Investigation into the Impact of the Composition of Ethanol Fuel Deposit Control Additives on Their Effectiveness
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Preparation of DCA
2.2.1. Preparation of 6-Dodecyl-3-(N,N-dimethylaminopropyl)-3,4-dihydro-2H-[1,3]-benzoxazine (DEM1)
2.2.2. Preparation of 2-(((3-Dimethylaminopropyl)amino)methyl)-4-dodecylphenol (DEM2)
2.3. Preparation of Detergent-Emulsifying Additive Batches
2.4. Experimental Apparatus and Procedure
- preparation of the engine for testing, including removal of all deposits and contaminants that formed on its internal components during the previous test (inlet and outlet valves, combustion chambers, intake pipes, intake channels in the engine head). For each test, a new set of injectors is assumed (brand new set).
- assembly of the engine for testing.
- preparation of the ethanol fuel to be tested, including the package of additives used in it, defined in a qualitative and quantitative manner.
- carrying out a full 100-h engine test under the conditions of a 4-phase cyclic test (Table 3).
- removing the head from the engine, and then removing the intake valves and fuel injection system components.
- mass evaluation of deposits formed on the intake valves and in the engine combustion chambers (according to CEC F-20-98—Mercedes Benz M111).
- 1—stage
- simulates unloaded engine operation at low speed (idle);
- 2—stage
- transition from 1st to 2nd stage and 2nd stage reflects engine operation at soft acceleration, low load and engine speed (conditions of starting and slow acceleration of the vehicle);
- 3—stage
- simulates prolonged operation of a lightly loaded engine (conditions of free movement of the vehicle in the city);
- 4—stage
- simulates the working conditions of a lightly loaded engine at medium speed (conditions of fast vehicle movement through the city streets).
3. Results and Discussion
3.1. Structural Analysis of 6-Dodecyl-3-(N,N-dimethylaminopropyl)-3,4-dihydro-2H-[1,3]-benzoxazine (DEM1)
3.2. Structural Analysis of 2-(((3-Dimethylaminopropyl)amino)Methyl)-4-dodecylphenol (DEM2)
4. Conclusions
- It was confirmed that deposit control additives (DCAs) used for the improvement of conventional hydrocarbon engine gasolines are not efficient enough when used in E85 fuels. DCAs specifically developed for E85 fuels should have a different chemical structure and be soluble in an ethanol-gasoline mixture at any ratio.
- The effectiveness of DCAs developed for E85 fuels is largely affected by the selection of the ratio between the detergent-emulsifying additive (DEM) and the carrier oil.
- When optimizing the effectiveness of DCAs developed for E85 fuels, a proper selection of dosage level of the detergent-emulsifying additive (DEM) and the carrier oil in the DCA batch should be taken into account.
- DCAs containing detergent-emulsifying additives with a benzoxazine structure and a Mannich base structure, when used with a proper amount of carrier oil and with a properly selected dosage level, can effectively reduce the mass of deposits forming on inlet valves at a level that is comparable to or greater than the level achieved by commercial additives, and can reduce deposit formation in combustion chambers at a level that is comparable to or slightly greater than the level achieved by the reference commercial additives.
- In the case of the FlexFuel-type engine with port fuel injection (PFI) used for the study, no correlation between the changes in the size of injector deposits and the changes in the size of deposits on the inlet valves and in combustion chambers was found.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Pałuchowska, M.; Stępień, Z.; Żak, G. The prospects for the use of ethanol as a fuel component and its potential in the reduction of exhaust emissions. Combust. Engines 2014, 158, 80–92. [Google Scholar]
- Stępień, Z. Multidirectional investigations of high-ethanol fuels on deposit formation in spark ignition engines. Combust. Engines 2015, 162, 608–618. [Google Scholar]
- Magaril, E.; Magaril, R.; Al-Kayiem, H.H.; Skvortsova, E.; Anisimov, I.; Rada, E.R. Investigation on the Possibility of Increasing the Environmental Safety and Fuel. Sustainability 2019, 11, 2165. [Google Scholar] [CrossRef] [Green Version]
- Kalghatgi, G. Fuel/Engine Interactions; SAE International: Warrendale, PA, USA, 2013; ISBN 978-0-7680-6458-2. [Google Scholar]
- Orhan, A.; Semith, E. Carbon Deposit Formation From Thermal Stressing of Petroleum Fuels. Prepr. Pap. Am. Chem. Soc. Div. Fuel Chem. 2004, 49, 764. [Google Scholar]
- Schwahn, H.; Lutz, U. Deposit Formation of Flex Fuel Engines Operated on Ethanol and Gasoline Blends; SAE Paper No. 2010-01-1464; SAE International: Warrendale, PA, USA, 2010. [Google Scholar]
- Parsinejad, F.; Biggs, W. Direct Injection Spark Ignition Engine Deposit Analysis: Combustion Chamber and Intake Valve Deposits; SAE Paper No. 2011-01-2110; SAE International: Warrendale, PA, USA, 2010. [Google Scholar]
- Stępień, Z. Intake valve and combustion chamber deposits formation–the engine and fuel related factors that impacts their growth. Nafta Gaz 2014, 4, 28–34. [Google Scholar]
- Vilardo, J.S.; Arters, D.; Corkwell, K.; Cerda de Groote, C.L. A Comprehensive Examination of the Effect Ethanol-Blended Gasoline on Intake Valve Deposits in Spark-Ignited Engines; SAE Technical Paper No. 2007-01-3995; SAE International: Warrendale, PA, USA, 2007. [Google Scholar]
- DuMont, R.J.; Cunningham, L.; Oliver, M.K.; Studzinski, W.M.; Galante-Fox, J.M. Controlling Induction System Deposits in Flexible Fuel Vehicles Operating on E85; SAE Technical Paper No. 2007-01-4071; SAE International: Warrendale, PA, USA, 2007. [Google Scholar]
- Russell, M.; Cummings, J.; Cushing, T.; Studzinski, W. Cellulosic Ethanol Fuel Quality Evaluation and its Effects on PFI Intake Valve Deposits and GDI Fuel Injector Plugging Performance; SAE Technical Paper No. 2013-01-0855; SAE International: Warrendale, PA, USA, 2013. [Google Scholar]
- Marrodán, L.; Fuster, M.; Millera, A.; Bilbao, R. Ethanol as a Fuel Additive: High-Pressure Oxidation of Its Mixtures with Acetylene. Energy Fuels 2018, 32, 10078–10087. [Google Scholar] [CrossRef] [Green Version]
- Tibaquirá, J.E.; Huertas, J.I.; Ospina, S.; Quirama, L.F.; Niño, J.E. The Effect of Using Ethanol-Gasoline Blends on the Mechanical. Energy and Environmental Performance of In-Use Vehicles. Energies 2018, 11, 221. [Google Scholar] [CrossRef] [Green Version]
- Gibbs, L.M. Gasoline Additives-When and Why. SAE Trans. J. Fuels Lubr. 1990, 99, 618–638. [Google Scholar]
- Danilov, A.M. Progress in research on fuel additives (review). Pet. Chem. 2015, 55, 69–179. [Google Scholar] [CrossRef]
- Graupner, O.; Mundt, M.; Schütze, A.; Louis, J.J.J.; Kendall, D.R.; Tait, N.P. Gasoline Additives. U.S. Patent 7901470, 8 March 2011. [Google Scholar]
- Mingxing, F.; Shumin, C.; Xinchang, Z.; Wenbiao, L.; Yongsheng, C. Petrol. Detergent Capable of Reducing Deposit of Gasoline Engine Combustion Chamber. Patent CN 101230297, 25 November 2009. [Google Scholar]
- Babic, G.T. Classification System for Gasoline Detergent Performance. International Symposium of Fuels and Lubricants; ISFL-1997; Proceedings: New Delhi, India, 1997; ISFL-1997. [Google Scholar]
- Srivastava, S.P.; Hancsók, J. Fuels and Fuel Additives; Wiley and Sons, Inc.: Hoboken, NJ, USA, 2014. [Google Scholar]
- Roberts, R.; Ross, A.N. Composition, Method and Use. Patent GB 201705089, 30 March 2017. [Google Scholar]
- Obiols, J. Composition of Fuel Additives. Patent FR 3074498, 17 April 2019. [Google Scholar]
- Lange, A.; Böhnke, H.; Grabarse, W.; König, H.M.; Hansch, M.; Völkel, L.; Castro, I.G. Polytetrahydrobenzoxazines and Bistetrahydrobenzoxazines and Use Thereof as a Fuel Additive or Lubricant Additive. U.S. Patent 9006158, 2015. [Google Scholar]
- Lange, A.; Rath, H.P.; Posselt, D.; Trötsch-Schaller, L.; Walter, M. Method for Producing Mannich Adducts that Contain Polyisobutylene Phenol. Patent WO 2001025293, 12 November 2004. [Google Scholar]
- Ali, R.; Filip, S.V. Fuel Compositions with Additives. Patent WO 2017137519, 17 August 2017. [Google Scholar]
- Schifter, U.; González, C.; González-Macías, R. Effects of ethanol, ethyl-tert-butyl ether and dimethyl-carbonate blends with gasoline on SI engine. Fuel 2016, 183, 253–261. [Google Scholar] [CrossRef]
- Sharudin, H.; Abdullah, N.R.; Najafi, G.; Mamat, R.; Masjuki, H.H. Investigation of the effects of iso-butanol additives on spark ignition engine fuelled with methanol-gasoline blends. Appl. Therm. Eng. 2017, 114, 593–600. [Google Scholar] [CrossRef] [Green Version]
- Najjar, R. Application and Characterization of Surfactants; BoD: Norderstedt, Germany, 2017. [Google Scholar]
- Shilbolm, C.M.; Schoonveld, G.A. Effect on Intake Valve Deposits of Ethanol and Additives Common to the Available Ethanol Supply; SAE Paper No. 902109; SAE International: Warrendale, PA, USA, 1990. [Google Scholar]
- Renewable Fuels Association (RFA) Fuel Ethanol Industry Guidelines, Specifications and Procedures. July 2018. Available online: https://ethanolrfa.org/wp-content/uploads/2018/07/Fuel-Ethanol-Industry-Guidelines-Specifications-2018.pdf (accessed on 19 June 2020).
- Aradi, A.A.; Evans, J.; Miller, K.; Hotchkiss, A. Direct Injection Gasoline (DIG) Injector Deposit Control with Additives; SAE Technical Paper No. 2003-01-2024; SAE International: Warrendale, PA, USA, 2003. [Google Scholar]
- Aradi, A.A.; Colucci, W.J.; Scull, H.M.; Openshaw, M.J. A Study of Fuel Additives for Direct Injection Gasoline (DIG) Injector Deposit Control; SAE Technical Paper No. 2000-01-2020; SAE International: Warrendale, PA, USA, 2000. [Google Scholar]
- Turovskii, F.V. In Proceedings of the V International Scientific-Practical Conference on New Fuels with Additives (APRIS), St. Petersburg, Russia, 20–23 May 2008; p. 23.
- Colucci, W.J.; Pettigrew, F.A.; Cunningham, F.J. Additives for Minimizing Intake Valve Deposits, and Their Use. U.S. Patent 5634951, 3 June 1997. [Google Scholar]
- Voelkel, L.; Hansch, M.; Hayden, Y.; Walter, M.; Kashani-Shirazi, N.; Weiss, T. Use of Polyalkylene Glycol to Reduce Fuel Consumption. U.S. Patent 20150113859, 30 April 2015. [Google Scholar]
- Wolf, L.R. Low Sulfur Fuel Compositions having Improved Lubricity. U.S. Patent 20130180164, 18 July 2013. [Google Scholar]
- Cunningham, L.J. Biodegradable Fuel Performance Additives. U.S.Patent 9562498, 7 February 2017. [Google Scholar]
- Burgess, V.; Reid, J.; Mulqueen, S. Gasoline Composition, Method and Use. U.S. Patent 9932536, 3 April 2018. [Google Scholar]
- Miller, F.P.; Vandome, A.F.; McBrewster, J. Mannich Base; Alphascript Publishing: Saarbrücken, Germany, 2010. [Google Scholar]
- Cummings, T.F.; Shelton, J.R. Mannich Reaction Mechanisms. Org. Chem. 1960, 25, 419–423. [Google Scholar] [CrossRef]
- Markowski, J.; Krasodomski, W. Synthesis of new surface-active substance. Przemysł Chem. 2016, 5, 920–927. [Google Scholar]
- Deng, Y.; Zhang, Q.; Zhang, H.; Zhng, C.; Wang, W.; Gu, Y. Kinetics of 3,4-Dihydro-2H-3-phenyl-1,3-benzoxazine Synthesis from Mannich Base and Formaldehyde. Ind. Eng. Chem. Res. 2014, 53, 1933–1939. [Google Scholar] [CrossRef]
- Ishida, H.; Agag, T. Handbook of Benzoxazine Resins; Elsevier: Amsterdam, The Netherlands, 2011. [Google Scholar]
- Danilov, A.M. Research on Fuel Additives During 2011–2015. Chem. Tech. Fuels Oil. 2017, 53, 705–721. [Google Scholar] [CrossRef]
- Deposit Forming Tendency on Intake Valves; Test Method No. CEC-F-20-98; The Coordinating European Council for the Development of Performance Tests for Fuels, Lubricants and other Fluids: Brussels, Belgium, 2019.
Properties | Base Gasoline E0 | Fuel E85 | Test Methods |
---|---|---|---|
Research Octane Number | 98.1 | 108.2 | EN ISO 5164 |
Motor Octane Number | 89.5 | 93.7 | EN ISO 5163 |
Lead, mg/L | <2.5 | - | EN 237 |
Density in 15 °C, kg/m3 | 725.6 | 784.0 | EN ISO 12185 |
Sulphur, mg/kg | <3 | <0.5 | EN 20846 |
Copper, mg/kg | - | <0.05 | EN 15837 |
Phosphorus, mg/L | - | <0.15 | EN 15487 |
Induction period, min. | >480 | >360 | ISO 7536 |
Gums content, mg/100 mL: | EN ISO 6246 | ||
- unwashed | |||
- washed | <1 | 1.0 | |
Copper corrosion | 1 A | 1 A | EN ISO 2160 |
Benzene, %(v/v) | 0.25 | - | EN 238 |
Oxygen, %(m/m) | 0.0 | - | EN 1601 |
Ethanol, %(v/v) | <0.1 | 70.5 | EN 1601 |
Methanol, %(v/v) | - | 0.3 | EN 1601 |
Inorganic chloride mg/kg | - | <4.0 | EN 15492 |
Vapor pressure (DVPE), kPa | 57.8 | 45.2 | ASTM D 4953 |
Distillation characteristics: Initial boiling point (IBP), °C | 33.4 | - | EN ISO 3405 |
- up to 70 °C distilled volume, %(v/v) | 21.1 | - | |
- up to 100 °C distilled volume, %(v/v) | 52.5 | - | |
- up to 150 °C distilled volume, %(v/v) | 93.1 | - | |
- end of distillation, °C | 181.9 | - | |
- residues, %(v/v) | 1.0 | - |
Components Used | Detergent-Emulsifying Additive | Carrier Oil | Solvent | Detergent-Emulsifying Additive–Carrier Oil Ratio | |
---|---|---|---|---|---|
DEM1 | DEM2 | DF 30 | Shellsol A150 | ||
Deposit Control Additives (DCA) | Dosage Level, mg/kg | ||||
DCA1 | 117 | 129 | 354 | 1.0:1.1 | |
DCA2 | 117 | 129 | 354 | 1.0:1.1 | |
DCA3 | 117 | 156 | 327 | 1.0:1.3 | |
DCA4 | 117 | 156 | 327 | 1.0:1.3 | |
DCA5 | 117 | 176 | 307 | 1.0:1.5 | |
DCA6 | 117 | 176 | 307 | 1.0:1.5 | |
DCA7 | 72 | 94 | 434 | 1.0:1.3 | |
DCA8 | 72 | 94 | 434 | 1.0:1.3 | |
DCA9 | 162 | 211 | 227 | 1.0:1.3 | |
DCA10 | 162 | 211 | 227 | 1.0:1.3 |
Work Cycle | 4-Stroke, with Spark Ignition |
---|---|
Fuel injection type | Indirect fuel injection electronically controlled by Visteon system |
Cylinder configuration | straight vertical |
Number of cylinders | 4 |
Firing order | 1-3-4-2 |
Timing gear type | DOHC/4 VPC |
Cylinder bore | 83.0 mm |
Piston stroke | 83.1 mm |
Engine displacement | 1798 cm3 |
Horsepower capacity | 125 hp (92 kW) at 6000 RPM |
Max. torque | 165 Nm at 4000 RPM |
Compression ratio | 10.8 |
Average fuel consumption (E85) in combined cycle | 10.5 L/100 km |
Valve lash | Hydraulic regulation |
Volume of the lubrication system with a filter | 4.3 dm3 |
The standard complied in the scope of emissions of hazardous substances to the atmosphere | Euro IV |
Stage | Total Cycle Time [s] | Stage Time [s] | Engine [RPM] | RPM Stabilization Time [s] | Engine Load [Nm] | Load Stabilization [s] | Recording Time [s] | Recording Start [s] | Coolant Temp. [°C] | Oil Temp. [°C] | Fuel Temp. [°C] |
---|---|---|---|---|---|---|---|---|---|---|---|
1 | 30 | 30 | 800 ± 50 neutral gear | 0 | 0 | 8 ± 2 | 10 | 20 | 105 ± 3 | 90 ± 5 | 27 ± 5 |
2 | 60 | 30 | 1800 ± 25 | 10 ± 2 | 40 ± 2 | 8 ± 2 | 10 | 20 | 105 ± 3 | 90 ± 5 | 27 ± 5 |
3 | 120 | 60 | 2500 ± 25 | 15 ± 2 | 40 ± 2 | 8 ± 2 | 10 | 40 | 105 ± 3 | 90 ± 5 | 27 ± 5 |
4 | 150 | 30 | 3800 ± 25 | 15 ± 2 | 60 ± 2 | 8 ± 2 | 10 | 20 | 105 ± 3 | 90 ± 5 | 27 ± 5 |
Deposit Control Additives (DCA) | Inlet Valve Deposits [mg/valve] | Combustion Chamber Deposits [mg] |
---|---|---|
DCA1 (DEM1) | 15 | 906 |
DCA2 (DEM2) | 19 | 1650 |
DCA3 (DEM1) | 6 | 1984 |
DCA4 (DEM2) | 14 | 2133 |
DCA5 (DEM1) | 16 | 1042 |
DCA6 (DEM2) | 8 | 2636 |
Deposit Control Additives (DCA) | Inlet Valve Deposits [mg/valve] | Combustion Chamber Deposits [mg] |
---|---|---|
DCA7 (DEM1) | 26 | 792 |
DCA8 (DEM2) | 21 | 1142 |
DCA3 (DEM1) | 6 | 1984 |
DCA4 (DEM2) | 14 | 2133 |
DCA9 (DEM1) | 27 | 1223 |
DCA10 (DEM2) | 7 | 1141 |
Fuel/Deposit Control Additives | Inlet Valve Deposits [mg/Valve] | Combustion Chamber Deposits [mg] |
---|---|---|
15% (v/v) Commercial petrol (RON 95) 85% (v/v) Ethanol | 59 | 2163 |
Base fuel + 85% (v/v) Ethanol | 30 | 426 |
Base fuel + 85% (v/v) Ethanol + DCA X1 | 6 | 2050 |
Base fuel + 85% (v/v) Ethanol + DCA Y1 | 20 | 807 |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
Stępień, Z.; Żak, G.; Markowski, J.; Wojtasik, M. Investigation into the Impact of the Composition of Ethanol Fuel Deposit Control Additives on Their Effectiveness. Energies 2021, 14, 604. https://doi.org/10.3390/en14030604
Stępień Z, Żak G, Markowski J, Wojtasik M. Investigation into the Impact of the Composition of Ethanol Fuel Deposit Control Additives on Their Effectiveness. Energies. 2021; 14(3):604. https://doi.org/10.3390/en14030604
Chicago/Turabian StyleStępień, Zbigniew, Grażyna Żak, Jarosław Markowski, and Michał Wojtasik. 2021. "Investigation into the Impact of the Composition of Ethanol Fuel Deposit Control Additives on Their Effectiveness" Energies 14, no. 3: 604. https://doi.org/10.3390/en14030604