Next Article in Journal
An Integrated Lightning Risk Assessment of Outdoor Air-Insulated HV Substations
Next Article in Special Issue
Water Energy in Poland in the Context of Sustainable Development
Previous Article in Journal
Eliminate Time Dispersion of Seismic Wavefield Simulation with Semi-Supervised Deep Learning
Previous Article in Special Issue
Closed-Loop Agricultural Production and Its Environmental Efficiency: A Case Study of Sheep Wool Production in Northwestern Kyrgyzstan
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Feasibility of Waste Engine Oil Electrooxidation with Ni-Co and Cu-B Catalysts

by
Paweł P. Włodarczyk
* and
Barbara Włodarczyk
*
Institute of Environmental Engineering and Biotechnology, University of Opole, ul. Kominka 6a, 45-032 Opole, Poland
*
Authors to whom correspondence should be addressed.
Energies 2022, 15(20), 7686; https://doi.org/10.3390/en15207686
Submission received: 14 September 2022 / Revised: 5 October 2022 / Accepted: 14 October 2022 / Published: 18 October 2022
(This article belongs to the Special Issue The Political Economy of Sustainable Energy)

Abstract

:
To implement a circular economy policy, methods of using waste products as a starting point for other technologies are constantly researched. One of the waste products that should be disposed of after use is waste engine oil (WEO). Despite the permanent introduction of the electrification of cars, the number of combustion vehicles (and, thus, the production of WEO) is constantly increasing. For these reasons, the reuse of WEOs is extremely important; e.g., to use these oils for energy purposes. One of the potential uses of this type of oil is as fuel for fuel cells (for direct electricity production). To lower the production costs of electrodes for fuel cells, catalysts that do not contain precious metals are being constantly sought. This work shows the research of WEO electrooxidation feasibility with Ni-Co and Cu-B catalysts. The results showed the feasibility of the electrooxidation of WEO emulsion on Ni-Co and Cu-B electrodes in an electrolyte (a water solution of sulfuric acid). Moreover, it was shown that the electrooxidation of the WEO emulsion occurred for all concentrations of WEO in the emulsion for all measurement temperatures (20–80 °C). The highest current density obtained in the measurements was 11 mA cm−2 (at 60 °C) for the Ni-Co electrode.

1. Introduction

The number of motor vehicles in the world is constantly increasing. The upward trend also continues in Poland [1]. Here, a total of over 1.8 million vehicles were registered in 2021 [1]. Figure 1 shows the number of newly registered cars (for the first time in the country) in Poland for the years 2011–2021. The temporary drop in sales in 2020 was a result of changes in the car sales market because of COVID-19 [2]. Since 2021, car sales have increased again.
The data (Figure 1) include all motor vehicles; e.g., cars, vans, trucks, agricultural tractors, special vehicles, motorcycles and mopeds. Currently, there are over 38 million registered vehicles in Poland, including over 10 million inactive registrations [1]. Inactive registrations are vehicles excluded from traffic, scrapped or left in parking lots, for example. However, over 28 million are active registrations; i.e., vehicles that travel on Polish roads. Each vehicle uses both engine oils and transmission oils. These oils are also regularly changed, generating huge amounts of waste oils. It should be noted that these are data from only one country.
The European Parliament voted to end the sale of combustion cars from 2035 [3]. However, the replacement of most vehicles in the EU will not abruptly happen. Vehicles of this type will be used for many, many years to come. Thus, the generation of huge amounts of waste oils (which have to be disposed of or reused; e.g., for the production of new oils or energy production) will also take place for a long time. For these reasons, the disposal of waste engine oils (WEOs) is a very important issue [4,5,6]. In most countries of the world, WEOs, waste transmission oils, used oil filters or oil packaging are classified as hazardous waste [7,8].
The parameters of waste oils (e.g., the amount of other contaminants or the oxidation state) depend on the type of oil, amount of improvers, operation time, operation temperature, oil oxidation rate, presence of different metals (e.g., catalytically active) and mechanical shear forces [7,9,10,11,12]. Moreover, the oil can be polluted by exhaust gases or other combustion products [13,14].
Activities for ecology require that the disposal process should be carried out in a way that has the least impact on the natural environment [15,16]. One of the rational forms of the disposal of used oils can be their industrial use [7,16,17]. Examples of ways to use waste oils include the restoration of oil properties by filtration, reprocessing oils to form a substitute fuel, recycling by adding a refining process, deep regeneration (re-refining) or re-using oil directly as a fuel [18,19,20,21,22,23,24,25]. Unfortunately, a few methods pose a threat to the natural environment [24,25].
One of the methods of WEO utilization may be electrooxidation. It is the research direction that (with a high probability) will allow, in the future, fuel cells to be powered by WEOs. Fuel cells operate without any intermediate steps (e.g., a combustion process) and are characterized by a high efficiency [26,27,28,29,30,31].
The feasibility of WEO utilization by electrooxidation was demonstrated in our previous work [32]. However, the previous work involved the research of electrooxidation on a platinum electrode. The high price of platinum has forced the search for other, cheaper catalysts that do not contain precious metals [33,34,35,36]. Another catalyst with good catalytic parameters is nickel. However, pure nickel (e.g., Raney Ni) can be very difficult to use due to fact that Raney Ni contains small amounts of absorbed hydrogen that may spontaneously ignite; thus, it should not be exposed to air. Therefore, this nickel form is most often supplied as an aqueous suspension [37]. For these reasons, nickel alloys (rather than pure nickel) is safer (and easier) to use compared with pure nickel. Other metals and metal alloys are also used as electrode catalysts; e.g., cobalt and its alloys or a metal alloy with boron [38,39,40,41,42,43,44]. It is essential to maintain the good catalytic properties of the new alloys.
Mainly to reduce costs (by reducing the use of precious metals) and also to obtain durable electrodes, it is extremely important to search for new metal (metal alloy) catalysts [34,35,36,39,40,41,42,43,44,45,46,47]. This paper presents our research of the electrooxidation feasibility of WEOs with the use of electrodes with Ni-Co and Cu-B catalysts.

2. Materials and Methods

In our research, WEOs from ten different cars were applied. The oils were obtained from a car service station from compression ignition engines (diesel) and spark ignition engines (gasoline and LPG). The mileage of the engines ranged from 10,000 to 30,000 km. Moreover, the age of the cars (and thus the engines) and their condition were not analyzed. Therefore, the engine oil wear was at different levels.
Mixed waste oils from car service stations (from various vehicles) are sent for reprocessing or disposal. Such mixtures of waste oils contain mainly engine oils, gearbox oils and oils from steering gear, for example. Our research plan assumed the measurements of the electrooxidation of oils using only WEOs.
The oils used in the measurements were collected when cars were serviced (as a result, the oils are exchanged). During the oil sampling, the engine type and mileage from the last oil change were simultaneously recorded. The data of the collected samples of WEOs are presented in Table 1.
To simulate the real oils sourced from car service stations, the WEOs were mixed in equal proportions (1:1:1:1:1:1:1:1:1:1). After mixing the oils, decantation was performed then filtering using a viscose filter. These treatments allowed the solid contaminants to be cleaned from the oil, resulting in normal engine operation. Figure 2 shows the WEO mixed in equal proportions.
To allow the oil to mix with the electrolyte and to ensure electricity conduction, an oil emulsion preparation was planned. Syntanol DS-10 was used to form the emulsion. That detergent is characterized by its emulsification, solubilization capabilities, dispersion and high superficial activity [48,49]. Moreover, Syntanol DS-10 is biodegradable (e.g., by bacteria) [50,51]. The WEO emulsion was obtained by mixing oil (WEO), water and Syntanol DS-10. The mixing was carried out by means of a mechanical stirrer (1200 rpm). The oil–water–detergent ratio was selected experimentally and was finally 1:2:1. This ratio of ingredients ensured a long emulsion stability of about 20 min. The stability of the WEO emulsion specified in the analysis changed the color uniformity of the images in the emulsion sample. The emulsion was exposed to white light on a white background and a photo was taken every minute. The comparison of changes in the color uniformity allowed the evaluation of the emulsion stability time.
The catalysts were electrochemically deposited onto a copper electrode. A copper electrode in the form of a foam was used. The electrode parameters were 20 × 40 × 5 mm with foamed copper at 100 PPI. Before the deposition, the foam copper was prepared in several steps [43,44,52,53]: the surface was degreased in a 25% aqueous solution of KOH to obtain the complete wettability of the electrode; the electrode was then digested in acetic acid and subsequently washed with alcohol.
To obtain the Ni-Co alloy, a mixture composed mainly of NiSO4 and CoSO4 was used [51,52]. For conducting the electrochemical deposition, temperatures of 20–50 °C and a pH range of 2.0–5.5 were used [54]. The obtain the Cu-B alloy, a mixture of mainly NaBH4 and CuSO4 was used [53]. To conduct this process, temperatures of 80–90 °C and a pH range of 2.0–5.0 were applied [44,52]. Current densities for both alloy types in the range of 1–3 A·dm−2 were used [52,54].
Based on experience from previous research [44,53,54,55,56,57], we chose catalysts (a Ni-Co alloy with 15% Co and a Cu-B alloy with 9% B) for the electrooxidation of the WEO emulsion. The electrodes with the Ni-Co and Cu-B catalysts were used as the working electrodes (WE).
Figure 3 contains a diagram of the measurement setup for the measurements of the WEO emulsion electrooxidation.
The measurements of the WEO emulsion electrooxidation were made using the method of polarization curves. Electrooxidation in a glass vessel (reactor) was made on an electrode (working electrode (WE)) with the new catalysts (Ni-Co and Cu-B) in a water solution of sulfuric acid (0.5 M and 2 M). The measurements were carried out using a potentiostat. A saturated calomel electrode (SCE) was used as the reference electrode (RE) [55,56,57,58,59]. It should be noted that the measurement results were not related to the real working electrode (WE) surface but only to its dimensions. Figure 4 contains a diagram of the reactor (number 12 from block C of Figure 3).
Figure 5 shows a view of the measurement setup for the measurements of WEO electrooxidation (block C of Figure 3).
The electrooxidation of the waste oil emulsions in a water solution of sulfuric acid (0.5 M and 2 M) for various concentrations of WEO and pure detergent at different temperatures (20–80 °C) were measured. The concentrations of the WEO emulsion were 0.005%, 0.010%, 0.030% and 0.060% of the reactor volume (electrolyte volume). The electrooxidation of pure Syntanol DS-10 (added to the electrolyte in the same percentage as the WEO) itself was then measured. A comparison of the electrooxidation of pure Syntanol DS-10 with the electrooxidation of the WEO allowed us to assess whether the electric current was generated from the WEO or only from the detergent.
A PowerLab 305D-II power supply (PowerLab, China) was used to electrochemically deposit the catalyst onto the copper electrodes. A LAC LH06/12 silt furnace (LAC s.r.o., Židlochovice, Czech Republic) was used for the electrode oxidation. The emulsion was mixed using a CAT R17 mechanical stirrer (Ingenieurbüro CAT M. Zipperer GmbH, Staufen, Germany). For the pictures for the emulsion separation analysis, a D5100 camera (Nikon Co., Tokyo, Japan) was used. A technoKartell model TK 22 magnetic stirrer with a hot plate (Kartell S.p.A.—LABWARE Division, Noviglio, Italy) was used to mix the electrolyte with the emulsion in the glass vessel (reactor). For the measurements of the electrooxidation of the WEO emulsion, an AMEL System 500 potentiostat (Amel S.l.r., Milano, Italy) was used. For the data collection and the electrooxidation analysis, CorrWare software (Scribner Associates Inc., Southern Pines, NC, USA) was used.

3. Results

3.1. Electrooxidation of Waste Engine Oil Emulsion on the Ni-Co Catalyst

Figure 6 presents the electrooxidation curves of the pure detergent (blue lines) and the WEO emulsion (black lines) in a 0.5 M water solution of sulfuric acid for temperatures of 20 °C and 40 °C on the Ni-Co catalyst. The concentrations of the pure detergent (blue lines) and the WEO emulsion (black lines) were in the range of 0.005–0.060% (of the electrolyte volume).
Figure 7 presents the electrooxidation curves of the pure detergent (blue lines) and the WEO emulsion (black lines) in a 0.5 M water solution of sulfuric acid for temperatures of 60 °C and 80 °C on the Ni-Co catalyst. The concentrations of the pure detergent (blue lines) and the WEO emulsion (black lines) were in the range of 0.005–0.060% (of the electrolyte volume).
Figure 8 presents the electrooxidation curves of the pure detergent (blue lines) and the WEO emulsion (black lines) in a 2 M water solution of sulfuric acid for temperatures of 20 °C and 40 °C on the Ni-Co catalyst. The concentrations of the pure detergent (blue lines) and the WEO emulsion (black lines) were in the range of 0.005–0.060% (of the electrolyte volume).
Figure 9 presents the electrooxidation curves of the pure detergent (blue lines) and the WEO emulsion (black lines) in a 2 M water solution of sulfuric acid for temperatures of 60 °C and 80 °C on the Ni-Co catalyst. The concentrations of the pure detergent (blue lines) and the WEO emulsion (black lines) were in the range of 0.005–0.060% (of the electrolyte volume).

3.2. Electrooxidation of Waste Oil Emulsion on the Cu-B Catalyst

Figure 10 presents the electrooxidation curves of the pure detergent (blue lines) and the WEO emulsion (black lines) in a 0.5 M water solution of sulfuric acid for temperatures of 20 °C and 40 °C on the Cu-B catalyst. The concentrations of the pure detergent (blue lines) and the WEO emulsion (black lines) were in the range of 0.005–0.060% (of the electrolyte volume).
Figure 11 presents the electrooxidation curves of the pure detergent (blue lines) and the WEO emulsion (black lines) in a 0.5 M water solution of sulfuric acid for temperatures of 60 °C and 80 °C on the Cu-B catalyst. The concentrations of the pure detergent (blue lines) and the WEO emulsion (black lines) were in the range of 0.005–0.060% (of the electrolyte volume).
Figure 12 presents the electrooxidation curves of the pure detergent (blue lines) and the WEO emulsion (black lines) in a 2 M water solution of sulfuric acid for temperatures of 20 °C and 40 °C on the Cu-B catalyst. The concentrations of the pure detergent (blue lines) and the WEO emulsion (black lines) were in the range of 0.005–0.060% (of the electrolyte volume).
Figure 13 presents the electrooxidation curves of the pure detergent (blue lines) and the WEO emulsion (black lines) in a 2 M water solution of sulfuric acid for temperatures of 60 °C and 80 °C on the Cu-B catalyst. The concentrations of the pure Syntanol DS-10 detergent (blue lines) and the WEO emulsion (black lines) were in the range of 0.005–0.060% (of the electrolyte volume).
An SCE was used as the reference electrode in the research. The use of the SCE made the measurements easier. However, all measurement results (Figure 6, Figure 7, Figure 8, Figure 9, Figure 10, Figure 11, Figure 12 and Figure 13) included in the study were converted and related to a reversible hydrogen electrode (RHE) [58,59].

4. Discussion

The electrooxidation of WEOs was carried out for both catalysts (Ni-Co and Cu-B) for all concentrations of emulsions and both concentration of electrolytes as well as for all temperatures (Figure 6, Figure 7, Figure 8, Figure 9, Figure 10, Figure 11, Figure 12 and Figure 13). It was demonstrated that with an increase in the temperature (from 20 to almost 80 °C), the value of the current density increased. This increase was continuous. However, based on the comparison of the measurements of the pure detergent electrooxidation (blue lines) and the measurements of the electrooxidation of the WEO emulsion (black lines), it was specified that the electrooxidation of the detergent (blue lines in Figure 7b, Figure 9b, Figure 11b and Figure 13b) took place first. At 80 °C, during the WEO emulsion electrooxidation, the obtained current density was lower (black lines in Figure 7b, Figure 9b, Figure 11b and Figure 13b). This was the case for both catalysts (Ni-Co and Cu-B) and for both electrolyte concentrations (0.5 M and 2 M). Therefore, this research made it possible for us to determine the boundary temperature of use of the WEO as a fuel with the use of Ni-Co and Cu-B catalysts (in an aqueous solution of sulfuric acid used as the electrolyte). It should be noted that this situation was similar to the measurement results obtained using a platinum catalyst [32].
The current density for all measurements (Ni-Co and Cu-B catalysts, for both electrolyte concentrations and for all measurement temperatures) of the electrooxidation of the WEO emulsion was in the range of 1–11 mA·cm−2. The highest value of current density (11 mA·cm−2) was recorded for the Ni-Co catalyst (0.010% concentration of the electrolyte volume) at a temperature of 60 °C (a 0.5 M aqueous solution of sulfuric acid) (Figure 7a). The maximum current density (7 mA·cm−2) for the Cu-B catalyst was recorded (0.030% concentration of the electrolyte volume) at a temperature of 60 °C (a 0.5 M aqueous solution of sulfuric acid) (Figure 11a).
It should be noted that the values of the current densities were slightly lower than the current densities obtained under the same conditions using the platinum catalyst (about half) [32]. These were comparable values regarding those related to the dimensions of the electrodes. However, these values cannot be directly compared in relation to the surface of real electrodes. This situation occurred due to the fact that the measurement results were not related to the real physical electrode surface but its dimensions, as noted beforehand. The measurements on the platinum electrode were carried out on a smooth surface electrode (with a Pt catalyst) whereas the measurements with the use of the Ni-Co and Cu-B catalysts were carried out on a foam copper electrode with a deposited catalyst [32]. The surface was defined as the visible surface (resulting from the dimensions).

5. Conclusions

Based on the data from the measurements, the feasibility of WEO electrooxidation with Ni-Co and Cu-B catalysts has been demonstrated. In a temperature range of 20–80 °C, the electrooxidation of the WEO emulsion took place for both catalysts (Ni-Co and Cu-B) for all emulsion concentrations and in both concentrations of acid electrolyte. The maximum current density was obtained for the Ni-Co catalyst at a temperature of 60 °C (0.010% of the WEO emulsion; 0.5 M H2SO4). The recorded value of the current density was 11 mA·cm−2.
As previously noted (in the Materials and Methods), the measurement results were not related to a real electrode surface, only to its dimensions. However, regarding the dimensions, the comparable size of the electrodes with the Ni-Co and Pt catalysts allowed us to obtain similar current density values (the measurements with the Cu-B catalyst resulted in lower current density values). Such measurement results allow us to hope to obtain catalysts that do not contain precious metals whilst maintaining a similar level of catalytic efficiency. Therefore, there is a chance for a significant reduction in costs when replacing platinum catalysts with a Ni-Co catalyst (or Cu-B, if it is possible to accept the lower performance).

Author Contributions

Data curation, P.P.W. and B.W.; investigation, P.P.W. and B.W.; methodology, P.P.W.; writing—original draft, P.P.W. and B.W.; writing—review and editing, P.P.W. and B.W.; supervision, P.P.W. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Centralna Ewidencja Pojazdów i Kierowców CEPiK. Data from 2022 Pursuant to art. 80a Paragraph. 1 and 100a sec. 1 of the Act of June 20, 1997—Road Traffic Law (Poland). Available online: http://www.cepik.gov.pl/statystyki (accessed on 13 October 2022).
  2. Automarket.pl (the Owner of the Automarket.pl Website is PKO Bank Polski). Available online: https://automarket.pl/blog/rynek/jak-pandemia-koronawirusa-zmienila-rynek-sprzedazy-samochodow/ (accessed on 28 July 2020).
  3. Communication From the Commission to the European Parliament, The Council, The European Economic and Social Committee and the Committee of the Regions Empty, ‘Fit for 55′: Delivering the EU’s 2030 Climate Target on the way to climate neutrality, European Commission, Brussels, 14 July 2021. Available online: https://eur-lex.europa.eu/legal-content/EN/TXT/?uri=CELEX%3A52021DC0550 (accessed on 2 February 2022).
  4. Hopmans, J.J. The Problem of the Processing of Spent Oil in the Member States of EEC; Report for the European Economic Community (EEC); National Institute for Wastewater Treatment: Dordrecht, The Netherlands, 1974. [Google Scholar]
  5. Kajdas, C. Major pathways for used oil disposal and recycling, Part 1. Tribotest J. 2000, 7, 61–74. [Google Scholar] [CrossRef]
  6. Fuentes, M.J.; Font, R.; Gómez-Rico, M.F.; Martín-Gullón, I. Pyrolysis and combustion of waste lubricant oil from diesel cars: Decomposition and pollutants. J. Anal. Appl. Pyrol. 2007, 79, 215–226. [Google Scholar] [CrossRef]
  7. Naima, K.; Liazid, A. Waste oils as alternative fuel for diesel engine: A review. J. Pet. Technol. Altern. Fuels 2013, 4, 30–43. [Google Scholar] [CrossRef]
  8. Hamawand, I.; Yusaf, T.; Rafat, S. Recycling of waste engine oils using a new washing agent. Energies 2013, 6, 1023–1049. [Google Scholar] [CrossRef]
  9. Whisman, M.L.; Reynolds, J.W.; Goetzinger, J.W.; Cotton, F.O.; Brinkman, D.W. Re-refining makes quality oils. Hydrocarb. Process. 1978, 57, 141–145. [Google Scholar]
  10. Nerin, C.; Domeno, C.; Moliner, R.; Lazaro, M.J.; Suelves, I.; Valderrama, J. Behavior of different industrial waste oils in a pyrolysis process: Metals distribution and valuable products. J. Anal. Appl. Pyrol. 2000, 55, 171–183. [Google Scholar] [CrossRef]
  11. Chen, G.; He, G. Separation of water and oil from water-in-oil emulsion by freeze/thaw method. Sep. Purif. Technol. 2003, 31, 83–89. [Google Scholar] [CrossRef]
  12. Kwon, W.-T.; Park, K.; Han, S.D.; Yoon, S.M.; Kim, J.Y.; Bae, W.; Rhee, Y.W. Investigation of water separation from water-in-oil emulsion using electric field. J. Ind. Eng. Chem. 2010, 16, 684–687. [Google Scholar] [CrossRef]
  13. Von Fuchs, G.H.; Diamond, H. Oxidation characteristics of lubricating oils. Ind. Eng. Chem. 1942, 34, 927–937. [Google Scholar] [CrossRef]
  14. Rahimi, B.; Semnani, A.; Nezamzadeh-Ejhieh, A.; Shakoori Langeroodi, H.; Davood, M.H. Monitoring of the physical and chemical properties of a gasoline engine oil during its usage. J. Anal. Methods Chem. 2012, 2012, 819524. [Google Scholar] [CrossRef] [Green Version]
  15. Bhaskar, T.; Uddin, M.A.; Muto, A.; Sakata, Y.; Omura, Y.; Kimura, K.; Kawakami, Y. Recycling of waste lubricant oil into chemical feedstock or fuel oil over supported iron oxide catalysts. Fuel 2004, 83, 9–15. [Google Scholar] [CrossRef]
  16. Demirbas, A.; Demirbas, I. Importance of rural bioenergy for developing countries. Energy Convers. Manag. 2007, 48, 2386–2398. [Google Scholar] [CrossRef]
  17. Boughton, B.; Horvath, A. Environmental assessment of waste oil management methods. Env. Sci. Technol. 2004, 38, 353–358. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  18. El-Fadel, M.; Khoury, R. Strategies for vehicle waste-oil management: A case study. Resour. Conserv. Recycl. 2001, 33, 75–91. [Google Scholar] [CrossRef]
  19. Rincón, J.; Cañizares, P.; García, M.T. Waste oil recycling using mixtures of polar solvents. Ind. Eng. Chem. Res. 2005, 44, 7854–7859. [Google Scholar] [CrossRef]
  20. Arpa, O.; Yumrutas, R.; Demirbas, A. Production of diesel-like fuel from waste engine oil by pyrolitic distillation. Appl. Energy 2010, 87, 122–127. [Google Scholar] [CrossRef]
  21. Maceiras, R.; Alfonsín, V.; Morales, F.J. Recycling of waste engine oil for diesel production. Waste Manag. 2017, 60, 351–356. [Google Scholar] [CrossRef]
  22. Littlepage, M. Waste Oil Recycling Apparatus. U.S. Patent 5,188,156, 23 February 1993. [Google Scholar]
  23. Betts, H.S. Diesel Engine Waste oil Recycling System. U.S. Patent 5,476,073, 19 December 1995. [Google Scholar]
  24. Beck, B.D.; Brain, J.D.; Wolfthal, S.F. Assessment of lung injury produced by particulate emissions of space heaters burning automotive waste oil. In Inhaled Particles VI, Proceedings of an International Symposium and Workshop on Lung Dosimetry Organised by the British Occupational Hygiene Society in Co-Operation with the Commission of the European Communities, Cambridge; Elsevier: Amsterdam, The Netherlands, 1988; pp. 257–265. [Google Scholar]
  25. Delistraty, D.; Stone, A. Dioxins, metals, and fish toxicity in ash residue from space heaters burning used motor oil. Chemosphere 2007, 68, 907–914. [Google Scholar] [CrossRef]
  26. Redey, L. Ogniwa Paliwowe; Wydawnictwa Naukowo-Techniczne: Warszawa, Poland, 1973. [Google Scholar]
  27. Hoogers, G. Fuel Cell Technology Handbook; CRC Press: Boca Raton, FA, USA, 2003. [Google Scholar]
  28. Larminie, J.; Dicks, A. Fuel Cell System Explained, 2nd ed.; John Wiley & Sons: Hoboken, NJ, USA, 2003. [Google Scholar]
  29. O’Hayre, R.; Cha, S.W.; Colella, W.; Prinz, F.B. Fuel Cell Fundamentals; John Wiley & Sons: Hoboken, NJ, USA, 2005. [Google Scholar]
  30. Stolten, D. Hydrogen and Fuel Cells. Fundamentals, Technologies and Applications; Wiley-VCH: Weinheim, Germany, 2010. [Google Scholar]
  31. Mekhilef, S.; Saidur, R.; Safari, A. Comparative study of different fuel cell technologies. Renew. Sustain. Energy Rev. 2012, 16, 981–989. [Google Scholar] [CrossRef]
  32. Włodarczyk, P.P.; Włodarczyk, B. Applicability of Waste Engine Oil for the Direct Production of Electricity. Energies 2021, 14, 1100. [Google Scholar] [CrossRef]
  33. Asazawa, K.; Yamada, K.; Tanaka, H.; Oka, A.; Taniguchi, M.; Kobayashi, T. A platinum-free zero-carbon-emission easy fuelling direct hydrazine fuel cell for vehicles. Angew. Chem. 2007, 119, 8170–8173. [Google Scholar] [CrossRef]
  34. Rolison, D.R.; Hagans, P.L.; Swider, K.E.; Long, J.W. Role of hydrous ruthenium oxide in Pt-Ru direct methanol fuel cell anode catalysis: The importance of mixed electron/proton conductivity. Langmuir 1999, 15, 774–779. [Google Scholar] [CrossRef]
  35. Steigerwalt, E.S.; Deluga, G.A.; Cliffel, D.E.; Lukehart, C.M.A. Pt-Ru/graphitic carbon nanofiber nanocomposite exhibiting high relative performance as a direct-methanol fuel cell anode catalyst. J. Phys. Chem. B 2001, 105, 8097–8101. [Google Scholar] [CrossRef]
  36. Serov, A.; Robson, M.H.; Halevi, B.; Artyushkova, K.; Atanassov, P. Highly active and durable templated non-PGM cathode catalysts derived from iron and aminoantipyrine. Electrochem. Commun. 2012, 22, 53–56. [Google Scholar] [CrossRef]
  37. Armour, M.A. Hazarodous Laboratory Chemicals Disposal Guide; CRC Press: Boca Raton, FL, USA, 2003. [Google Scholar]
  38. Gasteiger, H.A.; Koch, S.S.; Sompalli, B.; Wagner, F.T. Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl. Catal. B Environ. 2005, 56, 9–35. [Google Scholar] [CrossRef]
  39. Poynton, S.D.; Kizewski, J.P.; Slade, R.C.T.; Varcoe, J.R. Novel electrolyte membranes and non-Pt catalysts for low temperature fuel cells. Solid State Ion. 2010, 181, 219–222. [Google Scholar] [CrossRef] [Green Version]
  40. Othman, R.; Dicks, A.L.; Zhu, Z. Non precious metal catalysts for the PEM fuel cell cathode. Int. J. Hydrogen Energy 2012, 37, 357–372. [Google Scholar] [CrossRef]
  41. Williams, H.; Gnanamani, M.K.; Jacobs, G.; Shafer, W.D.; Coulliette, D. Fischer–Tropsch Synthesis: Computational Sensitivity Modeling for Series of Cobalt Catalysts. Catalysts 2019, 9, 857. [Google Scholar] [CrossRef] [Green Version]
  42. Jo, S.B.; Kim, T.Y.; Lee, C.H.; Woo, J.H.; Chae, H.J.; Kang, S.-H.; Kim, J.W.; Lee, S.C.; Kim, J.C. Selective CO Hydrogenation Over Bimetallic Co-Fe Catalysts for the Production of Light Paraffin Hydrocarbons (C2–C4): Effect of Space Velocity, Reaction Pressure and Temperature. Catalysts 2019, 9, 779. [Google Scholar] [CrossRef] [Green Version]
  43. Włodarczyk, P.P.; Włodarczyk, B. Microbial Fuel Cell with Ni–Co Cathode Powered with Yeast Wastewater. Energies 2018, 11, 3194. [Google Scholar] [CrossRef] [Green Version]
  44. Włodarczyk, B.; Włodarczyk, P.P. The Membrane-Less Microbial Fuel Cell (ML-MFC) with Ni-Co and Cu-B Cathode Powered by the Process Wastewater from Yeast Production. Energies 2020, 13, 3976. [Google Scholar] [CrossRef]
  45. Qasim, M.; Bashir, M.S.; Iqbal, S.; Mahmood, Q. Recent advancements in α-diimine-nickel and -palladium catalysts for ethylene polymerization. Eur. Polym. J. 2021, 160, 110783. [Google Scholar] [CrossRef]
  46. Abas, M.; Bahadur, A.; Ashraf, Z.; Iqbal, S.; Muhammad Shahid Riaz Rajoka, M.S.R.; Rashid, S.G.; Jabeen, E.; Iqbal, Z.; Abbas, Q.; Bais, A.; et al. Designing novel anticancer sulfonamide based 2,5-disubstituted-1,3,4-thiadiazole derivatives as potential carbonic anhydrase inhibitor. J. Mol. Struct. 2021, 1246, 131145. [Google Scholar] [CrossRef]
  47. Zhang, R.; Gao, R.; Gou, Q.; Lai, J.; Li, X. Recent Advances in the Copolymerization of Ethylene with Polar Comonomers by Nickel Catalysts. Polymers 2022, 14, 3809. [Google Scholar] [CrossRef]
  48. Paraska, O.; Karvan, S. Mathematical modelling in scientific research of chemical technology processes. Tech. Trans. Mech. Crac. Univ. Technol. Press 2010, 8, 203–210. [Google Scholar]
  49. Survila, A.; Mockus, Z.; Kanapeckaitė, S.; Samulevičienė, M. Effect of syntanol DS-10 and halides on tin(II) reduction kinetics. Electrochim. Acta 2005, 50, 2879–2885. [Google Scholar] [CrossRef]
  50. Ignatov, O.V.; Shalunova, I.V.; Panchenko, L.V.; Turkovskaia, O.V.; Ptichkina, N.M. Degradation of Syntanol DS-10 by bacteria immobilized in polysaccharide gels (article in Russian). Prikl. Biokhimiia Mikrobiol. 1995, 31, 220–223. [Google Scholar]
  51. Kravchenko, A.V.; Rudnitskii, A.G.; Nesterenko, A.F.; Kublanovskii, V.S. Degradation of Syntanol DS-10 promoted by energy transfer reactions. Ukr. Chem. J. 1994, 60, 11–13. [Google Scholar]
  52. Włodarczyk, P.P.; Włodarczyk, B. Wastewater Treatment and Electricity Production in a Microbial Fuel Cell with Cu–B Alloy as the Cathode Catalyst. Catalysts 2019, 9, 572. [Google Scholar] [CrossRef] [Green Version]
  53. Włodarczyk, P.P.; Włodarczyk, B. Ni-Co alloy as catalyst for fuel electrode of hydrazine fuel cell. China-USA Bus. Rev. 2015, 14, 269–279. [Google Scholar] [CrossRef] [Green Version]
  54. Włodarczyk, P.P.; Włodarczyk, B. Preparation and Analysis of Ni–Co Catalyst Use for Electricity Production and COD Reduction in Microbial Fuel Cells. Catalysts 2019, 9, 1042. [Google Scholar] [CrossRef] [Green Version]
  55. Włodarczyk, B.; Włodarczyk, P.P. Comparison of Cu-B Alloy and Stainless Steel as Electrode Material for Microbial Fuel Cell. In Renewable Energy Sources: Engineering, Technology, Innovation; Wróbel, M., Jewiarz, M., Szlęk, A., Eds.; Springer Proceedings in Energy; Springer: Cham, Switzerland, 2020. [Google Scholar] [CrossRef]
  56. Włodarczyk, B.; Włodarczyk, P.P. Electrooxidation of methyl alcohol with Ni-Co catalyst. In Infrastructure and Ecology of Rural Areas; Polish Academy of Sciences: Kraków, Poland, 2018; Volume 2, pp. 305–315. [Google Scholar] [CrossRef]
  57. Włodarczyk, B.; Włodarczyk, P.P. Microbial fuel cell with Cu-B cathode powering with wastewater from yeast production. J. Ecol. Eng. 2017, 18, 224–230. [Google Scholar] [CrossRef]
  58. Holtzer, M.; Staronka, A. Chemia Fizyczna. Wprowadzenie; Wydawnictwo AGH: Kraków, Poland, 2000. [Google Scholar]
  59. Bielański, A. Podstawy Chemii Nieorganicznej; Wydawnictwo Naukowe PWN: Warsaw, Poland, 2013. [Google Scholar]
Figure 1. Number of newly registered motor vehicles in Poland for the years 2011–2021 [1].
Figure 1. Number of newly registered motor vehicles in Poland for the years 2011–2021 [1].
Energies 15 07686 g001
Figure 2. The decantated, filtered and mixed in equal proportions waste engine oil (WEO).
Figure 2. The decantated, filtered and mixed in equal proportions waste engine oil (WEO).
Energies 15 07686 g002
Figure 3. Measurement setup for WEO electrooxidation with new catalysts. (A) Electrochemical deposition of the alloys: 1—components; 2—foam copper electrode; 3—chemical bath; 4—power supply. (B) Preparation of the WEO emulsion: 5—WEO samples; 6—filtration; 7—mixed oil; 8—water; 9—detergent; 10—emulsion preparation; 11—mechanical stirrer. (C) Electrooxidation of the WEO emulsion: 12—reactor (electrochemical cell); 13—magnetic stirrer; 14—potentiostat; 15—computer.
Figure 3. Measurement setup for WEO electrooxidation with new catalysts. (A) Electrochemical deposition of the alloys: 1—components; 2—foam copper electrode; 3—chemical bath; 4—power supply. (B) Preparation of the WEO emulsion: 5—WEO samples; 6—filtration; 7—mixed oil; 8—water; 9—detergent; 10—emulsion preparation; 11—mechanical stirrer. (C) Electrooxidation of the WEO emulsion: 12—reactor (electrochemical cell); 13—magnetic stirrer; 14—potentiostat; 15—computer.
Energies 15 07686 g003
Figure 4. Electrochemical cell (reactor): 1—WEO emulsion (or pure detergent); 2—auxiliary electrode (AE); 3—electrolyte; 4—stirrer bar; 5—connections; 6—reference electrode (RE); 7—Luggin capillary; 8—working electrode (WE) with Ni-Co or Cu-B catalyst.
Figure 4. Electrochemical cell (reactor): 1—WEO emulsion (or pure detergent); 2—auxiliary electrode (AE); 3—electrolyte; 4—stirrer bar; 5—connections; 6—reference electrode (RE); 7—Luggin capillary; 8—working electrode (WE) with Ni-Co or Cu-B catalyst.
Energies 15 07686 g004
Figure 5. Measurement setup for the measurements of WEO electrooxidation.
Figure 5. Measurement setup for the measurements of WEO electrooxidation.
Energies 15 07686 g005
Figure 6. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Ni-Co catalyst for an electrolyte concentration of 0.5 M. Electrooxidation: (a) temperature: 20 °C; (b) temperature: 40 °C.
Figure 6. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Ni-Co catalyst for an electrolyte concentration of 0.5 M. Electrooxidation: (a) temperature: 20 °C; (b) temperature: 40 °C.
Energies 15 07686 g006
Figure 7. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Ni-Co catalyst for an electrolyte concentration of 0.5 M. Electrooxidation: (a) temperature: 60 °C; (b) temperature: 80 °C.
Figure 7. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Ni-Co catalyst for an electrolyte concentration of 0.5 M. Electrooxidation: (a) temperature: 60 °C; (b) temperature: 80 °C.
Energies 15 07686 g007
Figure 8. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Ni-Co catalyst for an electrolyte concentration of 2 M. Electrooxidation: (a) temperature: 20 °C; (b) temperature: 40 °C.
Figure 8. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Ni-Co catalyst for an electrolyte concentration of 2 M. Electrooxidation: (a) temperature: 20 °C; (b) temperature: 40 °C.
Energies 15 07686 g008
Figure 9. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Ni-Co catalyst for an electrolyte concentration of 2 M. Electrooxidation: (a) temperature: 60 °C; (b) temperature: 80 °C.
Figure 9. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Ni-Co catalyst for an electrolyte concentration of 2 M. Electrooxidation: (a) temperature: 60 °C; (b) temperature: 80 °C.
Energies 15 07686 g009
Figure 10. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Cu-B catalyst for an electrolyte concentration of 0.5 M. Electrooxidation: (a) temperature: 20 °C; (b) temperature: 40 °C.
Figure 10. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Cu-B catalyst for an electrolyte concentration of 0.5 M. Electrooxidation: (a) temperature: 20 °C; (b) temperature: 40 °C.
Energies 15 07686 g010
Figure 11. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Cu-B catalyst for an electrolyte concentration of 0.5 M. Electrooxidation: (a) temperature: 60 °C; (b) temperature: 80 °C.
Figure 11. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Cu-B catalyst for an electrolyte concentration of 0.5 M. Electrooxidation: (a) temperature: 60 °C; (b) temperature: 80 °C.
Energies 15 07686 g011
Figure 12. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Cu-B catalyst for an electrolyte concentration of 2 M. Electrooxidation: (a) temperature: 20 °C; (b) temperature: 40 °C.
Figure 12. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Cu-B catalyst for an electrolyte concentration of 2 M. Electrooxidation: (a) temperature: 20 °C; (b) temperature: 40 °C.
Energies 15 07686 g012
Figure 13. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Cu-B catalyst for an electrolyte concentration of 2 M. Electrooxidation: (a) temperature: 60 °C; (b) temperature: 80 °C.
Figure 13. Electrooxidation curves of WEO emulsion (black lines) and detergent (blue lines) for various concentrations of detergent and emulsion on the Cu-B catalyst for an electrolyte concentration of 2 M. Electrooxidation: (a) temperature: 60 °C; (b) temperature: 80 °C.
Energies 15 07686 g013
Table 1. Summary of WEOs and the corresponding mileage.
Table 1. Summary of WEOs and the corresponding mileage.
Engine Oil Grade 1Type of Engine 1Capacity and Power 1Oil Mileage 1
5W30Diesel 21.5; 115 hp 430,000 km
5W30Diesel 21.5; 115 hp 415,000 km
5W30Diesel 21.6; 92 hp 415,000 km
5W30Diesel 23.0; 245 hp 415,000 km
5W40Petrol 31.0i; 68 hp 415,000 km
10W40Petrol 33.0i; 180 hp 415,000 km
15W40Petrol 32.0; 105 hp 410,000 km
10W40Petrol 31.0i; 72 hp 415,000 km
10W40LPG 32.0i; 115 hp 415,000 km
10W40LPG 31.4i; 75 hp 410,000 km
1 Data derived from the car service station; 2 turbo; 3 naturally aspirated; 4 metric horsepower; i: fuel injection.
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Włodarczyk, P.P.; Włodarczyk, B. Feasibility of Waste Engine Oil Electrooxidation with Ni-Co and Cu-B Catalysts. Energies 2022, 15, 7686. https://doi.org/10.3390/en15207686

AMA Style

Włodarczyk PP, Włodarczyk B. Feasibility of Waste Engine Oil Electrooxidation with Ni-Co and Cu-B Catalysts. Energies. 2022; 15(20):7686. https://doi.org/10.3390/en15207686

Chicago/Turabian Style

Włodarczyk, Paweł P., and Barbara Włodarczyk. 2022. "Feasibility of Waste Engine Oil Electrooxidation with Ni-Co and Cu-B Catalysts" Energies 15, no. 20: 7686. https://doi.org/10.3390/en15207686

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop