibration and
 The emission factors of 15 carbonyls were 1289 and 1600 lg/km
neat aldehydes (Sigma-Aldrich Inc.) were used for recovery tests.
for E0 and E3, respectively.
Medium blanks were measured, and the blank values were sub-
 The emission of acetaldehyde was significantly increased with
tracted from samples. Ranges of recovery, reproducibility (in terms
using E3 as fuel.
of coefficient of variation), linearity (in terms of R-square of the  For individual compounds, using E3 increased the emission of
regression line) and method of detection limit (in terms of emis- most carbonyls.
sion factors) were 77.1–98.2%, 3.28–6.47%, 0.990–0.998 and 0.002–  Acetaldehyde, formaldehyde, propionaldehyde and benzalde-
0.031 1 g/km, respectively. hyde were increased with using ethanol.

5.5.3. Results and discussion


5.6. H. Zhao and co-workers (2011)
The carbonyl emission factors for the nine test motorcycles
are listed in Table 23. The authors recorded that there was no Regulated and unregulated emissions from four passenger cars
significant difference for the carbonyl emission profiles between fueled with different methanol/gasoline blends were investigated
the two fuels. Acetaldehyde, formaldehyde, acetone and benzal- over the NEDC cycle in a study [187]. However, the influence of
dehyde were the major compounds, which account for 28.1%, different methanol/gasoline blends on unregulated emissions is
18.2%, 10.9%, 8.49% for E0 and 31.9%, 31.9%, 8.97%, 8.15% for E3 of only mentioned in the present literature review study.
the 15 carbonyls, respectively.
Total carbonyl (15 carbonyls) emission factors were 5.6.1. Test experimental setup and fuels
1289 7502 lg/km and 1579 7368 lg/km for E0 and E3, respec- Four passenger cars were tested in 13 configurations. Com-
tively. Using E3 as fuel resulted in a 22.5% increase of total car- mercial 93# gasoline was used as the base fuel. Industrial grade
bonyl emissions, but it was not statistically significant (p- methanol was mixed in fractions of 15%, 20%, 30%, 50%, 85% and
value ¼ 0.137). For individual compounds, using E3 increased the 100% by volume, and the fuel blends were named M15, M20, M30,
emission of most carbonyls. Acetaldehyde, formaldehyde, propio- M50, M85 and M100. Vehicle 1 (mileage: 1000 km), vehicle 3
naldehyde and benzaldehyde were increased by 40.9%, 37.0%, (mileage: 1000 km) and vehicle 4 (mileage: 22,751 km) were each
powered by 1.8 L gasoline engines and were tested in three con-
20.2% and 19.1%, respectively. However, they observed that only
figurations: (1) fueled with baseline gasoline and using the origi-
the increase of acetaldehyde was statistically significant (p-
nal equipment manufacturer (OEM)-installed TWC; (2) fueled
value ¼ 0.014). Carbonyls were formed primarily from the reaction
respectively with Ml5, M85 and Ml00 and using the OEM-installed
of hydrocarbons with OH radicals. Combustion of ethanol tended
TWC; (3) fueled respectively with Ml5, M85 and Ml00 and retro-
to form carbonyl compounds due to its hydroxyl structure. In
fitted with a new TWC which was designed specifically only for
addition, the combustion of ethanol with two carbons in structure each vehicle with a main aim to reduce formaldehyde emissions.
could easily form acetaldehyde which contains two carbons as Vehicle 2 (mileage: 105,000 km) was powered by a 1.6-L gasoline
well. Their observation followed same behaviors as other works. A engine and was only tested with different fuels namely, gasoline,
study by Pang also showed that the addition of ethanol in gasoline M20, M30 and M50 with the OEM-installed TWC.
resulted in higher emission of acetaldehyde [185]. In addition, the The emission testing was performed on a chassis dynam-
higher emission of carbonyls attributed to the addition of rich ometer. The drive cycle used was the New European Driving Cycle
oxygen-containing ethanol [172, 186]. (NEDC), which included four ECE (urban cycle) and one EUDC

Table 23
Carbonyl emission factors for E0 and E3 (mean7 SD, l g/km, n¼ 9) [184].

Carbonyls E0 E3 Reduction (%)a p-Value of paired-sample t-test

Formaldehyde 2357 108 322 7 129 37.0 0.179


Acetaldehyde 362 7 155 510 7 178 40.9 0.014
Acrolein 91.9 7 46.3 90.6 ¼ 56.9 1.42 0.946
Acetone 1417 114 1437 85.2 2.06 0.871
Propionaldehyde 67.6 7 37.1 81.3 7 46.0 20.2 0.320
Crotonaldehyde 26.0 7 16.6 28.4 7 16.1 9.27 0.543
Butyraldehyde 53.6 7 32.5 53.4 7 25.3 0.46 0.987
Benzaldehyde 1097 81.5 1307 63.2 19.1 0.189
Isovaleraldehyde 28.17 19.3 30.8 ¼ 14.8 9.71 0.705
Valeral dehyde 38.8 7 31.4 44.17 26.9 13.7 0.614
m-Tolualdehyde 35.87 15.4 39.8 7 15.1 11.2 0.408
o-Tolualdehyde 50.6 7 33.0 54.0 7 27.7 6.57 0.728
p-Tolualdehyde 17.4 7 17.0 30.0 7 26.3 3.98 0.127
Hexaldehyde 15.4 7 9.71 14.3 79.18 7.16 0.704
2.5-D imethylbenzaldehyde 16.0 7 10.8 17.7 7 4.4 10.8 0.229
15 Carbonyls 1289 7 502 15797 368 22.5 0.137

a
Reduction percentage (%) ¼(E0  E3)/E0*100 (%).
1472 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

(extra-urban cycle). The whole tests cycle lasted for 1180 sec. methanol/gasoline blends, total VOCs and BTEX emissions were
Before testing, all cars were conditioned at a temperature of decreased as compared with baseline vehicle fueled only with
(25 72 °C) over 16 h. The measurements were carried out twice at gasoline. For BTEX emissions, M85 showed the highest decrease
the same conditions, and all results were averaged over the two (97.4%) while M15 showed the lowest decrease (19.7%) compared
measurements. with the baseline. Toluene dominated BTEX and total VOC emis-
sions for all methanol/gasoline blends, accounting for approxi-
5.6.2. Emissions testing and analysis mately 40–50% of all VOCs. Unsaturated hydrocarbons in the fuel
The standard mixture of VOCs (SEPA, China) contains benzene, were precursors responsible for the formation of aromatic species.
toluene, ethylbenzene, p-xylene, m-xylene, o-xylene, styrene, n- Since methanol was free of unsaturated hydrocarbons, it had the
butylacetate and n-undecane. Fig. 35 shows a schematic diagram effect of reducing the aromatic precursors, leading to a reduction
of authors’ measurement system for vehicle exhaust emissions. of aromatics. Xylene emissions were related to the aromatic con-
VOCs from the CVS-diluted exhaust were collected through a tent of the fuel. Aromatics were not present in methanol; hence
battery-operated air pump at a flow rate of 750 mL/min using a xylene emissions were reduced when the cars were fueled with
Tenax TA sorbent tube. Tenax samples were analyzed by the methanol/gasoline blends.
thermal desorption pre-concentration method, followed by iden- Carbonyl compound emission factors from vehicles fueled with
tification by high resolution gas chromatography with a mass methanol/gasoline blends at different mixing ratios are presented
spectrometer detector (GC–MS). in Table 25. Formaldehyde emissions were the most abundant
Carbonyl compounds in the dilution tunnel were sampled carbonyl for all ethanol/gasoline blends followed by acetaldehyde,
through a battery-operated air pump at a flow rate of 1200 mL/ acrolein þacetone, benzaldehyde, and propionaldehyde. They
min using a 2,4-dinitrophenylhydrazine DNPH)-coated silica car- reported that, formaldehyde could be produced from alcohols and
tridge, standard technique. They also pointed out the standard paraffin, but the generation of formaldehyde from methanol oxi-
dation was easier than from hydrocarbons, which results in higher
mixture contains 14 components, namely, formaldehyde, acet-
formaldehyde emissions from engines fueled with methanol/
aldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde,
gasoline blends as compared with baseline gasoline-fueled
methyl ethyl ketone, methacrolein, butyraldehyde, benzaldehyde,
engines. With the increase in methanol content, the for-
valeraldehyde, tolualdehyde, cyclohexanone and hexanaldehyde.
maldehyde concentrations also increased. The authors compared
their results with previous studies which done by Zervas et al.
5.6.3. Results and discussion
[167] and Wei et al. [188]. Wei et al. [188] found that formaldehyde
The authors summarized the average VOC emission factors
emission characteristics were approximately linear to the amount
for vehicles fueled with methanol/gasoline blends at different
of cyclic-supplied fuel methanol. In their study, with low-to-
mixing ratios. BTEX (benzene, toluene, ethylbenzene, p/m and
middle ratio methanol/gasoline blends (M15, M20, M30 and
o-xylene) is shown for about 95% of total VOCs in Table 24. For all
M50), formaldehyde emissions had a slight increase compared
with the baseline, while that of high ratio blends (M85 and M100)
were three times higher than the baseline. However, there was a
decrease in acetaldehyde emissions of 13–65% with different ratios
of methanol/gasoline blends. In the case of other carbonyls, there
was an increase or decrease more or less. The sharp increase in
formaldehyde emissions eventually resulted in the increase of
total carbonyls with the exception of M20, which showed no
obvious change from the baseline. Although M20, M30 and M50
were all tested on Vehicle 2, the category and quantity of additives
of the three fuels were different, which resulted in the total car-
bonyls emitted from M50 being slightly higher than that from M20
but significantly lower than that from M30.

5.6.4. Summary
Regulated and unregulated emissions from four passenger cars
fueled with different methanol/gasoline blends (M15, M20, M30,
M50, M85 and M100) were investigated over the NEDC cycle.
Fig. 35. Schematic diagram of measurement system for vehicle exhaust emissions Commercial 93# gasoline was used as the base fuel. Emissions of
[187]. eight VOCs and 13 carbonyl compounds were identified and

Table 24
VOCs emission factors for different mixing ratios of methanol/gasoline fueled vehicles (mg/km) [187].

Vehicle 1 Vehicle 2 Vehicle 3 Vehicle 4

Gasoline M15 Gasoline M20 M30 M50 Gasoline M85 Gasoline Ml 00

Benzene 0.434 0.497 1.658 1.030 1.208 1.060 2.415 0.032 0.848 0.202
Toluene 1.559 1.231 7.594 4.338 4.963 2.375 4.957 0.152 1.875 0.588
n-Butylacetate 0.021 0.018 0.010 0.010 0.037 0.034 0.034 0.014 0.021 0.015
Ethyl benzene 0.335 0.217 2.396 0.943 0.803 0.319 1.313 0.026 0.402 0.110
p,m-Xylene 0.481 0.342 2.429 1.088 0.952 0.448 1.755 0.059 0.577 0.160
Sturene 0.089 0.037 0.352 0.271 0.130 0.099 0.401 0.013 0.116 0.020
o-Xylene 0.380 0.274 1.951 0.866 0.755 0.394 1.621 0.044 0.439 0.129
n-Undecane 0.028 0.015 0.099 0.047 0.035 0.010 0.016 0.008 0.037 0.009
Total VOCs 3.327 2.631 16.489 8.593 8.883 4.739 12.512 0.348 4.315 1.233
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1473

Table 25
Carbonyl compound emission factors for different mixing ratios of methanol/gasoline fueled vehicles (mg/km) [187].

Vehicle 1 Vehicle 2 Vehicle 3 Vehicle 4

Gasoline MI5 Gasoline M20 M30 M50 Gasoline M85 Gasoline M100

Formaldehyde 1.496 1.878 2.918 3.270 5.045 5.182 2.140 5.956 1.784 5.348
Acetaldehyde 0.386 0.317 2.628 2.148 2.291 1.504 1.319 0.954 0.761 0.268
Acrolein þ Acetone 0.241 0.263 0.821 0.614 0.684 0.541 0.696 0.460 0.474 0.181
Propionaldehyde 0.076 0.076 0.399 0.266 0.247 0.210 0.212 0.207 0.141 0.076
Crotonaldehyde 0 0.016 0.049 0 0 0 0.085 0.075 0.052 0
Methyl ethyl ketone 0.216 0 0 0 0.507 0 0.347 0.264 0.123 0.068
Methacrolein 0 0.159 0.303 0.281 0.150 0.439 0 0 0.039 0
Butyraldehyde 0 0 0.498 0.480 0 0 0.074 0.032 0 0.020
Benzaldehyde 0.133 0.138 0.181 0 0.105 0.080 0.565 0.332 0.258 0.121
Valeraldehyde 0.015 0.020 0.103 0.053 0 0 0.044 0 0 0
Tolualdehyde 0 0 0 0 0 0 0 0 0 0
Cyclohexanone 0 0 0 0 0 0 0 0 0 0
Hexanaldehyde 0 0.080 0 0 0 0 0 0 0 0.080
Total carbonyls 2.563 2.948 7.900 7.112 9.029 7.956 5.482 8.281 3.630 6.162

quantified. The effects of different mixing ratios and new TWCs on Table 26
emissions of regulated and unregulated VOC and carbonyl com- Engine specifications [189].
pounds were studied. The conclusions drawn from that study are
Model Isuzu 4HF1
the following points:
Type Water-cooled, in-line, four-cylinder, DI engine
 For all methanol/gasoline blends, total VOCs and BTEX Maximum power 88 kW/3200 rev/min
decreased relative to the baseline. Maximum torque 285 N m/1800 rev/min
 For BTEX emissions, as compared with the baseline, M85 had Bore/stroke 112 mm/110 mm
Displacement 4334/cm3
the highest decrease (97.4%) while M15 had the lowest decrease Compression ratio 19.0:1
(19.7%). Injection pump type Bosh in-line type
 With low-to-middle ratio methanol/gasoline blends (M15, M20, Injection nozzle 5-hole nozzle
M30 and M50) formaldehyde emissions had a slight increase;
while that of high ratio blends (M85 and M100) were three
times compared with gasoline counterparts.
 Total carbonyl emissions increased with increasing percentage
of methanol irrespective vehicle 2, M20.

5.7. Z.H. Zhang and co-workers (2010)

In Zhang's study et al. [189] the effect of the new combustion


scheme, coupled with the effect of a DOC, on regulated and
unregulated emissions, particulate number concentration and size
distribution was investigated based on the Japanese 13 Mode test
cycle with methanol. But, the effect of methanol on unregulated
emissions is mentioned in this literature review study.

5.7.1. Test experimental setup and fuels


The test engine was a 4-cylinder natural-aspirated direct-
injection diesel engine with specifications shown in Table 26.
The engine had been modified for the new combustion scheme.
The modification included the installation of a methanol injection
and control system to the air intake manifold of the diesel engine
with one fuel injector for each cylinder. The modification also
included a separate fuel tank and fuel pump for the methanol.
The experimental setup is shown in Fig. 36. The engine was
coupled with an eddy-current dynamometer and the engine speed
and torque were controlled by the Ono Sokki diesel engine test
system. A commercial Engelhard CCX8772 A DOC was installed at
the down-stream end, 850 mm from the exhaust manifold. The Fig. 36. Schematic diagram of experimental system [189].
used fuels included Euro V diesel fuel with less than 10-ppm by
weight of sulfur and industrial grade methanol.
(IMR) mass spectrometer, which allowed dynamic studies of gas-
5.7.2. Emissions testing and analysis eous emission in low concentration. The gas sample was taken
Unregulated gas emissions including methane, ethyne, ethene, directly from the exhaust pipe and maintained at 190 °C to the
1,3-butadiene, BTX, formaldehyde and unburned methanol were multi-component gas analyzer. In their experimental investiga-
online analyzed with an Air-Sense multi-components gas analyzer tion, benzene, toluene, and formaldehyde and methanol were
(V&F Airsense Net). The analyzer was an Ion Molecule Reaction calibrated directly using standard gases, while the other
1474 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

compounds were calibrated through an indirect way based on 20% and 30%. After passing through the DOC, there was still about
information provided by the equipment supplier. 0.028 g/kWh of methanol emission under different levels of
The test modes in the Japanese 13 Mode test cycle for diesel fumigation methanol. The results indicated that high methanol
vehicles were adopted to evaluate the effect of the DMCC and the emission occurred with fumigation methanol.
DOC on regulated and unregulated emissions. The detailed oper- They reported that, methanol in the engine exhaust was either
ating conditions of each mode and the methanol fumigation the intermediate product from the combustion of diesel fuel or the
strategy used are shown in Table 27. The emissions were weighted fumigation methanol which had not been burned. For diesel only
over the Japanese 13 Mode test cycle using a set of weighting operation, in the absence of fumigation methanol, the only source
factors. In authors’ study, fumigation methanol was applied only at of methanol was the intermediate combustion products of the
medium to high engine loads when the exhaust gas temperature is diesel fuel. The very low concentration of methanol in the diesel
fuel operation indicated that the intermediate products only had a
high enough to ensure proper DOC operation. Thus in their study,
small contribution to the methanol in the engine exhaust. When
fumigation methanol was applied in mode 6 to mode 12 only.
operating in the fumigation mode, the significantly higher
Moreover, mode 9 was selected to analysis the SOF in the parti-
methanol emission was mainly due to the quenched and trapped
culate while mode 9 and mode 11 were chosen to investigate the
methanol which could not be oxidized in the expansion stroke of
particulate number concentration and size distribution.
the combustion cycle.
High formaldehyde emission was also found in the DMCC
5.7.3. Results and discussion
mode, as shown in Fig. 37. Compared with the baseline engine,
Methanol and formaldehydes are the two major unregulated
there was an increase of 17%, 30% and 47% formaldehyde emis-
emissions associated with the combustion of methanol [189]. As
sions, respectively, for 10%, 20% and 30% fumigation methanol.
shown in Fig. 37, there is a sharp increase in methanol emission They found that formaldehyde was an intermediate combustion
when the engine was operated in the DMCC mode. For the base- product. The increase of fumigation methanol led to a reduction in
line engine, the weighted brake specific methanol emission was combustion temperature which might enhance the formation of
only 0.03 g/kWh, however it increased to 0.52 g/kWh, 0.68 g/kWh the intermediate combustion product and hence an increase of
and 0.86 g/kWh respectively at fumigation methanol level of 10%, formaldehyde. The authors compared their results with previous
studies. They indicated that, previous work of Rideout et al. [36],
Table 27 Sakamoto et al. [190], Kim [191] and Lipari [192] showed that
The Japanese 13 Mode test and methanol fumigation strategy [189].
methanol fueled engines had a tendency to emit significant
Mode No. Speed Torque (%) Weight Exhaust Methanol amount of formaldehyde. In addition, Chao et al. [193] also found a
(rev/ factor temp.a (°C) fumigation high formaldehyde emission from a diesel engine fueled with
min) diesel blended with up to 15% by volume of methanol. For-
maldehyde was an important secondary pollutant and played an
1 Idle 0 0.205 95 
2 1280 20 0.037 158 
important role in urban smog chemistry. Thus the high for-
3 1280 40 0.027 217  maldehyde emission was a disadvantage of DMCC operation.
4 idle 0 0.205 95  Among the various compounds in the exhaust emissions, the
5 1920 20 0.029 212  effect of DMCC on methane (CH4), ethyne (C2H2), ethene (C2H4),
6 1920 40 0.064 282 þ
1,3-butadiene (C4H6), benzene (C6H6), toluene (C7H8) and xylene
7 2560 40 0.041 341 þ
8 2560 60 0.032 481 þ (C8H10) was investigated in their experiment work based on the
9 1920 60 0.077 360 þ Japanese 13 Mode test cycle. The weighted brake specific emis-
10 1920 80 0.055 452 þ sions, together with the standard errors at 95% confidence level,
11 1920 95 0.049 532 þ are shown in Table 28. Table 28 shows that, compared with the
12 2560 80 0.037 507 þ
13 1920 5 0.142 188 
baseline engine, methane increased, while ethyne and ethene
decreased, with fumigation methanol. With increasing level of
a
Exhaust gas temperature of baseline engine. fumigation methanol, the combustion temperature decreased.
However, ethyne and ethene were the products of thermal pyr-
olysis of diesel fuel and methanol. Probably the combustion of
diesel fuel in fumigation methanol improved the diffusion com-
bustion, leading to the reduction of both ethyne and ethene.
1,3-butadiene is an air toxic commonly found in the exhaust
gas of diesel and petrol vehicles. The results showed a significant
reduction of the compound when the engine was operated in the
DMCC mode. Their results were in agreement with Takada et al.
[194] who suggested that 1,3-butadiene was emitted easily under
high exhaust gas temperature condition. Probably the high heat of
evaporation of methanol and thus low combustion temperature
could lead to the reduction of 1,3-butadiene.
Benzene, toluene and xylene (BTX) are air toxics emitted from
many sources, including motor vehicles. Benzene and toluene
emissions were higher in the DMCC mode. The increase in ben-
zene emissions were 20.4%, 19.1% and 14.1% respectively at 10%,
20% and 30% fumigation methanol; while the corresponding
increase in toluene emissions were 38.9%, 96.8% and 69.0%.
However there was no significant difference in xylene emissions.
Overall speaking, there was an increase in BTX emissions with
Fig. 37. Effect of DMCC and DOC on unburned methanol and formaldehyde fumigation methanol. The increase in BTX emissions were 25.4%,
emissions [189]. 48.6% and 35.6% respectively at 10%, 20% and 30% fumigation
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1475

Table 28
Hydrocarbon speciation with and without fumigation methanol (weighted brake specific emissions based on Japanese 13 Mode test cycle) [189].

lg/kWh Methane (CH4) Ethyne (C2H2) Ethene (C2H4) 1,3-butadiene (C4H6) Benzene (C6H6) Toluene (C7H8) Xylene (C8H10) BTX

M0 48 7 2 42017 180 20667 48 3955 7 182 161 711 1267 7 22 7 2 310 712
M10 567 3 3209 7 128 928 7 23 23077 140 194 714 1757 9 207 1 389 714
M20 627 2 3042 7 116 880 7 18 2168 7 166 193 716 248 7 15 21 7 2 461 711
M30 707 2 2903 7 107 849 7 12 22717 173 184 712 2137 11 187 1 421 713

methanol. The authors compared their observation with other


work. Tang et al. [6] found a high BTEX emission from a diesel
engine fueled with diesel–ethanol blends, and they attributed the
high BTEX emission to the increase in air/fuel ratio due to the
addition of ethanol as an oxygenate. According to their report,
methanol had high oxygen content and could also increase the
air/fuel ratio, and thus leading to higher BTX emissions when the
engine was operated in the DMCC mode.
The DOC was found to be effective also in reducing these
emissions. The percentage reduction in the Japanese 13 Mode
weighted brake specific emissions of them varies from 45% to 68%.
Thus the DOC was also effective in reducing the air toxics,
including 1,3-butadiene and the BTX.
The author selected the Mode 9 to investigate the effects of
fumigation methanol and the DOC on SOF on diesel particulate, for
diesel fuel and for 10% and 30% fumigation methanol. The SOF in
the particles were attributed to unburned, pyrolyzed or partially
oxidized fuel and lubricating oil and were transferred from the gas
phase to the particulate phase when the exhaust cooled [195].
With fumigation methanol, higher unburned hydrocarbon,
Fig. 38. Effect of DMCC and DOC on proportion of SOF in the particulate at mode 8
including unburned methanol and formaldehyde, might tend to [189].
increase the SOF in the PM. As shown in Fig. 38, the SOF in the PM
increased with the level of fumigation methanol. The SOF in the 5.8. Z.H. Zhang and co-workers (2010)
particulate was 65% in the baseline engine, which increased to 71%
and 80% respectively at 10% and 30% fumigation methanol. Their Zhang's work et al. [142] aimed to provide further experimental
observation followed same behaviors as others work. Lin [196] also data on the effect of fumigation methanol on the emissions of a
found increase of SOF when the engine was operated with diesel– diesel engine and the sensitivity of these emissions to the amount
methanol blends at different operating conditions. of fumigation methanol applied under different operating condi-
Due to oxidation of the SOF, the percentage of SOF in the par- tions. Besides the regulated emissions, certain unregulated emis-
ticulate with DOC was about 25–29% less than that without DOC. sions were also measured. But, the effect of methanol fumigation
Thus, the percentage of SOF in the PM was only 6.8% higher at 10% on unregulated emissions is only chosen in present literature
fumigation and 12.1% higher at 30% fumigation compared with survey work.
that of the baseline engine.
5.8.1. Test experimental setup and fuels
5.7.4. Summary Their experimental system and Engine specifications are shown
Experiments were conducted on a 4-cylinder direct-injection in Fig. 36 and Table 26, respectively. The Euro V diesel fuel and
diesel engine operating on the DMCC scheme. The effect of the industrial grade methanol were used.
new combustion scheme, coupled with the effect of a DOC, on
regulated and unregulated emissions was investigated based on 5.8.2. Emissions testing and analysis
the Japanese 13 Mode test cycle. The Euro V diesel fuel with less In their research unregulated gases including benzene, toluene,
than 10-ppm by weight of sulfur and industrial grade methanol formaldehyde and methanol were online analyzed with the Air
were used. The following conclusions are summarized from that sense multi-component gas analyzer. The gas sample was taken
work: directly from the engine exhaust and maintained at 190 °C to the
multi-component gas analyzer. In that study, benzene, toluene,
 Sharp increase in unburned methanol emission when the formaldehyde and methanol were calibrated directly using stan-
engine was operated in the DMCC mode. dard gases, while other compounds were calibrated indirectly
 High formaldehyde emission was also found in the DMCC mode. based on information provided by the equipment supplier.
 Compared with the baseline engine, methane increased, while Experiments were carried out at various steady state operating
ethyne and ethene decreased, with fumigation methanol. conditions. All the gas concentrations were continuously mea-
 A significant reduction of 1,3-butadiene was found when the sured for 5 min at the exhaust tailpipe of the diesel engine. Three
engine was operated in the DMCC mode. tests were carried out for each operating condition and the results
 Benzene and toluene emissions were higher in the DMCC mode; were found to agree with each other within the 95% confidence
however there was no significant difference in xylene level. They conducted the experiment operating the engine at
emissions. speed of 1920 rev min  1, and at engine loads of 46, 92, 138, 184
 Overall, there was an increase in BTX and SOF emissions with and 218 N m, corresponding to brake mean effective pressures of
fumigation methanol. 0.13, 0.27 0.40, 0.53 and 0.63 MPa, respectively. Experiments were
1476 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

Fig. 39. Effect of fumigation methanol on unburned methanol emission [142]. Fig. 40. Effect of fumigation methanol on formaldehyde emission [142].

firstly carried out with diesel fuel alone to build up a database for further oxidation depend on the species in the combustion
comparison with those obtained with fumigation methanol. chamber, the temperature and the time spent under these con-
Experiments were then carried out with the diesel fuel taking up ditions [197]. They reported that the increase of fumigation
90% of the desired engine load while the rest of the desired load methanol leads to a reduction in combustion temperature which
was taken up by fumigation methanol. Experiments were repeated might enhance the formation of the intermediate combustion
with the diesel fuel taking up 80% and 70% of the desired engine product and hence an increase of formaldehyde.
loads, with fumigation methanol providing respectively 20% and Besides methanol and formaldehyde, the authors also mea-
30% of the desired engine loads. sured the concentrations of the following hydrocarbons: ethyne,
ethene, 1,3-butadiene, benzene, toluene and xylene, because most
5.8.3. Results and discussion
of them had high reactivity and toxicity. Their results are shown in
The brake specific unburned methanol emission in the exhaust
Table 29. Ethyne (C2H2) and ethene (C2H4) emissions significantly
gas is shown in Fig. 39. The unburned methanol emission was no
decreased when fumigation methanol was applied. The average
more than 0.1 g kW  1 h  1 for the baseline engine but sig-
reduction of ethyne and ethene with different engine loads were
nificantly increased with fumigation methanol, especially at low
respectively 78% and 54% for 10% fumigation methanol; while the
engine load. At the engine load of 0.13 MPa, it increased to
corresponding reductions were 82% and 60% for 30% fumigation
14.4 g kW  1 h  1, 18.5 g kW  1 h  1 and 25.3 g kW  1 h  1
methanol. The authors compared their observation with other
respectively, for 10%, 20% and 30% fumigation methanol. At higher
works. Flynn et al. [198] developed a chemical kinetic and mixing
engine loads, the unburned methanol emissions for fumigation
model to study the premixed, rich ignition process, using n-hep-
methanol operation decreased rapidly but are still higher than that
tane, as a representative diesel fuel, blended with methanol. Flynn
for diesel fuel. They wrote that the possible reason was that with
results also showed that methanol addition could reduce the
increase of engine load, there was an increase in fuel burned and
hence combustion temperature. The increase in the amount of concentrations of ethyne and ethene. As explained in Flynn et al.
methanol in the fuel would cause an increase of unburned [198], methanol does not contain any C–C bonds and cannot then
methanol but the increase in combustion temperature tended to produce significant levels of these species. Ethyne and ethene
reduce the unburned methanol. were the products of thermal pyrolysis of diesel fuel and metha-
Their results vividly illustrated that similar to the brake specific nol. Probably the combustion of diesel fuel in fumigation methanol
unburned methanol emission, the brake specific formaldehyde improved the diffusion combustion, leading to the reduction of
emission increased with increase of fumigation methanol and both ethyne and ethene.
decreased with increase in engine load, as shown in Fig. 40. For each engine load, there was a significant reduction of the
Compared with the baseline engine, there were about 1.8–2.2 compound when the engine was operated with fumigation
times, 2.4–2.9 times and 3.4–4.5 times increase in formaldehyde methanol while the reduction was not directly related to the level
emission for different engine loads, for 10%, 20% and 30% fumi- of fumigation methanol. In fact, the reduction was about 57–69%
gation methanol respectively. They compared their observation with different engine loads and different levels of fumigation
with Chao et al. [193] who studied the effect of methanol on the methanol. The authors’ observation followed same behaviors as
emissions of carbonyl compounds generated from the diesel other works. Takada et al. [194] suggested that 1,3-butadiene was
engine operating on diesel/methanol blends. Chao found that the emitted easily under high exhaust gas temperature condition. The
formaldehyde emissions increased with the methanol fraction, cooling effect of methanol, associated with the high latent heat of
which matched with the results of their study. Their results fol- evaporation, could lead to the reduction of 1,3-butadiene. Flynn
lowed same behaviors as other works. Zervas et al. [167] found et al. [198] found that addition of methanol reduced 1,3-butadiene
that the formaldehyde emissions increased with the methanol emission and they attributed this to the same reasons leading to
fraction, and suggested that exhaust formaldehyde was mainly the reduction of ethyne and ethene emissions. Merritt et al. [199]
produced from methanol. Zervas had similar variation in for- recorded 24–82% reduction of 1,3-butadiene emission after the
maldehyde emission with percentage of methanol and engine addition of different percentage of ethanol in the diesel fuel, while
load. The formation of formaldehyde from hydrocarbons and their the reduction was not directly related to the percentage of ethanol
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1477

Table 29
Hydrocarbon speciation with different levels of fumigation methanol [142].

3 3 3 3 3 3 3
Engine load (MPa) % MeOH C2H2 (lg m ) C2H4 (lg m ) C4H6 (lg m ) C6H6 (lg m ) C7H8 (lg m ) C8H10 (lg m ) BTX (lg m )

0.13 M0 197.5 175.3 555.7 22.7 12.8 5.9 41.4


M10 86.9 34.2 206.3 23.9 26.7 2.5 58.1
M20 71.5 33.3 207.9 27.7 63.3 2.3 102.3
M30 62.4 30.2 205.7 26.1 56.5 3.2 85.6
0.27 M0 270.7 195.7 600.5 28.8 13.3 6.0 48.2
M10 121.2 48.7 257.6 36.7 35.1 2.9 74.7
M20 93.6 32.8 214.4 32.8 30.9 2.1 65.8
M30 76.4 30.8 204.7 30.2 52.1 1.8 84.2
0.40 M0 250.6 173.6 536.2 35.5 11.6 5.0 50.1
M10 106.1 38.4 191.7 33.1 25.7 2.2 61.0
M20 90.7 31.9 185.8 30.2 52.3 2.3 85.7
M30 84.8 30.2 184.1 22.4 44.5 1.7 68.5
0.53 M0 187.5 133.0 466.0 29.8 13.1 5.3 48.2
M10 82.2 28.8 141.5 27.1 21.6 2.1 50.8
M20 85.8 29.1 143.6 31.3 39.8 1.8 72.9
M30 76.7 26.9 146.9 27.1 31.5 1.3 59.9
0.63 M0 141.7 185.9 533.2 33.5 16.3 6.1 55.9
M10 79.6 40.6 206.8 30.7 212 2.5 54.0
M20 85.5 40.9 217.1 37.8 40.1 2.3 80.2
M30 90.5 37.2 212.2 36.4 30.7 1.4 68.5

in the fuel, which was in line with the results obtained in their methanol for 10%, 20% and 30% load displacement. The effect of
investigation. fumigation methanol on engine performance, regulated and
The authors found that, the effect of fumigation methanol on the unregulated emissions were investigated. The following conclu-
BTX emissions, as shown in Table 29, depended on both engine load sions can be drawn from that study:
and level of fumigation. There was a slight decrease or increase in
the benzene emission with different levels of fumigation methanol  Fumigation methanol decreased the emission of ethyne, ethene,
and engine loads. They had used a number of studies for proving 1,3-butadiene.
their obtained results. Takada et al. [194] suggested that benzene  Fumigation methanol significantly increased the emissions of
was easily oxidized at high temperature. When fumigation unburned methanol, formaldehyde and the BTX.
methanol was applied, the combustion temperature was reduced,
which might lead to increase in benzene emission. However, it had 5.9. C.S. Cheung and co-workers (2009)
been pointed out that the formation of mono and polynuclear
aromatic compounds was related with the lack of oxygen to convert In Cheung's experiment et al. [203] the engine performance,
carbon atoms to carbon dioxide [200]. Thus with increase in regulated emissions and unregulated emissions were studied on a
fumigation methanol, the increase of oxygen content could improve diesel engine fueled with Euro V diesel fuel, biodiesel, and three
combustion and promote the degradation of benzene and hence biodiesel–methanol blends. But, the unregulated emissions char-
reduce benzene emission. Moreover, as explained in Inal [201], acteristics of methanol blends are only presented in current lit-
unsaturated hydrocarbons in the fuel were precursors responsible erature review study.
for the formation of aromatic and PAH species. Since fumigation
methanol was free of unsaturated hydrocarbons, it had the effect of 5.9.1. Test experimental setup and fuels
reducing the aromatics precursors, leading to the reduction of the Their experimental system and Engine specifications are shown
aromatics. The above factors counteracted with each other, resulting in Fig. 36 and Table 26, respectively. The used fuels in that study
in slight increase or decrease of benzene emission with different included Euro V diesel fuel, biodiesel and biodiesel blended with
levels of fumigation methanol. Regarding toluene and xylene methanol. Biodiesel used in their study was manufactured from
emissions, for each engine load, there was an increase in toluene waste cooking oil by Dunwell Petro-Chemical Ltd. The blended
emission but decrease in xylene emission when fumigation fuels were prepared by mixing 5%, 10% and 15% by volume of
methanol was applied. Nelson et al. [202] found that benzene and methanol in biodiesel and identified as BM5, BM10, and BM15.
toluene were largely formed in the combustion process from fuel
fragments produced in the initial oxidative pyrolysis of the fuel. 5.9.2. Emissions testing and analysis
Thus, their formation was largely determined by combustion con- Unregulated emissions included unburned methanol, for-
ditions such as local stoichiometry and temperature. However, maldehyde, acetaldehyde, 1,3-butadiene, benzene, toluene and
xylene emission was related to the aromatic content of the fuel. The xylene, were measured with the Airsense multi-component gas
lower combustion temperature associated with the high latent heat analyzer. Standard benzene, toluene, methanol and formaldehyde
of vaporization of methanol might lead to higher toluene emission. gases were used to calibrate the Airsense multi-component gas
However, methanol was aromatic free and hence reduces xylene analyzer while the other unregulated gases were calibrated
emission when the engine was operated with fumigation methanol. indirectly with information provided by the equipment supplier.
Overall speaking, there was an increase of the BTX emission with The tests were conducted at a steady engine speed of
fumigation methanol, due mainly to the increase of toluene 1800 rev min  1, and at engine loads of 28 N m, 70 N m, 130 N m,
emission. 190 N m, and 240 N m, corresponding to the brake mean effective
pressures of 0.08 MPa, 0.2 MPa, 0.38 MPa, 0.55 MPa, and 0.70 MPa,
5.8.4. Summary respectively. At each engine operating mode, experiments were
Experiments were conducted on a 4-cylinder direct-injection carried out for the diesel fuel, biodiesel, BM5, BM10 and BM15. In
diesel engine operating on Euro V diesel fuel and fumigation order to ensure the repeatability of the measurements, the cooling
1478 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

water temperature was automatically controlled to 80 °C, and held They presented that with increase of methanol fraction in the
to within 72 °C, while the oil temperature was maintained at 90– blended fuel, the formaldehyde emissions increased. However, the
100 °C, depending on the engine load. Before recording the data, difference between the formaldehyde emissions between biodie-
the engine was allowed to operate for a few minutes until the sel and the blended fuels were small at the engine loads of
engine reached a steady state, as reflected by the lubricating oil 0.55 MPa and 0.70 MPa. From biodiesel to BM15, the change of
temperature and the cooling water temperature. Also, the diesel formaldehyde emissions were 59.8%, 33.2%, 16.3%, 10.3% and 11%,
engine used in the experiment was not modified during all for the engine loads of 0.08 MPa, 0.20 MPa, 0.38 MPa, 0.55 MPa
the tests. and 0.70 MPa, respectively. Their results were in agreement with
other studies. For instance, Zervas et al. [167] found that the for-
5.9.3. Results and discussion maldehyde emissions increased with the methanol fraction, and
Aldehydes emitted from internal combustion engines are concluded that exhaust formaldehyde was mainly produced from
intermediate products of hydrocarbons or oxygenated compounds fuel methanol. And Chao et al. [193] studied the effect of methanol
in the fuel [194]. The authors in their paper presented that for- on the emissions of carbonyl compounds generated from the
maldehyde was the most abundant aldehyde in the engine diesel engine. They found that the formaldehyde emissions
exhaust, followed by acetaldehyde. The variation of formaldehyde increased when methanol increased from 5% to 15%. In addition,
emissions is shown in Fig. 41. Formaldehyde emissions increased Zhang et al. [208] measured the formaldehyde emission on a
when the engine load increases from 0.08 MPa to 0.38 MPa, but diesel engine fueled with DME derived from methanol. They
decreased when the engine load increased from 0.38 MPa to concluded that the higher formaldehyde emission was attributed
0.70 MPa. Formaldehyde emissions attained the peak value at to the oxygen contents in the fuel.
medium engine load, which was similar to that of the total Fig. 42 shows the variation of acetaldehyde emissions in the
hydrocarbon emissions. engine exhaust. The acetaldehyde emissions vary narrowly
The formaldehyde emissions of the blended fuels were higher between 4 and 7 ppm which was similar to the results of He et al.
than those of biodiesel and the Euro V diesel fuel while the for- [209] in which the acetaldehyde emissions varied between 1 and
maldehyde emissions of biodiesel were higher than those of the 8 ppm. In general, they found that the maximum acetaldehyde
diesel fuel. The difference in formaldehyde emissions among the emission occurred at the engine load of 0.2 MPa. Compared with
fuels were higher at low and medium loads but were lower at high Euro V diesel fuel, the acetaldehyde emissions of biodiesel and the
engine loads. From Euro V diesel fuel to biodiesel, the increase of blended fuels were higher; and there were higher acetaldehyde
formaldehyde emission were 6.4%, 9.2%, 8.5%, 1.4% and 1.3%, emissions from the blended fuels except at certain operating
respectively, for the engine loads of 0.08 MPa, 0.20 MPa, 0.38 MPa, conditions. At the engine load of 0.20 MPa, compared with the
0.55 MPa and 0.70 MPa. The authors used other researchers’ ideas Euro V diesel fuel, they observed that the acetaldehyde emissions
for their results proving. Correa [204] studied the carbonyl emis- of biodiesel increased by 13% while the average acetaldehyde
emissions of the blended fuels increased by 21%. Their observation
sions of biodiesel blended with diesel fuel, and reported that the
followed same behaviors as other works. For example, Correa
formaldehyde increased 2.6%, 7.3%, 17.6% and 35.5% respectively
[204] also reported that the acetaldehyde increased by 1.4%, 2.5%,
for 2%, 5%,10% and 15% of biodiesel, compared with baseline diesel
5.4%, and 15.8% respectively for 2%, 5%, 10% and 15% of biodiesel,
fuel. The possible explanations were as follows. Firstly, since the
compared with baseline diesel fuel. And Arapaki et al. [206] found
biodiesel used in their study was produced from waste cooking oil
that acetaldehyde emission increased sharply with biodiesel–die-
which might contain aldehydes compounds formed during the
sel blend, compared with Euro V diesel fuel, and concluded that
frying or cooking process [205]. Thus, it was possible that the
the acetaldehyde emissions could be caused by a higher free gly-
formaldehyde emissions of biodiesel were higher than those of
cerol or total glycerol content of the methyl ester. In addition,
Euro V diesel fuel. Secondly, biodiesel from waste cooking oil
Turrio-Baldassarri et al. [210] reported a 6.3% increase of acet-
contains many short chain chemicals that favor the formation of
aldehyde emission using 20% (v/v) biodiesel. Petit [211] concluded
the shortest chain aldehyde, namely, formaldehyde, during com-
that a decrease of fuel aromatics increased acetaldehyde emission.
bustion [205]. Thirdly, formaldehyde could be produced by the
And acetaldehyde was the incomplete combustion product of
free glycerol which was formed during the esterification process
paraffin. The decreasing aromatic content might increase the
[206, 207].

Fig. 41. Effect of methanol and engine load on formaldehyde emissions [203]. Fig. 42. Effect of methanol and engine load on acetaldehyde emissions [203].
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1479

Fig. 43. Effect of methanol and engine load on unburned methanol [203]. Fig. 44. Effect of methanol and engine load on 1,3-butadiene emissions [203].

paraffin content. Thus, the acetaldehyde emission would increase unregulated emissions of a diesel engine and found that the 1,3-
with the reduction of fuel aromatics. In general, there was an butadiene emissions increased from 20% to 60% engine load and
increase of the acetaldehyde emission with increase of methanol decreased from 60% to 95% engine load. They also believed that the
in the blended fuel. formation of 1,3-butadiene was much easier to occur in O2 rich
Fig. 43 illustrates the unburned methanol emissions. In general, region with lower exhaust gas temperature and lower fuel
their results showed that the unburned methanol emissions of the equivalence ratio. Compared to Euro V diesel fuel, the 1,3- buta-
Euro V diesel fuel and biodiesel were very low. For the blended diene emissions of biodiesel and the BM blends were lower. The
fuels, the unburned methanol emissions decreased as the engine 1,3-butadiene emissions decreased 62%, 20%, 14%, and 12% on
increases from 0.08 MPa to 0.55 MPa but increased slightly from average, based on different engine loads, for biodiesel, BM5, BM10
0.55 MPa to 0.70 MPa. The possible reason was that with increase and BM15, respectively. In addition, Zervas et al. [178] concluded
of engine load, there was an increase in fuel burned as well as an that many straight-chain hydrocarbons could contribute to the
increase in the combustion temperature. The increase in the formation of 1.3-butadiene through H extraction and β-scission. So
amount of methanol in the fuel would cause an increase of the Euro V diesel fuel which contained straight-chain hydro-
unburned methanol but the increase in combustion temperature carbons was more liable to the formation of 1,3-butadiene. As the
led to a net decrease in the unburned methanol. They reported methanol fraction increased, 1,3-butadiene emissions also
when the engine load increased from 0.55 MPa to 0.70 MPa, the increased. However, the difference in 1,3-butadiene emissions
reverse might be true, leading to an increase in unburned between BM10 and BM15 was only slight. From biodiesel to BM15,
methanol. Compared to Euro V diesel fuel, the unburned methanol the 1,3-butadiene emissions increased by 1.4 times on average,
emissions of biodiesel were slightly higher because the biodiesel based on different engine loads. However, Merritt et al. [199]
might contain residual methanol which was used for producing reported a decrease of 1,3-butadiene emissions when the engine
the biodiesel. The methanol content in the blended fuels boosted was operated with ethanol–diesel blends. The addition of metha-
the unburned methanol emissions, especially at light engine load. nol could increase the oxygen contents leading to improvement of
They mentioned a researcher's idea in their work. Zervas et al. diffusion combustion and hence lower 1,3-butadiene emissions.
[167] reported that exhaust methanol could be produced from the On the other hand, according to Takada's conclusion mentioned
unburned fuel or from a recombination of CH3 and OH radicals or above, addition of methanol leading to lower fuel equivalence ratio
CH3O and H radicals. However the last two formation pathways and lower exhaust gas temperature which could increase the 1,3-
were more difficult than the first one. Moreover, with methanol in butadiene. Thus, in Cheung's study, methanol itself might have
the blended fuel, combustion would be delayed due to the higher positive effects on the formation of 1,3-butadiene.
latent heat of evaporation and lower cetane number of methanol, The authors concerned benzene, toluene and xylene (BTX);
in comparison with biodiesel. Thus, some of the blended fuel because they have been identified as carcinogenic, mutagenic, and
would be combusted in the late expansion stroke, leading to an teratogenic [213]. The main sources of benzene, toluene and xylene
increase of unburned methanol. are unburned molecules from fuel, prosynthesis and structural
1,3-butadiene is considered as the one of the most toxic pol- modifications during combustion [200]. Table 30 shows the BTX
lutants in the atmosphere because of its carcinogenic and muta- emissions at engine loads of 0.2 MPa, 0.38 MPa, and 0.55 MPa. It can
genic properties. Moreover, 1,3-butadiene can be converted to be seen from the Table 30 that benzene emissions decreased with
genotoxic products through photochemical reaction in the pre- the increase of engine load. Cheung's observations followed same
sence of nitrogen oxides [212]. For these reasons, the authors behaviors as other works. Di et al. [214] found higher benzene
presented that 1,3-butadiene was considered as a significant toxic emissions at lower engine loads. Takada et al. [194] also showed
pollutant, which was commonly found in the vehicle emissions. higher benzene emissions at lower engine loads and lower exhaust
The variation of 1,3-butadiene emissions is shown in Fig. 44. From gas temperatures, and concluded that benzene could be easily
0.08 MPa to 0.38 MPa, the 1,3-butadiene emissions increased with degraded at high exhaust gas temperature. Compared with Euro V
the engine load, then decreased from 0.38 MPa to 0.70 MPa, except diesel fuel, the benzene emissions of biodiesel were lower. Due to
for Euro V diesel fuel and biodiesel. For Euro V diesel fuel and the characteristics of non-light-aromatics, biodiesel had lower
biodiesel, the 1,3-butadiene emissions increased from 0.55 MPa to benzene emissions than Euro V diesel fuel [200]. With increase of
0.70 MPa. They had a number of proofs for their results from methanol in the blended fuels, benzene emissions decreased. Their
researchers as following. Takada et al. [194] studied the possible reasons were as follows. After addition of methanol in the
1480 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

blended fuel, the combustion temperature decreased, leading to the 5.10.1. Test experimental setup and fuels
increase in benzene emissions, especially at light engine load. On The experimental system and engine specifications are shown
the other hand, with increase of methanol, the increase of oxygen in Fig. 36 and Table 26, respectively. The used fuels include ULSD
content could improve combustion and promote the degradation of and its blends with ethanol and 1-dodecanol. They reported that
benzene and hence reduce the benzene emissions. Moreover, the stability of an ethanol–diesel blend depended on temperature,
unsaturated hydrocarbons in the fuel were precursors responsible water contamination level and the stability additive used [216]. In
for the formation of aromatic and PAH species [201]. Therefore, the that experimental work, anhydrous ethanol with a purity of 99.7%
methanol in the BM blends had a dilution effect to the aromatics was used, and the blended fuel was stored in an air conditioned
precursors, leading to the reduction of the aromatics. It had been room. They found that the blended fuel containing 5% ethanol and
pointed out that the formation of mono and poly-nuclear aromatic 95% ULSD could be maintained in a closed vessel for more than
compounds was related with the lack of oxygen to convert carbon 3 weeks. However, with the increase of ethanol in the blended
atoms to carbon dioxide [200]. Thus with an increase of oxygen in fuel, ULSD and ethanol tended to separate. In order to prevent the
the fuel, there was a reduction of benzene. Toluene and xylene separation, 1-dodecanol was employed as co-solvent.
emissions also decreased with engine load. However, toluene and ULSD and four blended fuels were used. The four blended fuels
xylene emissions had different trends compared with benzene. For were designed to have oxygen concentrations of 2% 4% 6% and 8%,
toluene the lowest emissions were obtained with biodiesel, while
taking into consideration the oxygen in both ethanol and 1-
the blended fuels and the diesel fuels had similar levels of toluene
dodecanol. The first three blends contain 1% 1-dodecanol while
emissions. For xylene, the levels of emissions from the different
blend-4 requires 1.5% of 1-dodecanol to ensure good mixing.
fuels were almost the same.
5.10.2. Emissions testing and analysis
5.9.4. Summary
The gaseous species in the engine exhaust were measured on a
Experiments were conducted on a naturally-aspirated, water-
continuous basis. Unregulated gases including benzene, toluene,
cooled, 4-cylinder, direct-injection diesel engine. In that experi-
formaldehyde, ethanol and the like were measured with the Air-
ment, the engine performance, regulated emissions and unregu-
sense multi-component gas analyzer. In that study, benzene,
lated emissions were studied on a diesel engine fueled with Euro V
toluene and formaldehyde were calibrated directly using standard
diesel fuel, biodiesel, and three biodiesel–methanol blends (BM5,
BM10 and BM15). The results lead to the following conclusions: gases, while ethanol and other compounds were calibrated
through an indirect way based on information provided by the
 Compared to the diesel fuel, biodiesel and the blended fuels had equipment supplier.
higher level of formaldehyde, acetaldehyde and unburned
methanol emissions. 5.10.3. Results and discussion
 With increase in methanol fraction in the blended fuel, the The unburned ethanol concentration in the exhaust gas is
formaldehyde, acetaldehyde, and unburned methanol emissions illustrated in Fig. 45. In general unburned ethanol concentration
increased. decreased with increase of engine load. For blend-1, blend-2 and
 1,3-butadiene emissions of biodiesel and the blended fuels were blend-3, it decreased from 0.08 MPa to 0.38 MPa, but increased
lower than those of the diesel fuel. slightly at 0.55 MPa, after that it decreased again. For example, for
 With increasing of methanol in the fuel, 1,3-butadiene emis- blend-3, it reduced from 287 ppm at 0.08 MPa to 208 ppm at
sions increased as well. 0.38 MPa, increased to 221 ppm at 0.55 MPa but again reduced to
 Compared to the diesel fuel, the benzene emissions of biodiesel 151 ppm at 0.67 MPa. With ethanol in ULSD, the unburned ethanol
and the blended fuels were lower. concentration increased sharply, especially at low engine load. At
 Benzene emissions also decreased with increasing of methanol 90.08 MPa, the concentrations were 5.6 ppm, 126 ppm, 9 160 ppm,
in the fuel. 287 ppm and 360 ppm, respectively, for ULSD, blend-1, blend-2,
 For toluene, the lowest emissions were obtained from biodiesel blend-3 and blend-4. Their results were in agreement with other
while the diesel fuel and the blended fuels generated the same studies. In He et al. [217] work, the unburned ethanol concentra-
level of toluene. The same order of xylene was generated by all tion also increased sharply with the ethanol content. Merritt et al.
the fuels. [199] measured the unburned ethanol concentration on three

5.10. C.S. Cheung and co-workers (2008)

The effect of engine load and ethanol content on engine per-


formance, regulated emissions and unregulated emissions was
investigated in Cheung's study et al. [215]. However, the effect of
ethanol blending percentage on unregulated emissions is selected
for this literature survey study.

Table 30
Benzene, toluene and xylene emissions with different fuels at various loads [203].

mg kW 0.20 MPa 0.38 MPa 0.55 MPa


1
h 1
C6H6 C7H8 C8H10 C6H6 C7H8 C8H10 C6H6 C7H8 C8H10

Euro V 156.24 11.74 27.19 57.49 4.75 10.59 29.67 2.49 4.91
Biodiesel 89.85 6.29 25.26 28.14 2.53 6.75 14.23 1.37 3.86
BM5 64.68 13.97 24.82 28.48 5.12 11.98 11.06 2.10 6.44
BM10 51.91 11.58 25.53 21.57 4.68 10.45 10.60 2.38 5.19
BM15 36.00 11.06 25.49 13.21 3.57 9.91 6.34 2.14 3.78
Fig. 45. Effect of ethanol and engine load on unburned ethanol emission [215].
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1481

0.38 MPa and 0.55 MPa. At 0.20 MPa, the decrease only happened
for blend-2 and blend-3. For each load, the most obvious decrease
occurred in blend-2. They proved the possible explanations as
follows. On the one hand, the addition of ethanol could improve
the diffusion combustion because of the increase of oxygen in the
fuel, which could lead to the reduction of C2H4 and C2H2. On the
other hand, it might cause the decrease of combustion tempera-
ture which was unfavorable for the oxidation C2H4 and C2H2. The
two conflicting factors led to lower C2H4 and C2H2 for blend-2.
Table 31 also illustrates the results of their experiments for 1,3-
butadiene which is an air toxic commonly found in the exhaust gas
of diesel and petrol vehicles. At 0.38 MPa and 0.55 MPa, there were
reductions of 1,3-butadiene with the blended fuel while at
0.22 MPa, there were reductions for blends 2 and 3 but slight
increased for blends 1 and 4. For each fuel, the 1,3-butadiene
emission decreased with the increase of engine load. In their work,
at the engine speed of 1800 rev min  1 0.55 MPa was corre-
sponding to about 67% engine load.
Benzene, toluene and xylene (BTX) are air toxics emitted from
Fig. 46. Effect of ethanol and engine load on formaldehyde emission [215]. many sources, including motor vehicles [118,119]. So it is necessary
to investigate the BTX emissions from diesel engine fueled with
ethanol–diesel blends. As shown in Table 32, benzene emission
decreased with an increasing of engine load. They observed higher
benzene emission under lower loads and lower exhaust tem-
perature, and they explained that benzene was easily oxidized at
high temperature. Thus, they concluded that lower engine loads
gave higher BTX emissions. At the engine load of 0.20 MPa, after
the addition of ethanol, they observed that benzene emission
increased. At the engine loads of 0.38 MPa and 0.55 MPa, benzene
emission decreased for blend-1, blend-2 and blend-3 but increased
for blend-4. They reported that temperature was an important
factor on BTX emissions. The addition of ethanol led to the
reduction of combustion temperature, which contributed to
increase in the benzene emission, especially at low engine load.
However, with the addition of ethanol, the oxygen enrichment
might promote the oxidization of benzene, which contributed to
the reduction in benzene emission. As a result, they found that
benzene emission decreased for blend-1, blend-2 and blend-3 at
0.38 MPa and 0.55 MPa, but, for blend-4, the reduction in gas
temperature might dominate, leading to the increase of benzene
emission. Regarding the toluene and xylene emissions, there were
Fig. 47. Effect of ethanol and engine load on acetaldehyde emission [215]. reductions at all engine loads. The toluene and xylene emissions
were lower for blend-1, blend-2 and blend-3, but higher for blend-
diesel engines on a test cycle and found that the concentrations 4. So it can be anticipated that the combustion temperature and
increased with the increase of ethanol in the fuel. oxygen content in the fuel are opposite factors which dominated
Formaldehyde is an intermediate product of the combustion of the BTX emissions.
diesel fuel [194] and ethanol [218]. Formaldehyde emission, as
shown in Fig. 46, was higher at higher engine loads and decreased 5.10.4. Summary
Experiments were conducted on a diesel engine using ethanol–
with the addition of ethanol in ULSD.
ULSD blended fuels, containing 1–1.5% by volume of 1-dodecanol
Acetaldehyde is converted from incomplete combusted ethanol
as the solvent. Blended fuels containing 6.1%, 12.2%, 18.2% and
[167,209,218]. In Fig. 47, acetaldehyde emissions are below 7 ppm
24.2% by volume of ethanol, corresponding to 2%, 4%, 6% and 8% by
for ULSD. For the blended fuels, with the increase of engine load,
mass of oxygen in the blended fuel, were used in the tests. The
acetaldehyde emission in general decreased except that there was
effect of engine load and ethanol content on engine performance,
a slight increase at 0.67 MPa. With the addition of ethanol, it
regulated emissions and unregulated emissions was investigated.
increased. The maximum acetaldehyde emission was observed
The main summaries are listed below.
23.4 ppm when the engine operated on blend-4 at 0.08 MPa.
Ethene (C2H4) and ethyne (C2H2) are the products of thermal  Formaldehyde emission increased with increasing of engine
pyrolysis from both diesel and ethanol [219,218]. The effect of load, but unburned ethanol, acetaldehyde, ethyne, ethene, 1,3-
ethanol content of the fuel on the concentrations of C2H4 and C2H2 butadiene and BTX all decreased with increasing of engine load.
in the exhaust gas, at the engine loads of 0.2 MPa, 0.38 MPa and  With the addition of ethanol in the blended fuel, the emissions
0.55 MPa, is shown in Table 31. For each fuel, the C2H4 and C2H2 of unburned ethanol and acetaldehyde increased. Formaldehyde
emissions decreased with the increase of engine load. It was likely emission decreased at high engine load, but there was no clear
that the higher combustion temperature at higher engine load trend at low engine load.
contributes to the oxidization of the pyrolytic products. After the  The hydrocarbons ethyne, ethene and 1,3-butadiene decreased
addition of ethanol, the C2H4 and C2H2 concentrations reduced at sharply with the addition of ethanol at 0.55 MPa, and reduced
1482 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

Table 31
Ethene, ethyne and 1,3-butadiene emissions at various engine loads [215].

1800 (rev min  1) 0.20 MPa 0.38 MPa 0.55 MPa

C2H4 (ppm) C2H2 (ppm) C4H6 (ppm) C2H4 (ppm) C2H2 (ppm) C4H6 (ppm) C2H4 (ppm) C2H2 (ppm) C4H6 (ppm)

ULSD 35.8 106 46.2 35 97.2 45.2 22.4 54.3 31.1


Blend-1 44.7 109 49.0 30.1 82.8 44.4 19.2 45.7 24.3
Blend-2 23.7 49.6 29.5 22 43.5 28.1 14.4 26.4 21
Blend-3 33.6 62.5 41.1 28.1 47.5 35.8 16.8 28.1 21.8
Blend-4 41 73.8 50.7 30.1 53.1 37.3 16.3 27.7 23.6

Table 32
Benzene, toluene and xylene emissions at various engine loads [215].

mg kWh  1 0.20 MPa 0.38 MPa 0.55 MPa

C6H6 C7H8 C8H10 C6H6 C7H8 C8H10 C6H6 C7H8 C8H10

ULSD 79.2 17.1 69.7 57.0 8.3 33.2 28.1 3.3 18.7
Blend-1 95.9 8.7 58.3 54.0 4.3 28.9 23.6 2.6 17.0
Blend-2 97.2 9.1 38.0 53.0 4.3 18.2 20.8 2.5 10.6
Blend-3 112.6 9.4 55.3 48.9 4.1 24.5 26.0 1.9 12.5
Blend-4 153.0 13.8 66.8 63.4 5.8 25.3 30.3 3.2 13.4

slightly at 0.38 MPa, but at 0.20 MPa, the reduction of these


hydrocarbons only occurred in blend-2 and blend-3.
 Addition of ethanol in the diesel fuel could either increase or
decrease the emissions of ethyne, ethene and 1,3-butadiene,
resulting in more reductions in blend-2.
 The effect of ethanol on BTX emissions depended on both
engine load and ethanol content. Fig. 48. VT shed container with mass spectrometer to the left [19].
 At 0.20 MPa, benzene emission increased with ethanol while at
0.38 MPa and 0.55 MPa, it decreased for blend-1, blend-2 and hydrocarbons. That instrument, along with an Air Sense Mass
blend-3 but increased for blend-4. Spectrometer, was used for the tests.
 Toluene and xylene reduced with ethanol in the fuel but the
reduction was higher for blend-1, blend-2 and blend-3, but 5.11.3. Results and discussion
lower for blend-4. Changes over time in the air levels of the measured constituent
as the tests progressed were presented in their study in chart form
to facilitate interpretation of the measurements. The final con-
5.11. M. Henke and co-workers (2005)
centrations at the end of the tests were also presented in bar graph
format.
The aim of Henke's project et al. [19] was to study the impact of
The authors reported that, unsurprisingly, the ethanol content
using such blends on evaporative emissions by carrying out
of the vapor proved to increase with increasing ethanol content in
measurements with different grades of base gasoline and different
the test container to some extent. However, the relationship was
blending proportions of ethanol.
not linear. Two factors contributed to this pattern. Naturally, the
vapor pressure was positively correlated to the ethanol content of
5.11.1. Test experimental setup and fuels
the blend in the container. In addition, however, ethanol enhanced
All tests were performed at AVL MTC in Haninge, Sweden, in
the vapor pressure according to a relationship that was not linear
February 2005. The AVL MTC Motor test center was an accredited
and peaks at relatively low ethanol contents of around 10% in
laboratory for automotive testing and had been in operation for
ethanol–gasoline blends. This was shown in their work since the
approximately 15 years. AVL MTC had experience of more than 10 vapor contents (ppm) were virtually the same for both the 5% and
years of testing for the Swedish Environmental Protection Agency 10% blends, while those of both the 0% and the E85 blends were
and the Swedish National Road Administration. considerably lower. Fig. 49 represents the changes over time in the
The evaporative emissions from two summer gasoline fuels ethanol concentration in the VT Shed.
(with Reid Vapor Pressures (RVPs) of 63 kPa and 70 kPa, respec- They indicated that butane is the main compound used to
tively) blended with low percentages of ethanol (0%, 5%, 10% and regulate the vapor pressure of gasoline. It was removed to reduce
15%) had been measured in a VT Shed. For reference purposes E85 the vapor pressure when required, for instance in summer gaso-
(85% ethanol) was also measured in the same manner. line, which was used in higher ambient temperature ranges. The
gasoline with the higher Reid Vapor Pressure (RVP) index was
5.11.2. Emissions testing and analysis therefore expected to have a higher content of vaporizing butane.
All tests were performed using a gas-proof test container (not This expectation was confirmed in their tests, as shown in Fig. 50.
the fuel container mentioned below) in which the evaporative In addition, the butane vapor pressure-enhancing effect of the
behavior of whole cars was normally tested. It was called a VT shed ethanol blended in the base gasoline was probably maximal at
as both its volume and temperature were controlled (Fig. 48). A contents between 5% and 10%.
standard component of that kind of equipment was a Flame The authors reported that benzene is an aromatic hydrocarbon
Ionization Detector (FID) for measuring the total emitted with both ozone formation and carcinogenic potential, so its
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1483

Fig. 49. Changes over time in the ethanol concentration in the VT shed [19]. Fig. 50. Changes over lime in the butane concentration in the VT shed [19].

emission levels were strictly restricted. Aromatics, however, were


widely used to substitute lead as an anti-knock compound in
gasoline. According to their results, benzene was also created
during the combustion process in engines and max concentration
increased compared to base levels approx. 20% with E5 (Fig. 51).
Fig. 52 shows the changes over time in the toluene con-
centration in the VT shed. And Fig. 53 represents the changes over
time in the xylene concentration in the VT shed. Max concentra-
tion increased compared to base levels, approx. 20% (with E5).
Max concentration increased compared to base levels,
approximation 20% (with E5) as shown in Fig. 54.
The concentrations of the measured emissions from E85 were
included as a separate series since they had no information on the
vapor pressure of the base gasoline used for blending. However, it
probably had a relatively high RVP since this level of ethanol
lowers the Reid Vapor Pressure of the final mix. It can be seen from Fig. 51. Changes over time in the benzene concentration in the VT shed [19].

Figs. 55–60 that the concentration at the end of the test (ppm) of
butane, benzene and MTBE for E5 was more compared to other
blend percentages. And the concentration at the end of the test
(ppm) ethanol, toluene and xylene of for E5 was more compared
to other blend percentages.

5.11.4. Summary
All tests were performed using a gas-proof test container in
which the evaporative behavior of whole cars was normally tested.
It was called a VT shed as both its volume and temperature were
controlled. The evaporative emissions from two summer gasoline
fuels (with Reid Vapor Pressures (RVPs) of 63 kPa and 70 kPa,
respectively) blended with low percentages of ethanol (0%, 5%, 10%
and 15%) had been measured in a VT Shed. For reference purposes
E85 (85% ethanol) was also measured in the same manner. The
results lead to the following conclusions: Fig. 52. Changes over time in the toluene concentration in the VT shed [19].

 The ethanol content of the vapor proved to increase with 5.12. P.M. Merritt and co-workers (2005)
increasing ethanol content in the test container to some extent.
 The gasoline with the higher Reid Vapor Pressure (RVP) index Merritt's project et al. [199] had generated information on the
was therefore expected to have a higher content of vaporizing
exhaust emissions effects of various blends of ethanol in diesel fuel
butane.
in non-road diesel engines.
 Benzene, Toluene, Xylene and Methyl Teriary Buthyl Ether
(MTBE) of E85 were lower compared to other fuels.
 Concentration at the end of the test (ppm) of butane, benzene 5.12.1. Test experimental setup and fuels
and MTBE for E5 was more compared to other blend Three heavy-duty, Tier II compliant, non-road diesel engines
percentages. were used. The engines represented different fuel system and
 Concentration at the end of the test (ppm) ethanol, toluene and emissions control technologies and varied in displacement from
xylene of for E5 was more compared to other blend percentages. 6.8 to 12.5 L. The engines characteristics are summarized in
1484 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

Fig. 57. Benzene concentration at the end of the test (ppm) [19].

Fig. 53. Changes over time in the xylene concentration in the VT shed [19].

Fig. 58. Toluene concentration at the end of the test (ppm) [19].

Fig. 54. Changes over time in the MTBE concentration in the VT shed [19].

Fig. 59. Xylene concentration at the end of the test (ppm) [19].

Fig. 55. Ethanol concentration at the end of the test (ppm) [19].

Fig. 60. MTBE concentration at the end of the test (ppm) [19].

Table 33 and include the three most common types of fuel injec-
tion systems.
The reference fuel for that program was No. 2D certification
diesel, with a nominal sulfur content of 400 ppm. Three different
blends of ethanol in that reference fuel were prepared, at 7.7%, 10%,
and 15% by volume. Three additive suppliers provided material to
enhance the stability and performance of the ethanol in diesel
Fig. 56. Butane concentration at the end of the test (ppm) [19]. blends.
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1485

Table 33 Table 34
Test engines characteristics [199]. Part 89 test modes and weighting factors [199].

Engine model 6081HRW28 6068HF275 6125HRW02 Mode 1 2 3 4 5 6 7 8


Displacement (L) 8.1 6.8 12.5 Speed Rated Intermediate Idle
Rated speed (rpm) 2200 2000 2100
Rated power (kW (hp)) 224 (301) 129 (172) 375 (500) Percent torque 100 75 50 10 100 75 50 0
Intermediate 1400 1400 1500 Weight factor 0.15 0.15 0.15 0.10 0.10 0.10 0.10 0.15
speed (rpm)
Peak torque (N-m (lb- 1361 (1004) 725 (535) 1989 (1467)
ft))
Inlet restriction (kPa) 2.99 2.99 2.99 Table 35
Exhaust 7.45 7.45 7.45 Soluble organic fraction by mode for 8.1-L-engine percent of total particulate matter
restriction (kPa) [199].
Turbocharged/inter- Yes/Yes Yes/Yes Yes/Yes
cooled Fuel type Baseline average 7.7% Ethanol 10% Ethanol 15% Ethanol
Inter-cooling type Air/Air Air/Air Air/Air
Inter-cooler outlet 60 60 60 Mode 1 40.5 56.3 58.2 58.0
temp. (°C) Mode 2 35.9 48.8 41.4 48.6
Inter-cooler ΔP (kPa) 12.45 (50) 12.45 (50) 12.45(50) Mode 3 38.2 40.2 39.4 39.0
Fuel system High pr., com- Rotary pump Electronic unit Mode 4 88.4 88.0 87.6 93.0
mon rail line nozzle injector Mode 5 33.6 39.7 37.1 45.1
Mode 6 30.8 44.1 38.4 49.5
Mode 7 46.7 66.5 48.8 67.7
Mode 8 87.9 93.6 82.9 90.0
Exhaust emission characterization was performed as specified
under CFR Title 40, Part 89. For non-road heavy-duty engines, the
regulation outlines specific requirements for setting up the test Table 36
engine and pre-test activities, as well as all aspects of conducting Unregulated emissions summary for 8.1-liter engine averaged, composite results
the testing and collection and analysis of gaseous samples. The over 8-mode test, mg/hp-h [199].
8-mode test cycle was utilized in that test program. Table 34
Fuel type Baseline fuel 7.7% 10% 15%
shows the Part 89 test modes and weighting factors. Ethanol Ethanol Ethanol
Two consecutive runs of the 8-mode test and two FTP smoke
tests (40 CFR Parts 86 and 89) were performed for each fuel Formaldehyde 9.56 10.21 10.52 11.00
Acetaldehyde 3.70 4.71 4.68 5.51
composition. In a regular 8-mode test they stabilize the engine for
Acrolein 1.87 1.83 1.43 1.59
5 min and sample for 5 min. To accumulate a sufficient dilute Propionaldehyde 0.68 0.83 1.18 1.22
exhaust sample for unregulated emissions analysis, each mode Methyl ethyl ketone 0.53 0.59 0.09 0.09
was run for a number of minutes equivalent to its weight factor in Ethanol 0.32 16.58 17.65 26.89
percent (stabilization time of 5 min was unchanged). For example, 1,3-Butadiene 0.90 0.92 0.68 0.68
Methane 2.09 0.32 0.53 0.15
a mode with a 0.10 weight factor received a 10-min sampling Benzene 0.81 0.70 0.69 0.72
period. This approach extended the total sampling duration for the Toluene 1.00 1.61 0.90 1.17
8-mode test from 40 to 100 min. For the PAH and NPAH sampling, Ethylbenzene 0.51 0.53 0.42 0.55
one set of collection media was used to collect a composite sample M-& P-Xylene 0.85 0.74 0.61 0.89
O-Xylene 0.39 0.34 0.38 0.43
for each 8-mode test.
Hexane 0.03 0.11 0.07 0.16
Styrene 0.12 0.07 0.11 0.10
5.12.2. Emissions testing and analysis
Their target list for unregulated emissions included the soluble
organic fraction of the PM (SOF), aldehydes and ketones (ALD), pyrene were higher. An increasing trend with alcohol content was
ethanol (ETH), individual hydrocarbons (IHC), polycyclic aromatic observable for benzo(a)anthracene and chrysene in this view. For
hydrocarbons (PAH), and 1-nitropyrene. For each mode, SOF was the lighter molecular weight compounds in the particulate-phase,
determined by extracting a 50% section of the particulate-laden all compounds were lower in the ethanol blends than in the
90mm Pallflex filters using a Soxhlet apparatus with toluene– baseline diesel. For the heavier molecular weight compounds in
ethanol solvent. Solvent was evaporated from the extracted par- the particulate-phase, benzo(b)fluoranthene, benzo(k)fluor-
ticulate filters and the filters were re-weighed. The difference in anthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, and dibenzo(a,
mass was the solvent-extractable material. h)anthracene were all higher for the ethanol blends, but 1-
nitropyrene was lower.
5.12.3. Results and discussion The soluble organic fraction of particulate matter is presented
Soluble organic fraction of particulate matter is summarized in in Table 38. For the 6.8-L engine, smoke opacity was reduced in
Table 35. SOF tended to increase with ethanol content as com- proportion to ethanol content for all operational modes. SOF was
pared to baseline diesel fuel. SOF levels were, as they expected, highest for modes 4 and 8 and in general was higher with
highest for the low load modes 4 and 8. Mode 7 exhibited the increasing ethanol content. Results for modes 1 and 8 did not
largest difference in SOF between baseline diesel fuel and an follow this trend, however, where SOF was reduced with the
ethanol blend (in this case the 15% blend). ethanol blended fuels.
Individual hydrocarbon emissions results are presented in Significant increases were observed in emissions of acet-
Table 36. Increasing of formaldehyde, acetaldehyde, and ethanol aldehyde (and of ethanol) with increasing ethanol content. They
were observed with increasing of ethanol content. Emissions of reported that, emissions of 1,3-butadiene were reduced with
1,3-butadiene and benzene were reduced slightly with the ethanol ethanol blends, but benzene emissions were not significantly
blends. PAH and NPAH results are presented in Table 37. It notes affected. Individual hydrocarbon emissions results are summar-
that PAH and NPAH compounds are expressed in nanograms ized in Table 39.
(10  9 g). In the vapor phase, acenaphthylene and fluorene were PAH results are presented in Table 40. For the lighter molecular
observed lower for the alcohol blends, but fluoranthene and weight compounds for the vapor phase only, phenanthrene was
1486 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

Table 37
PAH and NPAH compounds for 8.1-l engine, composite results over 8-mode test, ng/hp-h [199].

Fuel type Baseline Fuel 7.7% Ethanol 10% Ethanol 15% Ethanol

Compound/phase Vapor phase PM phase Vapor phase PM phase Vapor phase PM phase Vapor phase PM phase

Naphthalene 224,515 237 234,480 84 472,781 144 219,800 95


Acenaphthylene 1244 146 271 72 277 97 49 62
Acenaphthene 30,207 89 30,172 51 35,886 63 30,678 41
Fluorene 59,566 471 47,348 207 56,904 295 45,485 162
Phenanthrene 99,538 7419 91,207 3428 103,191 4084 76,198 2244
Anthracene 6519 710 6443 331 6842 368 5123 208
Fluoranthene 2274 2390 2935 348 3266 1627 2657 919
Pyrene 3674 5146 6413 3741 6267 3959 5685 2493
Benzo(a)anthracene 7 358 16 428 13 403 17 275
Chrysene 16 834 30 830 30 877 35 617
Benzo(b)fluoranthene 2 145 1 179 2 183 1 160
Benzo(k)fluoranthene 2 84 1 155 1 126 0 125
Benzo(a)pyrene 1 87 0 171 1 136 0 111
Indeno(1,2,3-c,d)pyrene 1 14 1 27 1 32 1 34
Dibenzo(a,h)anthracene 2 5 0 8 0 10 0 8
1-Nitropyrene 0 129 1 68 1 90 2 79

Table 38 Table 40
Soluble organic fraction by mode for 6.8-l engine, percent of total particulate PAH and NPAH compounds for 6.8-L engine, composite results over 8-mode test,
matter [199]. ng/hp-h [199].

Fuel type Baseline Fuel 7.7% Ethanol 10% Ethanol 15% Ethanol Compound/fuel type Baseline fuel 7.7% 10% 15%
Ethanol Ethanol Ethanol
Replicate Test 1 Test 2 Test 1 Test 2 Test 1 Test 2 Test 1 Test 2
Formaldehyde 16.56 14.77 14.88 20.11
Mode 1 12.8 16.6 11.4 12.7 11.7 13.8 15.3 12.4 Acetaldehyde 4.82 6.27 7.56 10.82
Mode 2 22.1 21.4 26.6 23.5 19.5 26.5 36.3 33.0 Acrolein 2.04 0.47 0.75 2.68
Mode 3 50.1 48.9 53.9 66.0 49.6 61.8 73.8 63.0 Propionaldehyde 2.35 1.32 1.39 1.81
Mode 4 78.9 83.5 84.8 80.4 75.8 84.3 83.4 88.5 Methyl ethyl ketone 0.15 0.13 0.30 0.16
Mode 5 6.8 11.7 10.9 9.3 8.5 11.8 14.7 14.4 Ethanol 0.44 23.22 32.82 52.66
Mode 6 28.7 21.8 26.5 22.2 29.9 27.2 34.1 33.2 1,3-Butadiene 1.70 1.40 0.56 1.03
Mode 7 46.5 48.8 60.5 48.4 58.7 60.1 58.3 62.2 Methane 0.71 1.14 2.37 3.11
Mode 8 91.4 85.9 61.3 75.2 92.8 88.2 67.9 499.0 Benzene 1.78 1.68 1.79 1.82
Toluene 3.05 0.84 1.80 1.83
Ethylbenzene 0.90 0.68 0.51 0.76
Table 39 m-& p-Xylene 1.36 0.97 0.95 2.08
Unregulated emissions summary for 6.8-liter engine averaged, composite results o-Xylene 0.63 0.50 0.60 1.50
over 8-mode test, mg/hp-hr [199]. Hexane 0.11 0.26 0.36 0.48
Styrene 0.26 0.18 0.11 0.19
Compound/fuel type Baseline fuel 7.7% 10% 15%
Ethanol Ethanol Ethanol
Table 41
Formaldehyde 16.56 14.77 14.88 20.11 Soluble organic fraction by mode for 12.5-L engine, percent of total particulate
Acetaldehyde 4.82 6.27 7.56 10.82 matter [199].
Acrolein 2.04 0.47 0.75 2.68
Propionaldehyde 2.35 1.32 1.39 1.81 Fuel type Baseline fuel 7.7% Ethanol 10% Ethanol 15% Ethanol
Methyl ethyl ketone 0.15 0.13 0.30 0.16
Ethanol 0.44 23.22 32.82 52.66 Replicate Test 1 Test 2 Test 1 Test 2 Test 1 Test 2 Test 1 Test 2
1,3-Butadiene 1.70 1.40 0.56 1.03
Methane 0.71 1.14 2.37 3.11 Mode 1 63.2 51.8 54.8 63.2 65.7 52.0 65.3 65.8
Benzene 1.78 1.68 1.79 1.82 Mode 2 49.1 41.1 59.7 49.1 55.6 58.7 67.5 61.4
Toluene 3.05 0.84 1.80 1.83 Mode 3 40.9 36.9 44.9 40.9 40.7 44.6 44.9 37.9
Ethylbenzene 0.90 0.68 0.51 0.76 Mode 4 44.4 32.0 44.6 44.4 42.0 42.2 49.7 47.8
m-& p-Xylene 1.36 0.97 0.95 2.08 Mode 5 74.6 68.0 67.7 74.6 65.6 68.8 85.4 62.0
o-Xylene 0.63 0.50 0.60 1.50 Mode 6 80.1 58.0 82.2 80.1 70.3 73.5 100 69.2
Hexane 0.11 0.26 0.36 0.48 Mode 7 63.2 65.7 72.4 63.2 69.0 56.7 56.4 62.4
Styrene 0.26 0.18 0.11 0.19 Mode 8 100 100 100 100 100 100 100 98.0

modes 2 and 4. SOF was highest in mode 8. In mode 8, there was


lower for the alcohol blends, but fluoranthene and pyrene were little difference in SOF for the four fuels.
higher. For the lighter molecular weight compounds in the parti- Individual hydrocarbon emissions results are summarized in
culate phase only most compounds were lower in the ethanol Table 42. Emissions of acetaldehyde and ethanol increased with
blends. They measured that, in the heavier molecular weight increasing of ethanol content. Other aldehydes tended to increase
compounds for the particulate phase, all compounds except 1- as well. Benzene and 1,3-butadiene increased with increasing
nitropyrene were higher in the ethanol blends. Lower emission ethanol content, but were all lower than base fuel.
rates were seen for 1-nitropyrene with the ethanol blends. PAH and NPAH results are presented in Table 43. For the lighter
Soluble organic fraction of particulate matter is summarized in molecular weight compounds in the vapor phase, an increasing
Table 41. SOF showed consistent increases with ethanol content in trend for pyrene was observed, and naphthalene, acenaphthene,
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1487

Table 42 Holden car decreased its benzene emissions with increased driv-
Unregulated emissions summary for 12.5-liter engine averaged, composite results ing distance. The benzene emission was lower when the E20 fuel
over 8-mode test, mg/hp-h [199].
was used as fuel and the emission was reduced at increased
Compound/fuel type Baseline fuel 7.7% 10% 15% driving distance. Comparative benzene emissions from the
Ethanol Ethanol Ethanol Hyundai car was that benzene emissions increased as the driving
distance increased which was valid for both fuels tested. Further-
Formaldehyde 9.16 10.50 11.04 11.78
more, the Subaru car had larger benzene emissions from the E20
Acetaldehyde 2.78 4.60 5.23 6.65
Acrolein 1.05 1.23 0.97 1.25 fuel compared to neat gasoline. From Fig. 61, it can be concluded
Propionaldehyde 0.93 0.95 1.42 1.11 that there was a relatively large variation in benzene emissions
Methyl ethyl ketone 0.12 0.15 0.13 0.12 due to fuel and accumulated driving distance and vehicle tested.
Ethanol 0.36 17.11 25.12 34.51
Because of this, they reported that it was difficult to make firm
1,3-Butadiene 1.16 0.21 0.56 0.74
Methane 1.64 1.66 1.47 1.01 conclusions with respect to benzene emissions vehicle
Benzene 1.13 0.57 1.01 0.98 dependency.
Toluene 1.09 1.20 1.65 1.60 Average acetaldehyde emissions from all vehicles tested and
Ethylbenzene 0.43 0.47 0.70 0.57
the results are shown in Fig. 62. It can be seen from Fig.62 that
m-& p-Xylene 0.89 0.74 1.12 0.73
o-Xylene 0.42 0.39 0.49 0.34 increasing of accumulate driving distance resulted in an increasing
Hexane 0.03 0.20 0.27 0.15 of acetaldehyde emission; however the Toyota car was excluded.
Styrene 0.11 0.11 0.09 0.08 This seemed to be fuel independent. They mentioned that, there
was a relatively large variation in acetaldehyde emissions due to
fuel and accumulated driving distance and vehicle tested as shown
fluoranthene were higher in the ethanol blends. Acenaphthylene
in Fig. 62. Because of this, they reported that it was difficult to
and acenaphthene were lower in the ethanol blends. For the
make firm conclusions with respect to formaldehyde emissions
heavier molecular weight compounds for the vapor phase, benzo
vehicle dependency.
(a)anthracene and chrysene showed a definite increasing trend
Average formaldehyde emissions from all vehicles tested is
with ethanol concentration. Benzo(a)pyrene was higher in the
shown in Fig. 63. All of the tested vehicles had increased for-
ethanol blends. However, 1-nitropyrene was lower in the ethanol
maldehyde emissions with respect to increased accumulative
blends. In the particulate-phase decreasing trends for ace-
driving distance. The relative emissions of formaldehyde were
naphthylene, fluorene, phenanthrene, anthracene, fluoranthene,
vehicle and fuel dependent.
and pyrene were seen with increasing ethanol content. The hea-
A report by Augin and co-workers in 2004 [221] with a limited
vier compounds were higher for the ethanol blends in the parti-
distribution from Environment Canada described a series of
culate phase, but 1-nitropyrene was lower.
comparative tests carried out on five vehicles using neat gasoline
5.12.4. Summary and ethanol–gasoline blends (with ethanol contents of 10%, 15%
The experiments were performed on three heavy-duty, Tier II and 20%). The aim of their program was to compare emissions
compliant, non-road diesel engines. Those engines represented from the vehicles when using neat gasoline and oxygenated fuel.
different fuel system and emissions control technologies and var- The vehicles used in the tests are listed in Table 44 and the fuel
ied in displacement from 6.8 to 12.5 l. The reference fuel for that properties are shown in Table 45.
program was No. 2D certification diesel, with a nominal sulfur The emission tests were carried out in accordance with the US
content of 400 ppm. Three different blends of ethanol in that Federal Test Procedure (FTP 75) and two repeats of each cycle were
reference fuel were prepared, at 7.7%, 10%, and 15% by volume. The performed on each vehicle in order to provide a minimal measure
conclusions drawn from that study are the following points: of the repeatability, according to the authors’ report. The results of
the emission tests are shown as means for the five vehicles in
 Emissions of benzene and 1,3-butadiene reduced with the Tables 46–48. The presented data provided clear indications that
ethanol fuels. the emissions of formaldehyde increased when using ethanol
 No clear trends were discernable for the PAH compounds, but 1- blended gasoline. The acetaldehyde emissions increased when
nitropyrene was consistently reduced with use of the ethanol using ethanol blended gasoline. The emissions of the measured
blends. specific hydrocarbons either decreased or increased when using
 Increasing ethanol concentration led to higher emissions of ethanol blended gasoline.
acetaldehyde and ethanol. He et al. [222] presented a study of exhaust emission char-
 Emissions of toxics such as benzene and 1,3-butadiene were acteristics from an engine with an electronic fuel injection (EFI)
reduced with the use of ethanol. system with and without a three-way catalyst (TWC) system. The
 1-nitropyrene decreased with use of ethanol in all cases. engine was run on neat gasoline, and both 10% ethanol (E10) and
 Heavy PAH compounds generally increased in the particulate 30% ethanol (E30) gasoline blends (Table 49). They conducted the
phase with ethanol use, and although less pronounced, a gen- experiment operating the engine at idle speed and using E30 as
eral decrease in light PAH compounds in the particulate phase fuel. It was observed that ethanol and acetaldehyde emissions
with ethanol use. were increased with increasing percentage of ethanol blending. It
was also found that the TWC system reduced acetaldehyde
5.13. Overview of researchers’ works since 2004 to 1983 emissions, but had a lower conversion efficiency for ethanol.
A series of emission tests from five vehicles fueled with a blend
In a study which carried out in Australia the unregulated of 10% ethanol in gasoline had been carried out by AEA Technology
emissions such as BTEX and aldehydes were measured by Orbital plc (AEA Technology is a British technology company), Harwell,
Engine Company in 2004 [220]. The emission measurements were UK, on behalf of the UK Department of Transport in 2002 [223].
made using fuels comprising of 20% ethanol (E20) in gasoline and The aim of the tests was to generate data to be used as emission
neat gasoline. Furthermore, the vehicle emissions were deter- factors for gasoline-fueled vehicles in the European context. The
mined at both 6400 and 80,000 km odometer readings. Fig. 61 five vehicles tested are listed in Table 50. The Toyota Yaris was
shows average benzene emissions from five tested cars. The tested twice, since significant changes in the test procedure for
1488 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

Table 43
PAH and NPAH compounds for 12.5-L engine, composite results of 8-mode test, ng/hp-h [199].

Fuel type Baseline Fuel 7.7% Ethanol 10% Ethanol 15% Ethanol

Compound/phase Vapor phase PM phase Vapor phase PM phase Vapor phase PM phase Vapor phase PM phase

Naphthalene 143,664 177 190,188 149 154,824 98 707,495 106


Acenaphthylene 28,398 91 22,296 64 23,297 56 24,732 35
Acenaphthene 30,382 67 32,291 41 31,932 25 42,270 25
Fluorene 70,822 269 56,947 184 74,026 151 78,878 105
Phenanthrene 129,464 5001 107,998 3246 124,868 2566 148,862 2054
Anthracene 11,327 549 9195 332 10,309 275 11,839 204
Fluoranthene 2583 1940 3162 1405 3225 1113 4398 1021
Pyrene 4573 4278 7756 4023 8929 3214 11,400 2775
Benzo(a)anthracene 18 238 27 368 31 368 66 311
Chrysene 33 601 56 745 76 713 128 668
Benzo(b)fluoranthene 6 71 5 130 8 122 8 142
Benzo(k)fluoranthene 7 73 4 126 5 130 7 115
Benzo(a)pyrene 0 51 0 93 2 118 4 75
Lndeno(1,2,3-cd)pyrene 3 13 0 33 3 40 3 35
Dibenzo(a,h)anthracene 0 5 0 6 0 7 0 7
1-Nitropyrene 6 28 1 18 1 18 1 23

Fig. 61. Benzene emissions (mg/km) gasoline versus E20 [220]. Fig. 63. Formaldehyde emissions (mg/km) gasoline versus E20 [220].

Table 44
Selected data for the tested vehicles [221].

Vehicle Model year Engine No. of Transmission Test


displace cylinders inertia
ment (L) (kg)

Pontiac 1999 3.4 V6 Automatic 1590


Grand Am
Honda 2000 1.0 3 Automatic 966
Insight
Chevrolet 1999 5.3 V8 Automatic 2160
Silverado
Toyota Echo 2001 1.5 4 Automatic 1136
Honda Civic 2001 1.6 4 Automatic 1250

Table 45
Fig. 62. Acetaldehyde emissions (mg/km) gasoline versus E20 [220]. Selected data for the used fuels in the emission tests [221].

unregulated emissions was made after the third vehicle was Fuel properties SGCa 10% Ethanol 15% Ethanol 20% Ethanol

tested.
% C by mass 86.7 82.8 81.0 79.3
The used fuels for the tests were neat gasoline and a blend of % H by mass 13.6 13.5 13.5 13.5
10% ethanol in gasoline. According to their report, an interesting % O by mass – 3.7 5.5 7.3
point to note is that the RVP of the neat gasoline and the blended Density [g/mL] 0.7453 0.7497 0.7519 0.7541

fuel was 60 kPa and 66.5 kPa, respectively. The emission tests were a
Summer Grade Commercial baseline tests of fuel.
conducted according to the current European test cycle, ECE/EUDC,
and six of the test cycles designed by the Warren Spring Labora-
tory (WSL), as listed in Table 51. decreased in most cases. There were significant differences between
Their tests results indicated that the unregulated emissions were vehicles, so for some vehicles the emissions were increased while
increased for a few components while the emissions were for others they were decreased. As they expected, the emission of
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1489

acetaldehyde was increased in most cases. In Table 58 the numbers particles and BaP of E5 observed higher than gasoline at tem-
of increases (þ) and decreases ( ) are presented. Unfortunately, perature of 22 °C. As can be seen from the data in Table 60 the
the unregulated emissions were only measured from three vehicles ambient temperature had a clear impact on the emissions, espe-
(plus a repeated measurement on the Toyota Yaris) and there were cially the particulate emissions and (thus) PAHs. Starting the
only four comparative measurements for benzene and nitrous oxide engine at low temperatures was known to have a stronger effect
as shown in Tables 52–57. As can be seen in Table 58, ammonia and on the emissions when using fuels with high contents of an
PAH emissions were only measured from three vehicles. alcohol than when using neat gasoline.
Schifter et al. [224] collected mean emission factors from three In addition an extensive investigation by Egeback and co-
TWC-equipped cars running on 3%, 6% and 10% by volume etha- workers in 1983 [90] was carried out in Sweden in which the
nol–gasoline blends in Table 59. They observed that benzene and amounts of both regulated and non-regulated constituents emit-
acetaldehyde emissions increased with increasing ethanol con- ted were compared when using various types of gasoline, LPG,
tents, while formaldehyde emissions and the ozone formation diesel oil, different blends of methanol and a blend with 23%
factor (g O3/g Non-Methane Organic Gases, NMOG) decreased. ethanol in lead-free gasoline (E23) to fuel the following vehicles:
In an investigation by Egeback et al. in 1984 [225] five well- five Saabs, five Volvos, one Volkswagen and one Mercedes Benz.
maintained and carefully-checked cars without catalytic con-
verters and one equipped with a three-way catalyst system were Table 49
used. The vehicles were tested with unchanged fuel–air ratio Fuel properties of ethanol gasoline fuel blends [222].

settings (which were set for neat gasoline) with three different Fuel parameters Neat gasoline E10 E30
fuels. The used fuels were neat gasoline, 5% ethanol mixed with
unleaded gasoline (E5), and 15% methanol mixed with a refinery- Density at 19 °C 0.736 0.741 0.751
RON 92.4 95.0 99.7
produced gasoline. All fuels were tested at 22 °C and the neat
MON 81.2 82.3 86.6
gasoline and ethanol mixture were also tested at þ5° and 7 °C. A IBP 36.0 37.5 40.0
comparison of the emissions from the catalyst-equipped vehicle 10% 55.2 49.0 52.7
adapted for the use of alcohol in neat lead-free gasoline can be 50% 92.5 73.2 72.5
90% 153.7 149.8 145.7
seen in Table 60.
FBP 184.5 181.0 181.5
Their results showed that formoaldehyde and PAH of E5 were
lower than those of gasoline at temperature of 22 °C. But acrolein,
Table 50
Table 46 Vehicles selected for emission testing and measurement of fuel economy [223].
Emissions of aldehydes when using neat gasoline and three different blends of
ethanol [221]. Vehicle Model Engine size Emission Mileage
identifier (L) Standards (km)
Vehicle Formaldehyde Acetaldehyde
1&6 Toyota Yaris 1.0 Euro III 22,000
Honda Insight Grand Am Honda Insight Grand Am 2 Vauxhall 2.2 Euro III 19,000
US FTP cycle mg/km mg/km mg/km mg/km Omega
3 Fiat Punto 1.2 Euro II 51,000
0% Ethanol 0.019 0.603 0.143 0.298 4 VW Golf 1.6 Euro III/IV 21,000
10% Ethanol 0.087 0.615 0.273 0.653 5 Rover 416 1.6 Euro II 117,000
15% Ethanol 0.491 0.516 0.373 0.926
20% Ethanol 0.665 0.578 0.385 0.814
Table 51
Test cycles [223].

Table 47 Cycle Cycle Hot/cold Duration (s) Target distance


Emissions of aldehydes when using neat gasoline and three different blends of identifier start (km)
ethanol [221].
1 ECE/EUDC Cold 1180 11.01
Vehicle Formaldehyde Acetaldehyde (Dir.98/69)
2&8 WSL Congested Hot 1030 1.91
Toyota Echo Honda Civic Toyota Echo Honda Civic 3&9 WSL Urban Hot 1205 6.14
US FTP cycle mg/km mg/km mg/km mg/km 4 & 10 WSL Suburban Hot 480 5.52
5& 11 WSL Rural Hot 586 10.95
0% Ethanol 0.534 0.311 0.261 0.099 6 & 12 WSL Motorway Hot 306 7.96
10% Ethanol 0.360 0.870 0.379 0.721 90
15% Ethanol 0.690 0.416 1.044 0.435 7 & 13 WSL Motorway Hot 256 8.18
20% Ethanol 0.671 0.572 1.311 0.597 113

Table 48
Emissions of specific hydrocarbons when using neat gasoline and three different blends of ethanol [221].

Vehicle Methane Ethylene Acetylene Ethylene

Toyota Echo Honda Civic Toyota Echo Honda Civic Toyota Echo Honda Civic Toyota Echo Honda Civic
US FTP cycle mg/km mg/km mg/km mg/km mg km mg/km mg/km mg/km

0% Ethanol 4.848 1.952 4.332 2.032 0.615 BDLa 1.311 0.640


10% Ethanol 4.338 1.417 4.406 1.554 0.622 BDL 1.212 0.261
15% Ethanol 4.406 1.212 4.344 1.423 0.640 BDL 1.293 0.553
20% Ethanol 4.829 1.846 4.375 1.541 0.472 BDL 1.181 0.423

a
BDL, Below Detection Limit.
1490 M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495

Table 52
Summary of FTIR emissions measurements for vehicles 4, 5 and 6, vehicle 6 Toyota (Yaris) (repeat)) running on base gasoline and E10 fuels [223].

Drive cycle Fuel Methane (mg/km) 1,3-butadiene (mg/km) Formaldehyde (mg/km) Acetaldehyde (mg/km) Nitrous oxide (mg/km) Benzene (mg/km)

Cold ECE Gasoline 79.593 3.007 0.974 9.042 0.660 N/D


E10 92.031 1.307 0.509 18.183 0.198 10.092
Cold EUDC Gasoline 13.173 0.326 0.288 1.003 0.095 3.124
E10 11.640 0.231 0.197 0.896 0.014 1.347

Table 53
Vehicle 4 Volkswagen (Golf) running on base gasoline and E10 fuels [223].

Drive cycle Fuel Methane (mg/km) 1,3-butadiene (mg/km) Formaldehyde (mg/km) Acetaldehyde (mg/km) Nitrous oxide (mg/km) Benzene (mg/km)

Cold ECE Gasoline 13.009 1.739 0.079 1.619 0.012 N/D*


E10 11.977 1.120 0.074 4.365 0.388 N/D*

Cold EUDC Gasoline 0.602 0.104 0.009 0.078 0.004 0.003


E10 0.655 0.076 0.031 0.163 0.001 N/D*

Table 54
Vehicle 5 Rover (416) running on base gasoline and E10 fuels [223].

Drive cycle Fuel Methane (mg/km) 1,3-butadiene (mg/km) Formaldehyde (mg/km) Acetaldehyde (mg/km) Nitrous oxide (mg/km) Benzene (mg/km)

Cold ECE Gasoline 69.302 4.011 0.220 13.846 N/Da N/Da


E10 50.244 2.334 0.107 12.660 N/Da N/Da

Cold EUDC Gasoline 11.260 0.183 0.124 1.225 N/Da N/Da


E10 7.247 0.107 0.039 1.408 0.007 N/Da

a
No data presented.

Table 55
Summary 2 of FTIR emissions measurements for vehicles 4, 5 and 6 Vehicle 6 Toyota (Yaris, repeat) running on base gasoline and E10 fuels [223].

Drive cycle Fuel Benzene (mg/km) Ammonia (mg/km) Formaldehyde (mg/km) Acetaldehyde (mg/km) Total PAHs (mg/km)

Cold ECEþ EUDC Gasoline 0.124 4.001 0.667 0.200 43.62*


E10 0.057 5.232 0.401 0.654 44.86*

Table 56
Vehicle 4 Volkswagen (Gulf) running on base gasoline and E10 fuels [223].

Drive cycle Fuel Benzene (mg/km) Ammonia (mg/km) Formaldehyde (mg/km) Acetaldehyde (mg/km) Total PAHs (mg/km)

Cold ECEþ EUDC Gasoline 0.347 4.567 0.114 0.049 113.71*


E10 0.056 2.755 0.072 0.178 30.22 *

Table 57
Vehicle 5 Rover (416) running on base gasoline and E10 fuels [223].

Drive cycle Fuel Benzene (mg/km) Ammonia (mg/km) Formaldehyde (mg/km) Acetaldehyde (mg/km) Total PAHs (mg/km)

Cold ECE þEUDC Gasoline 0.357 7.788 0.214 0.532 42.57a


E10 1.818 18.826 1.298 1.493 66.17a

a
Average value for Cold ECEþEUDC and the following driving cycles: WSL Congested, WSL Urban,

Table 58
Numbers of increases ( þ ) and decreases (  ) of unregulated emissions found in the tests using E10 compared to the tests using neat gasoline [223].
P
Changes Methane 1,3-butadiene Formaldehyde Acetaldehyde Nitrous oxide Benzene Ammonia PAH

Increase 2 2 2 6 1 1 2 2
Decrease 7 7 7 3 3 3 1 1
M.A. Ghadikolaei / Renewable and Sustainable Energy Reviews 57 (2016) 1440–1495 1491

Table 59  NOX emission was decreased with using alcohol fuels in fumiga-
Mean emission factors from three TWC-equipped cars running on 3, 6 and 10 vol. % tion mode compared to fossil fuels, though NOX emission was
ethanol gasoline blends [224].
increased with using alcohol fuels in blended mode in major tests.
Emission 3% Ethanol 6% Ethanol 10% Ethanol
Ethanol effect 6.2. Unregulated emissions

g O3/g NMOG 3.12 3.09 3.08 


Benzene (mg/km) 7.22 7.38 8.11 þ
Butadiene (mg/km) 0.83 0.77 0.83 þ/ 
 Total carbonyls were increased with using alcohol fuels in both
Formaldehyde (mg/ 1.32 0.78 1.01  modes compared to fossil fuels in all tests.
km)  Formaldehyde and acetaldehyde were the predominant carbonyls
Acetaldehyde (mg/ 1.12 1.25 1.62 þ in the exhaust for vehicles followed by butyraldehyde, benzalde-
km)
hyde, crotonaldehyde, methacrolein, and propionaldehyde.
 Formaldehyde was increased with using alcohol fuels in both
Table 60 modes compared to fossil fuels in most experiments.
Emissions of regulated and non-regulated emissions generated when using neat  Acetaldehyde was increased with using alcohol fuels in blended
gasoline and E5 at different ambient temperatures. US-73 test cycle [225]. mode compared to fossil fuels in major cases.
P  Unburned ethanol and methanol were increased with using
Fuel Temp. (°C) Formaldehyde Acrolein Particles B(a)
(mg/km) (mg/km) (mg/km) PAH P (l
alcohol fuels in both modes compared to fossil fuels in all tests.
(l/km) /km)  SOF was increased with using alcohol fuels in both modes
compared to fossil fuels in major cases.
Gasoline 22 6.6 o 0.1 8.2 49 0.9  BTEX emissions were decreased with using alcohol fuels in
5 2.3 o 0.1 30.1  
blended mode compared to fossil fuels in most cases, however,
E5 22 6.3 1.2 8.5 33 2.1
5 4.2 o 1.2    BTX was increased with using alcohol fuels in fumigation mode
6 1.4 0.6 26.8 71 2.2 in significant tests.
 1,3-butadiene emission was decreased with using alcohol fuels
in both modes compared to fossil fuels in all experiments.
None of these vehicles was equipped with a catalyst. All the tests  Ethyne and ethene were decreased with using alcohol fuels in
carried out only those involving use of E23 were of interest here. both modes compared to fossil fuels in all cases.
Considering both the amounts of the emissions, and their muta-  PAHs were decreased with using alcohol fuels in blended mode
genicity, the results suggested that use of E23 had both pros and compared to fossil fuels in major cases.
cons. For example, when comparing the use of the 23% ethanol
blend in gasoline with the use of neat gasoline, the emissions of
ethanol and acetaldehydes increased, while emissions of polycyclic Acknowledgment
aromatic hydrocarbons (PAHs) and especially benzo(a)pyrene
(BaP) were somewhat lower, as were the mutagenic effects. Author is thankful to Prof. C.S. Cheung (Professor of Depart-
ment of Mechanical Engineering, The Hong Kong Polytechnic
University, Hung Hom, Kowloon, Hong Kong) and Prof. Khalid
Zaidi (Professor, Department of Mechanical Engineering, Aligarh
6. Conclusion Muslim University, Aligarh, Uttar Pradesh, India) for their counsel
and guidance during progress of this work.
In this literature review work, a wide type of IC engines, such as
SI and CI engines and motorcycles were collected with different
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