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Refining-Petrochemicals-Chemicals-Engineering

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LUBE BASE OIL MANUFACTURING PROCESSES

1 - LUBRICANTS..................................................................................................................................1

2 - BASE OILS PROPERTIES.............................................................................................................1

3 - COMPOSITION OF MINERAL BASE OILS ..................................................................................2

4 - LUBE BASE OILS MANUFACTURING .........................................................................................2

APPENDICES

Recommended properties of lube base oils .................................................................................4


Lubricating oil..................................................................................................................................5
Structure to property relation for hydrocarbons present in lube oil cuts.......................................6
Standard base oil manufacturing processes .................................................................................7
Paraffinic base oil manufacturing scheme - Block flow diagram ..................................................8
Example of obtained product yields in a classic lube base oil refining unit .................................9
Manufacturing of paraffinic lube oils by hydrotreating.................................................................10
Base oil manufacturing - Propane deasphalting..........................................................................11
Base oil manufacturing - Furfural extraction................................................................................12
Base oil manufacturing - Solvent (MEK + Toluene) Dewaxing...................................................13

RA HDB - 00014_C_A - Rev. 7 06/04/2009


© 2009 - IFP Training
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1- LUBRICANTS
Lubricants are made of finished base oils blended with one another and with additives. There are
several types of lubricants:

- engine oils
- industrial oils
- metal working fluids
- medicinal white oils
- greases

The main purpose of a lubricant is to reduce friction: the reduction of friction is accomplished by
maintaining a film of lubricant between surfaces that are moving with respect to each other, thereby
preventing the surfaces from coming into contact and subsequently causing damage.

Besides the reduction of friction, lubricating oils also perform a large number of other functions:
removal of heat, prevention of rust and corrosion, dispersion, sealing. These functions are provided
by the base oil, and are enhanced by the use of additives in amounts ranging from 1 to 25% or more.
The main market for additives is the engine oils. The purpose of these additives is to:

- protect metal surfaces


- extend the range of lubricant applicability
- extend lubricant file

The Society of Automotive Engineer, USA has established that twelve viscosity grades are suitable
for engine lubricating oils. The 0W, 5W, 10W, 15W, 20W, 25W engine oils refer to a low temperature
viscosity while the 20, 30, 40, 50, 60 engine oils refer to a high temperature viscosity.

2- BASE OILS PROPERTIES (figures 1 and 2)


a - Origin of base oils

The general term lube base oils cover a number of different types of material including vegetable oils,
synthetic oils, mineral oils and re-refined oils. This dossier only covers mineral oils which are produced
from the distillation of crude oils.

b - Viscosity

Viscosity is one of the most important properties of a lubricating oil. It is one of the factors responsible
for the formation of lubricating film under both thick and thin film conditions.

Base oils are defined as either light or heavy according to their kinematics viscosity at 40°C. Those
having viscosities above 35 cSt at 40°C are described as heavy and those below light. Most refiners
produce three to four grades from which are blended the finished oils.

c - Viscosity index

The viscosity index (VI) is a number characterizing the degree of change in viscosity of an oil within a
given temperature range. A high VI signifies a relatively small change in viscosity with temperature
whereas a low VI reflects a large viscosity change with temperature. Calculation of an oil’s viscosity
index requires the determination of kinematic viscosities at 40°C and 100°C.

d - Other properties

Specifications for lubricating oils cover such properties as density, kinematic viscosity at 40 and 100°C,
viscosity index, pour point and flash point. At ambient temperature, almost all lubricating base stocks
are liquid with negligible vapor pressure.
00014_C_A © 2009 - IFP Training
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3- COMPOSITION AND CLASSIFICATION OF MINERAL BASE OILS


a - Composition (Figure 3)
The major types of hydrocarbons present in crude oils are linear paraffins (n-paraffins), branched
paraffins (iso-paraffins), cycloparaffins (naphtenes) and aromatics.
Mineral base oils consist of two types: the naphtenic and the paraffinic base oils depending on the
dominant hydrocarbons type present. The paraffinic base oils are the preferred stocks used for engine
oils.
The proportion of the various base oils components determines the characteristics of the base oils.
Viscosity increases with the length of the carbon atom chain.
Most favored crude are paraffinic crude which give good yields of high VI stocks. For certain
applications, naphthenic crudes are selected because they yield stocks with little wax and naturally low
pour points.

b - Classification
ATIEL, the Technical Association of the European Lubricants Industry defines 5 base oil groups, of
which 3 are mineral base oils. This classification allows to establish guidelines for interchanging base
oils in lubricants.

Base oil Satuates Sulfur


category % %m Viscosity Index

Group I < 90 and/or > 0,03 and  80 < 120


Group II  90  0,03 and  80 < 120
Group III  90  0,03  120

The manufacturing of the different groups from crude oil is related to the refining processes which are
used.

4- LUBE BASE OILS MANUFACTURING (figures 4, 5 and 6)


The manufacture of lube base stocks consists of several steps.

a - Vacuum distillation and deasphalting

VACUUM

The residues from atmospheric distillation


D1 of crude oils are further fractionated in a
vacuum distillation (VDU) to produce two,
D2 three or four vacuum distillates of different
viscosities.
D3
Atmospheric
residue The vacuum residue contains lubricant
DAO stock of high viscosity mixed with asphalt
and resins. This oil (DAO) is produced by
D PCD 2397 B

Deasphalting solvent deasphalting which precipitates


Vacuum asphaltenes and resins with liquid propane.
residue Asphalt

00014_C_A © 2009 - IFP Training


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b - Solvent extraction (figure 9)


The vacuum distillates and the deasphalted oil (DAO) contain aromatic and naphtenic hydrocarbons
which must be removed to increase the viscosity index. The process consists of separately treating
each distillate and the DAO with a solvent (furfural, n-methyl-pyrrolidone).
The solvent is mixed with the liquid feedstock and dissolves the components to be extracted. The
mixture settles in two phases: an extract phase rich in aromatics and a raffinate phase rich in paraffins.
Raffinate
Distillates
Solvent (rich in paraffins)

D PCD 2398 C
Dewaxing Extract
DAO
(rich in aromatics)

Deep hydrotreating (figure 7) is sometimes used instead of solvent extraction. This process converts
aromatics into naphthenes, breaks naphthene rings and isomerizes the linear paraffins. As a result low
VI materials are converted to higher VI materials, but the deep hydrotreating markedly reduces the
viscosity of the base oil.

c - Solvent dewaxing (figure 10)


Solvent dewaxing is used to reduce the n-paraffins content of the base oils in order to improve their low
temperature properties and thus preventing wax crystals forming within the normal working
temperature range of the lubricant. Each raffinate is diluted and chilled with a mixture of
methylethylketone (MEK) and toluene. Wax crystallizes and is removed from the oil by filtration to
produce a lube base oil in the – 9 to – 20°C pour point range according to specifications. The slack
wax from the dewaxing step may be deoiled to produce a hard wax and a by product (soft wax).

Solvent Dewaxed oil


D PCD 2399 B
Raffinates Dewaxing
MEK-Toluene Deoiling Hard wax
Slack
wax

Catalytic dewaxing (hydrodewaxing) is used as an alternate to solvent dewaxing. However no wax is


produced from the catalytic dewaxing (selective hydrocracking of the waxy components).

d - Finishing processes
Some base stocks, particularly premium stocks, are hydrofinished or treated with clay to improve color
and oxidation stability. A severe hydrofinishing is used in the manufacture of medicinal white oils.

Hydrogen
D PCD 2398 D

Dewaxed Finishing Finished base


oil processes oil

For solvent extracted oils or conventional base oils, the VI is in the range of 90-100. Non conventional
base oils with VI over 100 are usually manufactured using deep hydrotreating which substitutes for
solvent extraction.

e - Lube crude selection

The lube base oil refiner selects the crude that will provide a consistent quality of the base oils taking
into account the slate of the base oil demand for a lube plant or for a system of several lube plants (for
a refiner operating several lube plants).

00014_C_A © 2009 - IFP Training


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RECOMMENDED PROPERTIES OF LUBE BASE OILS

• Base oils are blended with additives to yield commercial finished lubricants.

about 20% vol. additives

D LUB 032 B
Automotive
lubricant about 80% vol. blended
lube base oils

• RECOMMENDED PROPERTIES FOR BASE OILS - (automotive base oil case)

VISCOSITY

Lubricant film
Fluid bases  20 cSt at 40°C
Viscous bases  100 cSt at 40°C
D LUB 033 B

Heavy bases  30 cSt at 100°C

VISCOSITY INDEX VI

– not too high viscosity under cold temperature (start-up in winter)


– not too low viscosity under hot temperature (lubricant film at 200°C)

High VI = small variation in viscosity with temperature

Automotive base oil VI  100


Automotive multigrade lubricant VI  150

POUR POINT

Base oil ability to remain liquid at low temperature


– 9°C specification for most automotive base oils

OXIDATION RESISTANCE AND STABILITY

Characteristics deterioration under oxygen and temperature influences.

00014_C_A © 2009 - IFP Training


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LUBRICATING OIL

FRENCH CUSTOM SPECIFICATIONS

Loi Arrêté
n°66-923 du 14/12/66 du 1/3/76
J.O. 15/12/66 J.O. 31/3/76

DISTILLATION (NF M 07-002) < 65% at 250°C


% vol (including loss) < 85% at 350°C

EXAMPLES OF LUBE BASE OIL SPECIFICATIONS (INDUSTRY IN FRANCE)

Kinematic viscosity (cSt) Viscosity Pour point Flash Conradson Acidity

at 40°C at 100°C index point residue index

DESIGNATION min max min max min max min max max

NF T 60-100 NF T 60-136 NF T 60-105 NF T 60-118 NF T 60-116 NF T 60-112

NAPHTHENICS
Spindle 18.7 21.0 – 33 160 0.10
100 pale
Movements
550 pale 95 103 – 24 195 0.10
1800 red 14.5 15.5 –9 230 0.10
Engines
60 pale solvent 7.9 8.9 – 57 150 0.05
90 pale solvent 13.1 16.3 25 – 42 160 0.10 0.05
750 pale solvent 10,- 11.2 25 – 21 205 0.10 0.05
1300 pale solvent 15.3 16.3 40 – 15 235 0.10 0.05
PARAFFINICS
Spindle
100 pale 19 24 – 15 160 0.10
Movements
900 red (movem. V14) 170 210 –9 225 0.10
Cylinders
C1-160 30.0 33.5 –3 275 0.10
C1-180 36.3 41,- 0 290
C1-200 800 1000 0 300
Engines
100 solvent 17 23 80 –9 180 0.10 0.10
60 neutral solvent 8.8 9.6 95 – 15 150 0.01 0.05
90 neutral solvent 14.5 16,- 100 – 12 180 0.02 0.05
100 neutral solvent 18,- 23,- 100 –9 190 0.02 0.05
150 neutral solvent 28 32.5 97 –9 200 0.05 0.05
175 neutral solvent 32 35.5 102 –9 210 0.05 0.05
200 neutral solvent 37.5 43.5 97 –9 210 0.05 0.05
250 neutral solvent 45,- 51,- 97 –9 215 0.10 0.05
350 neutral solvent 66 75 95 –9 225 0.15 0.05
400 neutral solvent 76 85 95 –9 230 0.15 0.05
500 neutral solvent 92 102.5 95 –9 230 0.15 0.05
600 neutral solvent 109 125 95 –9 240 0.20 0.05
Bright stock
Bright stock solvent 30 35 95 –9 280 0.90 0.05
Bright stock MIV (V40) 32.5 38 80 –9 280 1.80 0.10

00014_C_A © 2009 - IFP Training


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STRUCTURE TO PROPERTY RELATION


FOR HYDROCARBONS PRESENT IN LUBE OIL CUTS

HYDROCARBON MAIN PROPERTIES


TYPICAL STRUCTURE
FAMILIES DESIRABLE DETRIMENTAL

• HIGH VI • HIGH POUR POINT


LINEAR
PARAFFINS • GOOD OXIDATION
STABILITY

• MEDIUM TO HIGH
VISCOSITY INDEX

BRANCHED • MEDIUM TO GOOD


PARAFFINS OR OXIDATION
PARAFFINS STABILITY
WITH FEW
CYCLES • GENERALLY LOW
POUR POINT

• GOOD OXIDATION • LOW VI


STABILITY

NAPHTHENES • LOW POUR POINT

• GENERALLY LOW • LOW VI


POUR POINT
AROMATICS • VERY POOR
OXIDATION
STABILITY

00014_C_A © 2009 - IFP Training


STANDARD BASE OIL MANUFACTURING PROCESSES
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Vacuum system
Lube base oils

VI
Pour point

Very high VI High VI Medium to low VI


Distillate 1
High Pour Point Acceptable Pour Point Low Pour Point

nP iP and P with few rings N-A


LUBE OIL 3 2
VACUUM
DISTILLATION
VI
Pour point

Distillate 2 Very high VI High VI Medium to low VI


High Pour Point Acceptable Pour Point Low Pour Point
nP iP and P with few rings N-A
3 2

VI
Pour point

Distillate 3 Very high VI High VI Medium to low VI


High Pour Point Acceptable Pour Point Low Pour Point

nP iP and P with few rings N-A


ATMOSPHERIC
RESIDUE 3 2

VI
Vacuum Pour point
residue
Very high VI High VI Medium to low VI
Resins
High Pour Point Acceptable Pour Point Low Pour Point Asphalts
nP iP and P with few rings N-A
3 2 1
1 Deasphalting with propane
2 Naphtene - Aromatics extraction (with solvent)
D PCD 367 B

3 Dewaxing
© 2009 - IFP Training
PARAFFINIC BASE OIL MANUFACTURING SCHEME
— Block flow diagram —

FUNCTION OF UNITS

• Flash point • Viscosity index (VI) • Pour point • Colour


• Viscosity • Stability

Gas + naphtha
Vacuum Waxy Dewaxed
distillates raffinates raffinates
GO

Kerosene Distillate 1
ATMOSPHERIC DISTILLATION

VACUUM DISTILLATION

SOLVENT DEWAXING
Light gas oil Distillate 2 EXTRACTION FINISHING
- MEK - Toluene HYDROTREATING LUBE OIL
- Furfural - MIBK - MEK STEPS BASES
Distillate 3 - NMP
Heavy gas oil
DAO
CRUDE
OIL Vacuum
residue
Refined
DEASPHALTING Aromatic Waxes HYDROTREATMENT
waxes
extracts
D LUB 009 C

Atmospheric
residue Asphalt

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© 2009 - IFP Training
EXAMPLE OF OBTAINED PRODUCT YIELDS
IN A CLASSIC LUBE BASE OIL REFINING UNIT

100 58 48 47

AROMATIC
DEWAXING HYDROFINISHING LUBE BASE OIL
EXTRACTION
VGO 150 NS
58% 82% 98% VI: 102

42 10
Mass flowrate
Aromatic Paraffins
Yield (% mass) extracts

100 35 17.5 13.1 12.9

AROMATICS LUBE BASE OIL


DEASPHALTING EXTRACTION DEWAXING HYDROFINISHING
VACUUM BRIGHT STOCK
RESIDUE SOLVENT
35% 50% 75 % 98% VI: 102

65 17.5 4.4

Asphalt Extract Wax


D PCD 363 B

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© 2009 - IFP Training
MANUFACTURING OF PARAFFINIC
LUBE OILS BY HYDROTREATING
10

Distillates

HYDROFINISHING
HYDROTREATING

Paraffinic base oils


DEWAXING
ATMOSPHERIC
DISTILLATION

DISTILLATION
VACUUM

DAO
PARAFFINIC
CRUDE OIL
PROPANE
DEASPHALTING Paraffins
Atmospheric Vacuum
residue residue
Asphalt

Hydrocarbons used as
for lube base oils

Vacuum nP iP + P with few rings N A


distillates

DEWAXING
HYDROTREATMENT DEASPHALTING
or isomerization

Vacuum nP
residue iP + P with few rings N A ASPHALT
D PCD 364 G

© 2009 - IFP Training


BASE OIL MANUFACTURING
— Propane deasphalting —

Deasphalted oil + propane DEASPHALTED


Deasphalted oil /
55 to 70°C OIL
Propane separation D.A.O.
30
bar

Steam
Heating area
FEEDSTOCK by steam coils Propane
VACUUM
RESIDUE

EXTRACTION
COLUMN
Dilution rate 5 to 12/1
Propane
Propane
40 to 50°C

Asphalt / Propane
ASPHALT

D PCD 076 B
separation
Asphalt 70%
Propane 30%

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© 2009 - IFP Training
BASE OIL MANUFACTURING
— Furfural extraction —

EXTRACTOR
Paraffinic oil + furfural Oil - Furfural PARAFFINIC
130°C separation OIL

Solvent ratio
2 to 3/1

Vacuum
Furfural
FEED
DISTILLATE
or DAO

DEAERATOR

Furfural

D PCD 365 D
90°C Aromatic extract + Furfural Extract - Furfural AROMATIC
separation EXTRACT

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© 2009 - IFP Training
BASE OIL MANUFACTURING
— Solvent (MEK + Toluene) dewaxing —

Solvent (MEK + Toluene) Rotative filter


principle

Oil remains liquid Paraffin


phase by solvent cake
reaction IN
F F
A
Raffinate Liquid + solid R
PA
Liquid raffinate
at 20°C at – 20°C
+ solvent at 50°C Oil + solvent
Paraffin
aspiration
Washing solvent cake
Oil kept in solid phase Oil + solvent
by paraffin crystalls + paraffin crystalls
REFRIGERATION FILTRATION
UNIT
Paraffin - solvent
PARAFFIN
separation
CHARGE
FEED Cooling system
Solvent
CRYSTALLIZATION - 10 to -20°C
Paraffin + solvent

Oil + solvent
Oil - solvent DEWAXED
Solvent ratio 1 to 5/1 separation OIL
Around 50% MEK Solvent
D PCD 366 B

Solvent
Around 50% toluene
recovery

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© 2009 - IFP Training

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