An Extraction - Adsorption Combo-Process for Re-refining of Used Oil

Ranvir Singh#, Manoj Srivastava, Manoj Kumar, U.C. Agrawal and M.O.Garg
Indian Institute of Petroleum, Dehradun-248005, India

Abstract

Lubricating oil has wide range of applications. It‟s by far major application is in motor vehicles and engines
where it is used to smoothen the functioning of engine parts and thereby improve the performance as well
as extend the life of engine. Periodically, it has to be replaced at regular intervals because of
contamination of oil caused by inclusion of „wear „and „tear‟ of metal parts in it. Worldwide, the earlier
practice of dumping the contaminated oil after use poses many serious environmental problems. The rising
crude prices are also adversely affecting the margins of lube refineries. This scenario is leading to thinking
in favour of „re-refining‟ and „re-use‟ of used lube oils.

Generally, used oil contains wide range of hydrocarbons (C 15–C50), but its actual chemical composition
depends largely on the „crude source‟, „mother distillates‟ and nature of „virgin base oils‟. In a study carried
out at Indian Institute of Petroleum, Dehradun and being reported in the present paper, used oil distillate
from a leading re-refiner in USA was selected as feed stock. The oil sample was characterized for ASTM
distillation D-1160, specific gravity, sulphur content, color and odor etc. The used oil was subjected to
„solvent extraction‟ (where NMP was taken as solvent in „continuous phase‟ and used oil distillate as
„dispersed phase‟). Typical process parameters such as temperature of the single stage glass extractor,
solvent-to-feed ratio and water content in NMP (to provide more affinity towards the aromatics) were
varied. The paper discusses effect of these parameters in terms of quality of oil product (raffinate obtained
after extraction). In order to attain the stringent limits for sulfur content in re-refined used oil, solvent free
raffinate was percolated through „charcoal bed‟ to further complement „extraction step‟. Significant
improvement in the quality of re-refined used oil in terms of sulfur content, color and odor has been
achieved through the combo process which has been discussed in the paper in detail.

Keywords: adsorption, charcoal bed, NMP extraction, re-refining, used lube oil.

Introduction

Lubricating oil serves as a sink to the wear and tear of engine parts and other waste material gases
generated in internal combustion processes. This lubricating oil after use for a recommended period is
turned into used lubricating oil which contains absorbed condensates and accumulated polyaromatic
hydrocarbons and looses several of its desirable properties. Further, used oil also contains degraded
additives such as high percentage of detergents/additives/dispersants, synthetic VI improvers, pour point
depressant etc. Due to all these, it has to be replaced with fresh oil after certain time to restore/improve the
engine performance. Further use of used oil as such - without any re-processing – or dumping it as such is
strictly banned worldwide, as it creates serious health hazard and poses other „ecological‟ and
„environmental problems‟. Hence, re-refining of used oil is regarded these days as one of the areas of
prime importance and further re-refined oils are considered to be equivalent to the virgin base oils.

Since olden days, reclamation of used oil by „acid- clay process‟ has been extensively used to recover
valuable „base oil‟ present in used oil samples collected from various sources and has also played an
important role in terms of recycling of product in the market. Due to stringent environmental conditions,
need of time is to shift to some alternative technologies e.g. UOP Hylube process, Meinken/Hybrid
Meinken process, IFP- Snamprogratti process, KTI process, CEP-Mohwak process, PROP process, DEA
technology etc. Each of these developed technologies has specific „advantages‟ or „disadvantages‟ over
other alternatives in terms of cost and availability of ternary components such as hydrogen availability,
solvent requirement, or energy inputs in case of energy intensive process (i.e. incineration). In the context
of all these, there is no universally accepted well defined technology available for application to all of the
used oils of different grades.

*Corresponding author: Tel: +91-135-2660113-116 ; Fax No: +91-135-2660098 /2660202;

Email: rvsingh@iip.res.in
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„Solvent extraction‟ is relatively simple process where solvent and feed are mixed in appropriate quantity
and left for sufficient residence time, allowing the feed –solvent mix to settle in two separate „phases‟ viz.
raffinate and extract. Most of the carbonaceous impurities present in used oil get concentrated in extract
leaving the raffinate relatively enriched with purer base oil. A literature survey shows use of various polar
and non-polar solvents for re-refining of used oils.

Crowley (US Patent 4,169,044) described technology for used oil re-refining by using „propane‟ as solvent.
The patent claims advantage of using propane as solvent to eliminate the carbon, lead, phosphorous,
calcium and other metal additives in used oil. Solvent-to-feed ratio in extraction step was reported to be in
the range of 0.6 to 1 and recycling of raffinate into previous step to improve the yields of finished product.
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Top and bottom temperatures of solvent extraction unit were maintained in the range of 170 to 200 C and
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160-185 C respectively.

Fletcher et al (US Patent 4,399,025) described a process for re-refining of used oil by using tetra hydro
furfural alcohol as solvent. Further, solvent was recovered from the raffinate and extract stream by distilling
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under vacuum of (2.5 mm Hg) and at 200 F and steam stripping for removing trace components An yield
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of ~ 82 % was reported at extraction temperature of 130 F and solvent-to-feed ratio of 1. Applicability of
process for light as well heavy fraction of lube oil was also reported.

Elbashir et al studied the method to predict effective solvent extraction parameters for recycling of used
lubricating oil. For this purpose, three extracting solvents namely 2-propanol, 1-butanol, methyl-ethyl-
ketone were tried on the basis of their solubility parameter; MEK was found by them to be better than 2-
propanol and 1-butanol.

Liquid supercritical ethane was employed as a solvent for the re-refining of used lubricant oils by (Jesusa
Rinc´on). They claimed that the waste oil contaminated with heavier compounds present in used oil get
dissolved in „ethane‟ under the super critical conditions. The pressure variation in the range of 40–145
2 0
Kg/cm and temperature from 20- 95 C showed improvement in its yield, quality and separation efficiency.
However, they reported that a soft finishing treatment is further required in order to attain the specifications
required for base oil.

Fontana et al showed the effectiveness of „ultrasonics‟ on removal of lead content in waste oil. The waste
oil was mixed with aqueous solution of HNO 3 and further sent to „sonicator‟ which drastically reduces time
of normal extraction step as high frequency ultrasonic waves break the „chemical bonds‟ by „mechanical‟
means and results in improvement in yield.

In the study discussed in this paper, a combo process (solvent extraction and adsorption) was employed to
re-refine used oil to meet required leveling desired properties in respect of colour and sulfur and pass the
API a Group – II specifications.

Experimental Study

Materials & Test Methods Employed :

Used oil distillate sample received from small a prominent used oil refiner in USA was obtained and
phyisio-chemically characterized; the data has been reported in Table 1. Commercial grade NMP supplied
from BASF, Germany has been used as solvent along with appropriate quantity of distilled water for
extraction studies.

The percentage of water in solvent was determined by standard Karl-Fisher method. Various types of
hydrocarbons in used oil were determined by using ASTM D 2549 method using AR/LR grade hexane,
benzene, toluene, di-ethyl ether, chloroform, methanol and ethanol. Standard ASTM/BIS procedures were
used to characterize feed and products. Activated charcoal was used as adsorbent to improve the colour
of re-refined oil.

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Table 1: Physico–chemical Characteristics of Used Oil Distillate

Properties
60
Specific gravity60 0.8592
o
Refractive Index (at 20 C) 1.4720
Viscosity index (VI) 87
0
Pour point ( C) -15
Sulphur (ppm) 1519.5
Hydrocarbon type analysis (ASTM-2549)

Saturates 90.53
Aromatics 9.47
Sulphur (ppm) in saturates 37.1
Sulphur (ppm) in aromatics 1.6

LLE Setup & Procedure :

The single stage extractor of one liter capacity with multi-pronged stirrer attached with electric motor (50
Hz/220V AC) was used for mixing solvent and feed for extraction. The speed of stirrer in the extractor can
be varied 0-1200 rpm. Oil flows through oil circulation bath in the annulus space of around 2 mm to
maintain the constant temperature throughout the extractor. Known quantity of solvent and feed were
added in the extractor where it was continuously stirred at constant speed at 400rpm for 45-60 minutes to
allow continuous molecular interaction between the Hydrocarbon and solvent molecules at selected
temperature and normal atmospheric pressure conditions. The well mixed solution was separated into two
phases which were then allowed to settle for about two hours at the same temperature. The settled phases
namely „raffinate‟ and „extract‟ were withdrawn separately. Both, phases contain solvent but in different
proportions due to variation of solubility of solvent with different hydrocarbons. Both, the extract and
raffinate phases were made solvent free by atmospheric distillation under nitrogen stripping to avoid
oxidation. Solvent free raffinate and extract samples were characterized for their important physico-
chemical properties. Recovered solvent from experiment was in admixture reused with fresh solvent in
further experiments.

RESULTS & DISCUSSION

The physico-chemical properties of the used oil distillate are given in Table- 1. The specific gravity of the
used oil distillate at 60/60 is 0.8592 and refractive index at 20°C is 1.4720, which reflects that used oil
distillate is predominantly rich in paraffins. The viscosity index (VI) of used oil distillate is 87, which falls in
the range of group-I base oil. The pour point of distillate is -15°C which is good enough to serve even in
extra cold weather conditions. The hydrocarbon type analysis by ASTMD – 2549 also revealed that it
contains 90.53wt% saturates (i.e.> 90%), but presence of high sulphur 1519.5 ppm (more than 300 ppm)
put this used oil distillate into group-I base oil category. The ASTM distillation data (ASTM D-1160) of the
distillate has been plotted in Figure - 2. The graph shows that the initial boiling point (IBP) of distillates is
~250°C and final boiling point (FBP) is ~450°C. The lower IBP indicate that the used oil distillate is
contaminated with lower boiling hydrocarbons coming from extraneous sources such as washing solvents,
naphtha, furnace oil etc. at garages/collection centers. These light hydrocarbons are not the part of lube oil
and can be separated and rejected during fractionation step and can be blended in furnace oil or any other
low value products.

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 Figure - 2 : ASTM D1160 curve for used Oil distillate
500

450
Temperature(deg C)
400
R² = 0.9627
350

300

250

200
0 10 20 30 40 50 60 70 80 90 100
% Volume Distilled

Effect of Temperature:

To see the effect of extraction temperature on used oil quality, single stage extraction runs under identified
conditions except the operating temperature were given. In two sets of these extraction runs, solvent-to-
feed ratio was kept at 1 and temperature at 50/90C. The average results of these runs are summarized in
the Table 2.

Table 2: Effect of Temperature on Desulfurization of Used Oil

Run 1 Run 2
O
Extraction temperature C 50 90
Solvent neat NMP neat NMP
Solvent-to-feed ratio 1.0 1.0
Raffinate yield ( % wt) 89.5 76.0
15
Raffinate density D4 (g/ml) 0.8532 0.8526
Used oil distillate sulfur (ppm) 1519.5 1519.5
Raffinate sulfur (ppm) 678.4 563.4
0
It is clear from Table-2 that on increasing the extraction temperature from 50 to 90 C, solubility of
hydrocarbons in solvent gets improved with the result that raffinate yield comes down from 89.9% (at
0 0
50 C) to 76% (at 90 C). The increase in solubility of solvent led to more removal of sulphur containing
aromatic hydrocarbons from raffinate as shown by more reduction in sulfur (563.4 ppm) at higher
0
extraction temperature i.e. at 90 C rather than less reduction in sulfur (678.4 ppm) at lower extraction
0
temperature i.e. at 50 C as compared to used oil distillate. Higher extraction temperature leads to greater
improvement in raffinate quality but at the cost of yield.

Effect of Solvent Composition:

The effect of solvent composition i.e. NMP and water percentage on raffinate yield and sulphur reduction is
shown in Figure 3.

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 Fig 3: Sulphur Reduction Vs Solvent Composition
With Effect on Raffinate Yield
102 102
100 100
% NMP Content

98 98
96 96
94 % yield 94
% NMP Content
92 92
90 90
88 88
53 55 57 59 61 63 65
Sulphur reduction in %

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Figure-3 Effect of solvent composition on sulfur reduction at Temperature 50 C

Fig 4 : Sulphur-reduction Vs Solvent Composition

with Effect on Raffinate Yield
102
100
100
% NMP Content

98 90

% Raffinate yield
96
80
94

92 % NMP Content 70
90 % yield
88 60
48 49 50 51 52 53 54 55 56 57
Sulphur-Reduction in %

0
Figure-4: Effect of solvent composition on sulfur reduction at Temperature 90 C

The results show that addition of water in solvent NMP leads to increase its selectivity toward aromatics,
present in feed. The addition of 5% water in NMP leads to reduction in sulfur to 653.8ppm. The most of
sulfur molecules attached with aromatic ring structure compounds goes in aromatic rich phase (extract
phase) and leaves the raffinate phase lower in sulfur at 563.4ppm, which is still moderate value and fails to
meet group-II base oil specifications; at the same time yield of raffinate goes on increasing but quality of
raffinate product deteriorates, as density of raffinate goes up (0.8541 g/ml). Similar trend is observed for
follows at the addition of 10% water in solvent in which case yield goes up to 95.3% but sulfur in raffinate
also goes up a little higher to 700.5ppm and density of product goes to 0.8544 g/ml. Hence, an
optimization has to be made in respect of water content in solvent based on trade –off between the yield
and product quality. A similar trend was also observed when extraction was carried at higher temperature,
0
90 C as shown in Figure 4.

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Effect of Solvent-to-feed ratio:

Solvent treat rate, also commonly known as solvent- to- feed ratio (S/F), plays a significant role in
achieving desired product quality. To see the effect of solvent-to-feed ratio on product quality, extraction of
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used oil was carried out at fixed temperature (90 C) but varied solvent- to - feed ratio of 1 and 1.4. It has
been observed that sulfur get reduced to 678.4ppm from 1519.5 in used oil distillate at s/f of 1.0 as shown
in Figure-5. It has also been shown that on increasing treat ratio (~1.4), there is some further reduction in
sulfur level in product. This suggest that to improve product quality or lower sulphur level, higher solvent-
to- feed ratio are desirable but this also leads to some reduction in product yield.

1600
1400
S-value(ppm)
1200
S-Value (ppm)

1000
800
600
400
200
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
S/F ratio
Effect of S/F on S-reduction

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Figure-5: : Effect of solvent-to-feed ratio on sulfur reduction at Temperature 90 C

Activated Carbon Bed Treatment

A 50 gram of raffinate oil sample obtained from one of the extraction run was percolate through an
„activated carbon Bed‟. For this, 50 gm of activated carbon was filled in a glass column having length 400
mm and diameter 20 mm. The adsorption process was carried out at ambient temperature. The sample
collected after passing through activated carbon bed was characterized for sulfur. Results of this
experiment showed that reduction in sulfur in oil is from 392.5 to 308.5 ppm. Although, there is a significant
reduction in sulfur, but it could meet the specification of group-II base oil which is 300 ppm.

Conclusion:

Based on the analysis of experimental data of the feed and product, including their physico-chemical
characterization, following are the important conclusions may be drawn:
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i. The initial boiling point (IBP) of feed stock of sample was 250.5 C, which shows presence of lighter
components of gas oil range in the feed stocks. Presence of these lighter components (which may be
lost during solvent recovery) is affecting the consistency of viscosity of oil and its raffinate products.

ii. The feedstock contains around 1519 ppm of sulfur, which is more than 5 times of prescribed limit of
API standard Group–II oil (300 ppm). It may be desirable to determine the source/check at collection
points, if contamination from furnace oil etc is occurring. The feed stocks have poor color and color
stability, whereas raffinate products obtained after NMP extraction have shown improved „color‟ and
very good „color stability‟. Similarly, after NMP extraction, odor of product is also much reduced as
compared to used oil distillates samples as such.

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iii. Study of effect of operating temperature NMP Extraction of used oil distillates reveals that increase in
temperature beyond a certain range neither improves raffinate yield nor it helps in reduction of sulfur in
the raffinate.
iv. Addition of water in NMP (modification in solvent composition) for enhanced selectivity/increased
affinity towards aromatics leads to improvement in raffinate yield but at the same time it also reduces
desulfurization capacity of solvent.
v. The minimum level of sulfur in refined oil that could be achieved using NMP, extraction was 392.5 ppm
with a VI of 95 in the raffinate product. It seems that for meeting group –II quality, mild „hydrogenation
step‟ is also needed to further process the product obtained by „solvent extraction‟.
vi. The principal reason for inadequate removal of sulfur to the required level may be due to the fact that it
may be present in the form of aliphatic type of sulfur compounds attached to the main chain of
saturates which are very difficult to remove by NMP extraction or other physical separation methods.
vii. To cope up with problem of inadequate desulphurization, attempts were made by modification in
process scheme i.e. combination of extraction with adsorption with charcoal bed at specified
conditions. This combo-processing brought sulfur down to 308ppm but tradeoff between processing
cost and other process needs to be carefully evaluated.

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