Department Of Chemical Engineering

Reaction Kinetic and Catalysic

INTERNATIONAL UNIVERSITY
SCHOOL OF BIOTECHNOLOGY

Bio-lubricant Production From

Vegetable Oil And Animal Fat
PhD. Phung Thanh Khoa

GROUP MEMBER:
NGUYEN THI TUYET NGAN; ID:BTCEIU18062
PHAM NGOC HOANG MAI; ID:BTCEIU18063
NGUYEN PHUONG ANH KIET; BTCEIU18053
HUYNH KIEN THANH; ID:BTCEIU19005
NGUYEN NGOC PHUONG THAO; BTCEIU18075
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 OUTLINE
HUYNH KIEN THANH

NGUYEN NGOC PHUONG THAO

1 General information about the topic

Biolubricants from rapeseed and NGUYEN PHUONG ANH KIET

castror oil transesterification by using
titanium isopropoxide as a catalyst:
production and characterization
5 2 TMP-based-cottonseed oil-
lubricant

NGUYEN THI TUYET NGAN

PHAM NGOC HOANG MAI

4 3
Green Preparation Of Branched
Screening of solid base
Biolubricant By Chemically
catalysts on palm oil based
Modifying Waste Cooking Oil
biolubricant
With Lipase And Ionic Liquid
 General overview of the
research field
The increasing global population together with industrialization
and modernization has led to an increase in energy
consumption (have strongly depended on fossil fuels)

Biomass is the only renewable source from which energy and

chemical products can be obtained; therefore, this is the only
current alternative able to replace petroleum.

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Biolubricant applies to all lubricants that are easily biodegradable and non-toxic
They are unstable at high temperatures and form compounds that are harmful to
equipment and machines.
The conversion of triglyceride to esters can be followed or preceded by one or more
reactions to improve reactions such as epoxidation and hydrogenation.
Biolubricants have higher quality and longer lifespans than minerals

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 Introduction of topic
Solid catalysts were developed as sustainable
alternative to carry out esterification and
transesterification reactions

Using basic catalysts, mainly CaO, obtaining

full conversion during transesterification

The other alternative involves using solid acid

catalysts, such as cationic exchange resins,
zeolites, or oxides (Al2O3, ZrO2, TiO2, WO3,
Nb2O5, Ta2O5), which can also be sulfated to
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improve their catalytic activity
Biolubricants can be classified according to their
chemical fluid composition in natural and
synthetic oils.

Natural oils are made using vegetable oils or animal

fats, while synthetic oils use the natural oils as starting
materials to form more advanced biolubricants.

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Esterification/Transesterification ( synthetic oils )

These reactions take place using

basic catalysts, mainly CaO,
obtaining full conversion during
transesterification

As esters are susceptible to hydrolysis and thermal degradation, their thermal

properties can be improved by alcohol substitution with longer alkyl chains or
branched chains such as trimethylolpropane (TMP) trimethylolhexane
(TMH), and trimethylolethane (TME) www.yourwebsite.com 7
 TMP-based-cottonseed
oil-lubricant
- Among edible oil, cottonseed oil is less preferred.
- Has 15-22% of Oleic acid and 49-58% of Linoleic acid
- Have the ability to develop effective fatty acid monolayer to reduce
metal-metal contact and minimize frictional force
- Cheap synthesis procedure and potential effective biobube.

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 Density and Viscosity

- With increasing portions of cotton-biolubricant proportion, density

increases while viscosity decreases
- Quicker liquid flow with high concentration of CBL
- High concentration cotton bio-lubricant blends are not good for
higher ISO VG-grade applications.

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Coefficient of Friction
(COF)
- With increasing portions of cotton-biolubricant proportion, COF
decreases up to 30%
- Polar heads of long-chain saturated fatty acids in CBL have a higher
tendency to adsorb and react with metallic surfaces, resulting in
boundary lubrication effects.
- High concentration of oleic acid also develops an effective FA-
monolayer between the sliding surfaces

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Coefficient of Friction
(COF)

- During run-in-period, COF remained unstable initially

- After some time contacting surface becomes smoother as steady state is achieved
- COF decreases with the increase of CBL concentration because a stable film is formed between sliding surface

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Surface analysis

- Boundary lubrication regime:

adhesive, abrasive, corrosive,
fatigue wears were observed
- Wear increase with concentration
because lower viscosity, protective
film got broken
- This promotes corrosive oxidation
to produce peroxides and fatty
acids

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 Green Preparation Of Branched Biolubricant By
Chemically Modifying Waste Cooking Oil With Lipase
And Ionic Liquid
• Low volatility
• Wide viscosity range
• High temperature tolerance
ADVANTAGE • Good viscosity-temperature
property
• Sustainability
• Environmental friendliness

• Conflict between energy

sustainability and food safety
DISADVANTAGE • Limitation of planting regions and climates
• High raw materials cost, about 70-80% of the total cost, while the
cost of WASTE COOKING OIL is 2-3 times lower than that of animal
and vegetable oils

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In China, about 5 million tons of WCO is
produced every year, 40-60% is illegally
returned to kitchen
About 15-18 million tons of WCO around
the world is discharged into water or soil
randomly per year

Therefore, employing WCO to produce high

value chemicals as showed in Table 1
Bioproducts obtained from waste cooking oil and performance evaluation
Therefore, this study provided a Developing a green and efficient strategy for the
critical synthetic strategy for
preparing high-performance
preparation of octylated branched biolubricant from
biolubricants from WCO waste cooking oil

01 WCO was hydrolyzed by a lipase

The produced UFAs were collected from the

02 hydrolysates by the urea complexation separation.

Another lipase was used to catalyze the

03 esterification of UFAs with 2-ethylhexanol and the

new esters products were further epoxidated.

The cheaper nucleophilic reagent (octanoic acid) was used for

04 nucleophilic disubstitution of the epoxy groups under the
catalysis of ionic liquid to obtain octylated branched biolubricant.
 Hydrolysis of waste cooking oil and removal of
saturated fatty acids
WCO was enzymatically hydrolyzed for 72h and
subsequently centrifuged and dried to collect fatty
acids.
The hydrolysis yield was 90.57%
The saturated fatty acids and urea formed
complex crystallization were removed by
filtration. The contents of UFAs in the
filtrate was 98.04%.
Epoxidation of C=C double bond, hydroxylation
of epoxy groups and further acylation are the
noteworthy method for the chemical
modification

However, by introducing epoxy groups to

increase intermolecular force and accelerate
crystallization resulted in a poor low-
temperature performance

For improving the low-temperature

performance of epoxy 2- ethylhexyl esters, the
epoxy group was cleaved by a nucleophilic
reagent (octanoic acid) under the catalysis of
[HMIm][PF6] to form a dioctylated branched
biolubricant.
 • The low-temperature
performance of modified
The main challenges for the lubricant
products was evaluated
from natural vegetable oils is the poor through determining pour
low-temperature performance point
• The FP of lubricant was an • The viscosity and VI of
important index in measuring lubricants play a critical
the safety of storage and role in lubrication
transportation. performance
• The rheological behaviors of WCO and octylated
branched biolubricant were shown Figure a and b.
• The linear relationship between shear stress and shear
rate all were excellent at different temperature (30, 40,
50, 60, 80 and 100 oC )
The lubrication performance of WCO and
octylated branched biolubricant were
evaluated comparing with a mineral
based lubricant with the same viscosity
grade through HFRR
Screening of solid base
catalysts on palm oil
based biolubricant
synthesis
 Purpose of Solid base
Definition
this research catalyst

The activity of solid base The activity of solid base

catalysts with selected • CaO
catalysts with selected
dopants on the synthesis of • SrO
dopants on the synthesis
trimethylolpropane CaOxSrO, where x = 5,
of trimethylolpropane
triesters(TMPTE) 10, 15 and 20 %w/w
triesters (TMPTE)
biolubricant from palm oil of SrO on CaO
biolubricant from palm oil
methyl esters (POME) methyl esters (POME)
 of catalyst
Characterization

Characterization of catalyst
01

Basicity of the catalyst

02

Surface area of the catalyst

03

Surface area of the catalyst

04
 1. Structure of the catalyst

• The XRD patterns of catalysts were obtain

the mixed oxides of Ca and Sr by
comparing them to their pure oxides form
(pure CaO, SrO and CaOxSrO)
• The peaks of hydroxide species of
strontium was detected indicating the
hydration of SrO due to its hygroscopic
nature.

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 2.Basicity of the catalyst

Temperature programmed desorption with CO2 as

probe molecule (TPD-CO2)
• The characteristics of adsorptionand desorption of
CO2 on the basic sites of the catalysts.
• The stronger CO2 adsorb on the catalyst’s surface,
higher energy or temperature will be needed to
desorb it from the surface
 The mixed oxides system provide stronger basic
strength on the catalytic site.

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 3. Surface area of the catalyst

Total surface area of the catalysts were

characterized by Brunauer-Emmer-Teller (BET)
method:
The Company • The transesterification reaction depends on the
About us basicity of the catalyst
• High basicity of the catalyst may reduce the
yield of the TMPTE due to the saponification
reaction.

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 d) Surface morphologies of catalysts

This method is use field emission scanning electron

microscopy (FE-SEM):
• All the catalysts showed irregular shapes throughout
their surface with agglomerated particles.

• Surface morphology of CaO has slightly smoother and

rounder edges compared to the rest of catalysts that
contained SrO.

 The highest surface area was obtained from the

CaO15SrO catalyst may be contributed by the smaller
particles.
2.Production of trimethylolpropane
triesters
The reaction took place on the surface of the catalyst

with Sr, Ca and O act as active sites to accelerate the

transesterification reaction:

• 1st step: the adsorption of the ester and alcohol onto

the catalytic sites

• 2nd step: the new vacant active site of the catalyst to

react with TMPME

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3. Effect of catalyst type on yield

b)Effect of catalyst d)Effect of reaction

loading on yield time on yield
a)Effect of catalyst c)Effect of temperature
type on yield on yield

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4.The optimized reaction condition
•   1 %w/w mixed oxides of Ca and Sr
catalyst with 5 %w/w SrO on CaO
• 180 C
• 2 mbar pressure
• 240 min of reaction
88% of yields TMPTE
The results from the BET and TPD-CO2
revealed that the high yield of TMPTE
largely depends on the basicity rather
than the surface area of the catalyst

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BIOLUBRICANTS FROM RAPESEED

AND CASTOR OIL

TRANSESTERIFICATION BY USING

TITANIUM ISOPROPOXIDEAS A

CATALYST: PRODUCTION AND

CHARACTERIZATION

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Ingredient of
Rapeseed and
Castor oil
Oleic, linoleic, and linolenic acid
Rapeseed oil

Castor oil

Ricinoleic acid
First Transesterification

Reaction conditions:
• Temperature of around 65◦C
• Time: 60 min
• Methanol/oil ratio is 6:1
• Catalyst (potassium hydroxide) is 1% w/w
=> The FAME content of the product was over 96.5%
 Raw material
characterization

• Methyl ricinoleate: hydroxyl groups

=> high viscosity
Rapeseed oil Castor oil • Methyl oleate: monounsaturation fat
• Methyl oleate (63.07%) • Methyl ricinoleate (over => low viscosity
• Methyl linoleate 88%)
(21.15%) • Methyl linoleate (4.5%)
• Linolenate (8.71%)
Second Transesterification Reaction
Influence of Temperature
Biolubricant yield:
• 150◦C: 89%
• 160◦C: 94.26%
• 170◦C: 95.38%

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Influence of Catalyst
Concentration Biolubricant yield:
• 0.5% catalyst: under 80%
• 1% catalyst: 89.40%
• 2% catalyst: 90.18%

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Influence of Alcohol/FAME
Molar Ratio
Biolubricant yield:
• 1:1 molar ratio: under 50%
• 2:1 molar ratio: 81.71%
• 3:1 molar ratio: 89.40%

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The most suitable values for the second
transesterification:
• Temperature: 160 °C
• Time: 120 min
• Catalyst (titanium isopropoxide): 1% w/w
• Alcohol/FAME molar ratio: 3:1
Comparison between Rapeseed, Castor
and two commercial lubricants (L1 and L2)
Yield and density CFPP and Pour point

Flash and Combustion point Viscosity at 40 ◦C and 100 ◦C

Oxidative stability Viscosity index

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Yield and density

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Flash and Combustion point

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Oxidative stability

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CFPP and Pour point

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Viscosity at 40 ◦C and 100 ◦C

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Viscosity index

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 References
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and Engineering Chemistry. 2016 Apr;36:1–12.
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of the Biolubricant Production Process: Challenges and Future Perspectives. Processes. 2020 Feb 25;8(3):257.
4. Encinar JM, Nogales-Delgado S, Sánchez N, González JF. Biolubricants from Rapeseed and Castor Oil Transesterification by
Using Titanium Isopropoxide as a Catalyst: Production and Characterization. Catalysts. 2020 Mar 29;10(4):366.
5. Gul M, Zulkifli NWM, Masjuki HH, Kalam MA, Mujtaba MA, Harith MH, et al. Effect of TMP-based-cottonseed oil-
biolubricant blends on tribological behavior of cylinder liner-piston ring combinations. Fuel. 2020 Oct;278:118242.
6. Ho CK, McAuley KB, Peppley BA. Biolubricants through renewable hydrocarbons: A perspective for new opportunities.
Renewable and Sustainable Energy Reviews. 2019 Oct;113:109261.
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Lubricants. Sci Rep. 2019 Dec;9(1):11711.
8. Ivan-Tan CT, Islam A, Yunus R, Taufiq-Yap YH. Screening of solid base catalysts on palm oil based biolubricant synthesis.
Journal of Cleaner Production. 2017 Apr;148:441–51.
9. Zhang W, Ji H, Song Y, Ma S, Xiong W, Chen C, et al. Green preparation of branched biolubricant by chemically modifying
waste cooking oil with lipase and ionic liquid. Journal of Cleaner Production. 2020 Nov;274:122918.
10. Bahadi M, Salimon J, Derawi D. Synthesis of di-trimethylolpropane tetraester-based biolubricant from Elaeis guineensis
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kernel oil via homogeneous acid-catalyzed transesterification. Renewable Energy. 2021 Jun;171:981–93.
Q&A
Thank you