Egyptian Journal of Petroleum xxx (2017) xxx–xxx

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Egyptian Journal of Petroleum

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Recycling of used engine oil by different solvent

Doaa I. Osman ⇑, Sayed K. Attia, Afaf R. Taman
Egyptian Petroleum Research Institute, Analysis and Evaluation Department, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: The refining of lubricating oils from waste lubricating oil was examined utilizing a novel blend of solvent
Received 15 November 2016 extraction and activated alumina adsorbent. The activity of these solvent extraction blends {toluene,
Revised 8 May 2017 butanol and methanol (A)}, {toluene, butanol and ethanol (B)} and {toluene, butanol and isopropanol
Accepted 30 May 2017
(C)} was evaluated experimentally, oil to solvent proportions from 1:1 to 1:3 were analyzed for mixture
Available online xxxx
blend (C). The results confirm solvent mixture (A) gave good efficiency with the highest percent sludge
removal. The maximum percent of sludge removal improves with the increase of solvent to oil ratios.
Keywords:
The physical properties of the recycle oil were measured. The results show the change in the properties
Re-recycling used lube oil
Solvent extraction
of recycling oil and have good efficiency.
Adsorption Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction followed by adsorption is more effect processes for recycling of

waste lubricating oils [4–13]. It is aimed to conserving natural
The most important petroleum fraction is Lubricating oil that is resources and recovering (rather than destroying) the lubricating
used in almost all vehicles and machines. Lube oils are used to oil. This is a mostly attractive cleaner technology. The solvent
decrease rubbing between surfaces in moving parts. After oxida- selected should have a maximum solubility for base oil and mini-
tion, most impurities are generated in base oil, during its applica- mum for additives carbonaceous. The solvent is then recovered
tion in internal combustion engine. This contamination contains by distillation for recycle reason [3]. The key commitment of this
unsaturation, phenolic compound, aldehyde, acidic compound, examination is to diminish the percent oil misfortunes utilizing
additive, metals, varnish, gums and other asphaltic compounds suitable solvent extraction. Different parameters i.e. the proportion
originating from the overlay of bearing surfaces and degradation of solvent to oil, extraction condition and kind of solvents are also
of the base oil components [1]. In spite of impurities, most of the studied.
base oil part in the waste oil is not exhausted. The chemical com-
position of the lubricating oil is usually preserved to a large
2. Experimental
amount because of the high stability of the heavy compounds con-
tain in the base oil [2]. Used lubricating oils which difficult to han-
2.1. Material
dle anthropogenic pollutant due to its toxicity and become
undesirable for use. Its transfer strategies of the past, for example,
Used lubricating oil was obtained and collected from EPRI
arrive filling, street oiling, dump on the ground diminishes soil effi-
(Egyptian petroleum institute) oil service station. All reagents (pur-
ciency and makes the plants developed on the dirt to be unsatisfac-
chased from Merck Co., Aldrich, and Fluka chemical Co.) (Toluene,
tory for food and forage. The recycling of waste oil may be an
1-butanol, ethanol, methanol, isopropanol and alumina).
appropriate and cheap alternative to and burn incineration [3]. Dif-
ferent recycling techniques have been proposed for refining of used
lubricating oils. During refining, the chemical, physical and 2.2. Procedure
mechanical impurities are removed with the following processes:
distillation, acidic refining, clay treatment and hydrogenation. The- The used oil is subjecting filtration before to treatment. This
ses processes give different yield and product. Solvent extraction was done using a funnel with a filter paper placed in it, and then
a vacuum pump was connected to the filtering flask to which the
funnel was fixed with the aid of a rubber stopper. 100 ml of used
Peer review under responsibility of Egyptian Petroleum Research Institute. lubricating oil was mixed with a blend comprised of 100 ml of
⇑ Corresponding author. toluene, 100 ml of 1-butanol and 100 ml of methanol in a closed
E-mail address: [email protected] (D.I. Osman). vessel. The whole mixture in a beaker was placed on a magnetic

http://dx.doi.org/10.1016/j.ejpe.2017.05.010
1110-0621/Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: D.I. Osman et al., Recycling of used engine oil by different solvent, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.
ejpe.2017.05.010
2 D.I. Osman et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

stirrer and stirred for one hour. Then it was allowed to stand for Table 2
24 h. The clear surface oily layer containing solvents and oil was Effect of activated alumina on the raffinates.

transferred to a rotary evaporator in order to separate the solvents A B C

from the regenerated lubricating oil. The separated base oil was Raffinate, wt% 48 42.8 44
then mixed with activated alumina at a proportion of 1:5 alumina. Sludge, wt% 52 57.2 56
The alumina was added to remove the dark color. The same Color, wt% YELLOW YELLOW YELLOW
method was employed in the Toluene, 1-butanol, and ethanol
and also with Toluene, 1-butanol and isopropanol. The same
method was working in the Toluene, 1-butanol, and isopropanol Table 3
by solvent to oil ratio 1:2 and 1:3 Solubility and dielectric constant of the three solvent mixtures.

Solvent sample Solubility Dielectric

(j/m3) constant
3. Results and discussion Toluene + butanol and methanol (A) 23.2 6.994
Toluene + butanol and ethanol (B) 22.2 6.993
Waste oil is a blend of combustion product such as water, fuel, Toluene + butanol and iso propanol (C) 21.5 6.992
road dust, wear metal and oxidation product which form complex
and corrosive organic acids. The latent heat of vaporization is the
amount of Vander Waals forces that hold liquid molecules together
[14]. An important experimental measurement of the solvent Table 4
Effect of solvent: oil ratio on the refining of used oil using solvent mixture C.
extraction re-refining process is normally represented by the
amount of sludge removed from the used oil. This may be Solvent: Oil Ratio 1:1 1:2 1:3
expressed as the percent sludge removal (PSR) which is the mass RAFFINATE 81.1 70.1 55.6
of sludge removed in gram/100 g of used oil. SLUDGE 18.9 29.9 44.4
The experimental results indicate that the more effect for COLOR BLACK BLACK BLACK

sludge removal capability of solvent mixtures A, B and C as shown

in the Tables 1 and 2 It is found that mixture A removed maximum
sludge percent (52%) followed by mixture B (36.7%) and mixture C Table 5
Effect of activated alumina on the refining for raffinates.
removed lower percent (18.9%). these attribute to the solubility of
the base stock oil in these solvent and their dielectric constant as C1:1 C1:2 C1:3
shown in Table 3. The raffinate percent decrease from solvent mix- RAFFINATE 41.3 37.9 36.9
ture A followed by solvent mixtures B and C as given in Tables 1 SLUDGE 58.7 62.1 63.1
and 2. The raffinate produced from solvent mixture A is yellow COLOR YELLOW YELLOW YELLOW
in color because of it free from sludge as shown in Table 1 and 2.
This result is due to the solubility of solvent mixture A is higher
23.2 (g/m3)1/2 as compared with that of solvent mixture B and C, ishing stage. It is found that the results for 1:3 solvent oil ratio of
(22.2 and 21.5 g/m3) respectively. Also, the dielectric constant of all inside the requirement of the base stock oil.
solvent mixture A is higher than the other solvent mixtures (B After alumina treatment for sludge removal as given in Tables 4
and C) as given in Table 3 These results indicate that as chain and 5 it is clear that there is a decrease in the oil loss and incre-
length of carbon atoms in the solvent and polarity decreases, its ment in the sludge separation. This is attributed to that the adsor-
ability to eliminate sludge increase, although the solvent become bent activity of raffinate oil depends on the ability of an adsorbent
more miscible in the oil as shown in Table 1–3. It is clear that sol- to selectivity remove resinous, compounds containing sulfur,
vent mixture A has higher solubility and dielectric constant. So, has unsaturated, polycyclic aromatic materials.
maximum efficiency for sludge removal. Methanol removes the
heavy components more than the other two solvent mixtures
because of its dielectric constant is higher. 5. Effect of alumina adsorption

The ion adsorption behavior of alumina (Al2O3) arises from the

4. Study of solvent–oil ratio acid–base surface hydroxyl groups. The protonation and deproto-
nation of these surface hydroxyl groups effect the oxide surface
The effect of the solvent–oil ratio on the percent of sludge to develop an electrical charge promoting adsorption. The cation
removal for the solvent mixture at 25 °C was shown in Tables 4 and anion exchange takes place at the acid (–OH) and the base (–
and 5. It is clear that as the solvent oil ratio increase, the maximum OH) hydroxyl sites Fig. 3.
percent sludge removal increase and the raffinate oil decreased. Although the activated alumina improved the color of the oil.
This is because as the oil to solvent proportions increases the med- The physical method of refining with the adsorbent is a surface
ium mutual solubility of the oil in the solvent increase. The more phenomenon depending on the specific affinity between the adsor-
percent of sludge removal means good efficiency of re-refining bent and the adsorbate dispersed in the spent engine oil. It can be
oil, these process is cheaper than refining stages such as vacuum seen that the properties of the treated oil with activated alumina
distillation and finishing stage by alumina adsorption or hydro fin- has the best performance.
The treated oil with solvent extraction and activated alumina
was analyzed according to the standard method in ASTM [15] IP
Table 1
[16] for density, carbon residue, ash content, pour point, water
Effect of different solvent mixtures on the refining of used oil.
content, sulfur content, viscosity and total acid number as shown
A B C in Tables 6, 7 and Figs. 1 and 2.
Raffinate, wt% 48 63.3 81.1 The results in Tables 6 and 7 and Figs. 1 and 2 indicate the phys-
Sludge, wt% 52 36.7 18.9 ical characteristics of used oil, refined oil by solvent extraction pro-
Color, wt% YELLOW BLACK BLACK
cess and after activated alumina treatment. It is clear that the

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ejpe.2017.05.010
 D.I. Osman et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 3

Fig. 2. Change in Sulfur Content with Refining Processes.

dewaxing has been done affected on pour point. All measured

properties have been improved to reasonable values such as Water
content, ash content, carbon residue, sulfur content and given in
Tables 6 and 7 and Figs. 1 and 2. The value of Ash content shows
the presence of metallic impurities which has been reduced by
89.5% in case of solvent mixture A in the raffinate oil, showing
the removal salts. Acid value is also reduced as shown in the Table 6
and Fig. 1 Due to organic, inorganic acids, esters, phenolic com-
Fig. 1. Change In Total Acid Number With Refining Processes.
pounds, lactones, and resins have been separated out suitably.
The results also show that the viscosity gave higher viscosity
improvements after the refining process. This is because of the pos-
density of the used oil is higher than that for the treated oils. This is sible conversion of possible impurities in the used oil. In observa-
due to the presence of sludge and a higher percent of sulfur com- tion of the interest of the oil to act as a coolant or heat transfer
pounds. For used oil, the pour point is lower as compared with that medium, it must be capable of maintaining adequate fluidity at
of refined oil. The lube oil and the method of refining; especially it high film temperature. The sulfur content is reduced from

Please cite this article in press as: D.I. Osman et al., Recycling of used engine oil by different solvent, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.
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4 D.I. Osman et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

Fig. 3. Mechanism of the effect of hydroxyl groups of alumina surface and carboxylic acid of (organic group).

Table 6
Physicochemical Properties of Used Oil and Refined Oil By Solvent Extraction And Alumina Treatment.

Experiment Origin sample A B C

[email protected] 0.9116 0.8810 0.8847 0.8826
Specific [email protected] 0.9125 0.8818 0.8855 0.8834
Viscosity, cSt, @40 °C 107.48 51.66 76.02 83.67
@100 °C 12.93 8.48 12.1 9.98
V.I 115.1 139.55 155.76 98.4
Pour point, °C 0 3 3 0
Water content,ppm 2573.2 143.4 94.1 49.9
Ash content,wt% 1.05 0.0094 0.046 Nil
Carbon residue, wt% 1.12 Nil 0.01 Nil
Total acid number, mg KOH/g 7.8 1.47 0.79 0.59
Sulfur content 0.82 0.74 0.67 0.66

Table 7
Physicochemical Properties For Refined Oil Using Different Solvent: Oil Ratio Using Solvent Mixture C and Fresh Co Operation Company Oil.

Experiment 1:1 1:2 1:3 Result of Fresh Cooperation Company Oil

[email protected] 0.8826 0.8825 0.8816 0.8817
Specific [email protected] 0.8834 0.8834 0.8825
Viscosity, cSt, @40 °C 83.67 74.14 72.08 52.34
@100 °C 9.98 11.80 11.59 7.41
V.I. 98.4 154.31 155.15 92
Pour point, °C 0 3 0 3
Water content,ppm 49.9 86.6 3.7
Ash content,wt% Nil nil Nil 0.003
Carbon residue, wt% Nil nil Nil –
Total acid number, mg KOH/g 0.59 0.15 0.06 0.067
Sulfur content 0.66 0.42 0.25 0.34

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ejpe.2017.05.010