Refining-Petrochemicals-Chemicals-Engineering

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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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.

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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 40C. Those having viscosities above 35 cSt at 40C 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 oils viscosity index requires the determination of kinematic viscosities at 40C and 100C. d - Other properties Specifications for lubricating oils cover such properties as density, kinematic viscosity at 40 and 100C, viscosity index, pour point and flash point. At ambient temperature, almost all lubricating base stocks are liquid with negligible vapor pressure. 2009 - IFP Training

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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 A ssociation 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 category Group I Group II Group III

Satuates % < 90  90  90

Sulfur %m and/or > 0,03
0,03
0,03

Viscosity Index and  80 and  80  120 < 120 < 120

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

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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

D1 D2 Atmospheric residue D3 DAO Deasphalting Vacuum residue Asphalt

D PCD 2397 B

The residues from atmospheric distillation of crude oils are further fractionated in a vacuum distillation (VDU) to produce two, three or four vacuum distillates of different viscosities. The vacuum residue contains lubricant stock of high viscosity mixed with asphalt and resins. This oil (DAO) is produced by solvent deasphalting which precipitates asphaltenes and resins with liquid propane.

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2009 - IFP Training

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.
D PCD 2398 C

Distillates DAO

Solvent Dewaxing

Raffinate (rich in paraffins) Extract (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 20C 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).
D PCD 2399 B

Raffinates

Solvent Dewaxing MEK-Toluene

Dewaxed oil Deoiling Slack wax Hard 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 oil

Finishing processes

Finished base 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).
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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

Automotive lubricant

about 80% vol. blended lube base oils

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

VISCOSITY
Lubricant film
D LUB 033 B

Fluid bases
20 cSt at 40C Viscous bases
100 cSt at 40C Heavy bases
30 cSt at 100C

VISCOSITY INDEX VI not too high viscosity under cold temperature (start-up in winter) not too low viscosity under hot temperature (lubricant film at 200C) 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 9C specification for most automotive base oils

OXIDATION RESISTANCE AND STABILITY Characteristics deterioration under oxygen and temperature influences.

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D LUB 032 B

LUBRICATING OIL
FRENCH CUSTOM SPECIFICATIONS
Loi n66-923 du 14/12/66 J.O. 15/12/66 Arrt du 1/3/76 J.O. 31/3/76

DISTILLATION (NF M 07-002) % vol (including loss)

< 65% at 250C < 85% at 350C

EXAMPLES OF LUBE BASE OIL SPECIFICATIONS (INDUSTRY IN FRANCE)

Kinematic viscosity (cSt) at 40C DESIGNATION min max at 100C min max Viscosity index min NF T 60-136 NAPHTHENICS Spindle 100 pale Movements 550 pale 1800 red Engines 60 pale solvent 90 pale solvent 750 pale solvent 1300 pale solvent 18.7 21.0 33 160 0.10 max NF T 60-105 Pour point Flash point min NF T 60-118 Conradson residue max NF T 60-116 Acidity index max NF T 60-112

NF T 60-100

95

103 14.5 15.5

24 9 57 42 21 15

195 230 150 160 205 235

0.10 0.10 0.05 0.05 0.05 0.05

7.9 13.1

8.9 16.3 10,15.3 11.2 16.3

25 25 40 PARAFFINICS

0.10 0.10 0.10

Spindle 100 pale Movements 900 red (movem. V14) Cylinders C1-160 C1-180 C1-200 Engines 100 solvent 60 neutral solvent 90 neutral solvent 100 neutral solvent 150 neutral solvent 175 neutral solvent 200 neutral solvent 250 neutral solvent 350 neutral solvent 400 neutral solvent 500 neutral solvent 600 neutral solvent Bright stock Bright stock solvent Bright stock MIV (V40)

19 170

24 210 30.0 36.3 33.5 41,-

15 9 3 0 0 80 95 100 100 97 102 97 97 95 95 95 95 30 32.5 35 38 95 80 9 15 12 9 9 9 9 9 9 9 9 9 9 9

160 225 275 290 300 180 150 180 190 200 210 210 215 225 230 230 240 280 280 0.10 0.01 0.02 0.02 0.05 0.05 0.05 0.10 0.15 0.15 0.15 0.20 0.90 1.80

0.10 0.10 0.10

800 17 8.8 14.5 18,28 32 37.5 45,66 76 92 109

1000 23 9.6 16,23,32.5 35.5 43.5 51,75 85 102.5 125

0.10 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.10

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STRUCTURE TO PROPERTY RELATION FOR HYDROCARBONS PRESENT IN LUBE OIL CUTS

HYDROCARBON FAMILIES
TYPICAL STRUCTURE

MAIN PROPERTIES DESIRABLE HIGH VI GOOD OXIDATION STABILITY MEDIUM TO HIGH VISCOSITY INDEX DETRIMENTAL HIGH POUR POINT

LINEAR PARAFFINS

BRANCHED PARAFFINS OR PARAFFINS WITH FEW CYCLES

MEDIUM TO GOOD OXIDATION STABILITY GENERALLY LOW POUR POINT

GOOD OXIDATION LOW VI STABILITY

NAPHTHENES

LOW POUR POINT

AROMATICS

GENERALLY LOW LOW VI POUR POINT VERY POOR OXIDATION STABILITY

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2009 - IFP Training

STANDARD BASE OIL MANUFACTURING PROCESSES

7

Vacuum system
Lube base oils

VI
Pour point Very high VI High Pour Point High VI Acceptable Pour Point Medium to low VI Low Pour Point

Distillate 1

nP
LUBE OIL VACUUM DISTILLATION
3

iP and P with few rings

2

N-A

VI
Pour point

Distillate 2

Very high VI High Pour Point

High VI Acceptable Pour Point

Medium to low VI Low Pour Point

nP
3

iP and P with few rings

2

N-A

VI
Pour point

Distillate 3

Very high VI High Pour Point

High VI Acceptable Pour Point

Medium to low VI Low Pour Point

ATMOSPHERIC RESIDUE

nP
3

iP and P with few rings

2

N-A

Vacuum residue
Very high VI High Pour Point

VI
Pour point High VI Acceptable Pour Point Medium to low VI Low Pour Point Resins Asphalts

nP
1 2 3

iP and P with few rings

3 2

N-A
1

Deasphalting with propane Dewaxing

2009 - IFP Training

D PCD 367 B

Naphtene - Aromatics extraction (with solvent)

PARAFFINIC BASE OIL MANUFACTURING SCHEME Block flow diagram

FUNCTION OF UNITS Flash point Viscosity

Gas + naphtha

Viscosity index (VI)

Pour point

Colour Stability

Vacuum distillates
GO

Waxy raffinates

Dewaxed raffinates

ATMOSPHERIC DISTILLATION

Kerosene
VACUUM DISTILLATION

Distillate 1 Distillate 2 Distillate 3 DAO

SOLVENT EXTRACTION - Furfural - NMP DEWAXING - MEK - Toluene - MIBK - MEK FINISHING HYDROTREATING STEPS

Light gas oil Heavy gas oil

LUBE OIL BASES

CRUDE OIL

Vacuum residue
DEASPHALTING

D LUB 009 C

Aromatic extracts Asphalt

Waxes

HYDROTREATMENT

Refined waxes

Atmospheric residue

2009 - IFP Training

EXAMPLE OF OBTAINED PRODUCT YIELDS IN A CLASSIC LUBE BASE OIL REFINING UNIT

100
AROMATIC EXTRACTION

58

48

47

VGO

DEWAXING

HYDROFINISHING

58%

82%

98%

LUBE BASE OIL 150 NS VI: 102

Mass flowrate Yield (% mass)

42
Aromatic extracts

10
Paraffins

100

35
AROMATICS EXTRACTION

17.5

13.1

12.9

VACUUM RESIDUE

DEASPHALTING

DEWAXING

HYDROFINISHING

35%

50%

75 %

98%

LUBE BASE OIL BRIGHT STOCK SOLVENT VI: 102

65
D PCD 363 B

17.5
Asphalt Extract

4.4
Wax 9

2009 - IFP Training

MANUFACTURING OF PARAFFINIC LUBE OILS BY HYDROTREATING

10

HYDROFINISHING

HYDROTREATING

ATMOSPHERIC DISTILLATION

VACUUM DISTILLATION

DAO

PARAFFINIC CRUDE OIL

Atmospheric residue

Vacuum residue

PROPANE DEASPHALTING

Paraffins Asphalt

Hydrocarbons used as for lube base oils Vacuum distillates

nP

iP + P with few rings

DEWAXING or isomerization

HYDROTREATMENT

DEASPHALTING

Vacuum residue

nP

iP + P with few rings

ASPHALT

Paraffinic base oils

D PCD 364 G

Distillates

2009 - IFP Training

DEWAXING

BASE OIL MANUFACTURING Propane deasphalting

Deasphalted oil + propane

55 to 70C
30 bar

Deasphalted oil / Propane separation

DEASPHALTED OIL D.A.O.

Steam
FEEDSTOCK VACUUM RESIDUE

Heating area by steam coils

Propane

EXTRACTION COLUMN Dilution rate 5 to 12/1 Propane

40 to 50C

Propane

Asphalt 70% Propane 30%

2009 - IFP Training

D PCD 076 B

Asphalt / Propane separation

ASPHALT

11

BASE OIL MANUFACTURING Furfural extraction EXTRACTOR Paraffinic oil + furfural

130C

Oil - Furfural separation

PARAFFINIC OIL

Solvent ratio 2 to 3/1 Vacuum Furfural FEED DISTILLATE or DAO DEAERATOR

Furfural
D PCD 365 D

90C

Aromatic extract + Furfural

Extract - Furfural separation

AROMATIC EXTRACT
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2009 - IFP Training

BASE OIL MANUFACTURING Solvent (MEK + Toluene) dewaxing

Solvent (MEK + Toluene)

Rotative filter principle Oil remains liquid phase by solvent reaction

Paraffin cake

Raffinate at 20C Oil kept in solid phase by paraffin crystalls

Liquid raffinate + solvent at 50C

Liquid + solid at 20C Washing solvent Paraffin cake FILTRATION

Oil + solvent aspiration Oil + solvent + paraffin crystalls

PA

I F F

REFRIGERATION UNIT

CHARGE FEED

Paraffin - solvent separation Cooling system CRYSTALLIZATION - 10 to -20C Paraffin + solvent Oil + solvent Solvent ratio 1 to 5/1 Oil - solvent separation Solvent Solvent

PARAFFIN

DEWAXED OIL

D PCD 366 B

Around 50% MEK Around 50% toluene

Solvent recovery

13

2009 - IFP Training