Presentation

On

CRUDE OIL CHARACTERISTICS

AND
REFINERY PRODUCTS
By

DGM (Technical) U.Venkata Ramana,

Refinery HQ, IOCL, New Delhi

Industry Academia
Workshop On Refining & Petrochemicals
25th28 AUG 2010

Petroleum/Crude oil

It is Natures gift to man-kind.

Crude Oil means all kinds of hydrocarbons in liquid form in their

natural state or obtained by Natural Gas by condensation or extraction.
It is a hydrocarbon
mixture having simple to most complex
structures such as resins, asphaltenes etc.

Crude oil is formed by bacterial transformation of Organic matter

(carbohydrates/proteins/from plant &
animal origin) by decay in
presence and/or absence of air into HC rich sediments by undergoing
biological/physical and chemical alterations

Chemical Composition
Carbon
Hydrogen
Sulphur
Nitrogen
Oxygen
Metals

to 87.0% 83.0
% to 14.0 10.0
to 6.0 % 0.05
% 0.1 to 2.0
to 1.5 % 0.05
% 0.00 to 0.14

The majority of crude oil is alkanes, cycloalkanes (naphthenes), aromatics,

.polycyclic aromatics, S-containing compounds, etc
Gasoline: branched alkanes
Diesel: linear alkanes

Sulphur Compounds
Thiols
Sulphides
Cyclic sulphides
Disulphides
Thiophenes
Benzothiophenes
Dibenzothiophenes
Naphthobenzothiophe
nes

Effect of sulphur compounds

environmental Great to contributeconcern,
,matterparticulate
obnoxiousof emission
odoured sulphur oxide gases
level sulphurReceding
in products

petroleumall

to shifted FocusTechnology& Refining

sulphur removal from hydrocarbons

Oxygen compounds
Alcohols/Ether/Cyclic ether/furan
Carboxylic acids
Naphthenic acids
American crude oils to 0.35%wt 0.006:
Russian crudes oils to 1.05 %wt 0.2:
North Gujarat crude oil : 0.2%wt

Increasingly High TAN Crude is

being processed

Nitrogen Compounds
Pyrrole
Indole
Carbozole
Benzocar
bozole

Pyridine
Quinoline
Indoline
Benzoquinoline

Effect:
Catalysts poison Nitrogen oxide emission&

Metals
Present as inorganic salts & organic
porphyrins ( Ni, V, Mg etc.) in ppm
desalting in
removedmostlySalts
operation
catalyst are porphyrinsV & Ni
poisons

Crude Oil Characterization

: Density, API GravityTRADING
,RVP, Pour Point, KVTRANSPORTATION
Wax content
: Salt content, BS&WCONTAMINATION
,: Sulfur, Nitrogen, TANPROCESSABILITY
Asphaltene, MCR
: ASTM DistillationCRACKING POINT
LPG POTENTIAL Light hydrocarbons (GC):
CLASSIFICATION Characterization factor:

Classification of Crude Oil

API Gravity
API =(141.5/sp.gravity)-131.5
Light Crude Oil

31<
Mixed Based

22-31
Heavy crude

22>
API is a major factor for Crude pricing

API & Sulphur

50

Deg. API

40

Light
Petroelum

30
20

Heavy oils
and residua

10
0
0

Wt. % Sulphur

5.0

API & Nitrogen

50

Deg. API

40

Light
Petroelum

30
20

Heavy oils
and residua

10
0
0.0

0.2

0.6

0.4

Wt. % Nitrogen

0.8

1.0

API & Asphaltene

50

Deg. API

40

Light
Petroelum

30
20

Heavy oils
and residua

10
0
0

Wt. % Asphaltene

5.0

Types of Crudes
BITUMINOUS
Lube bearing Basrah Light Arab mix

Non-lube bearing Suez Mix

Dubai

NON-BITUMINOUS
High sulphur
Arab
medium
Kuwait
Low sulphur
Qua I boe
Miri light

Hydrocarbon Classification
PARAFFINIC BASE
SULPHUR, WAXY, LESS ASPHALTIC, LOW
HIGH POUR

NAPHTHENIC BASE
NAPHTHENIC BASE STOCKS, LESS WAX,
LESS ASPHALTIC, LOW POUR

ASPHALTIC BASE
HIGH SULPHUR, NITROGEN, SUITABLE FOR
BASE OILS

Hydrocarbon Classification
UOP Characterization factor
KUOP : Cube root of average boiling
point(R) divided by specific gravity
Paraffinic

12.1< :
Mixed based 11.5 - 12.1 :

Naphthenic 11.5>:

Types of Crudes-Imported
Low Sulphur Crudes
High sulfur Crudes
Lube & Bitumen producing
.Suitable for Lube producing refineries

Non Lube Producing & Bitumen Producing

Suitable during Non Monsoon periods when Bitumen
demand takes place

Non Lube / Non Bituminous

Suitable during Monsoon period when Bitumen production is
. not required

Crude oils for Blending at Mundra-Heavy, High

acidic etc (LS or HS)

World Crude Oil Quality

Properties

1985

1990

1995

2001

2010
(Proj)

of Crude Oil
1.14

1.12

1.31

1.41

1.51

API Gravity of Crude oil

32.7

32.6

32.4

32.2

31.8

Metal in crude oil

Residue (ppm wt)

275

286

297

309

320

Residue in crude (vol%)

19

19.4

19.8

20.2

21.3

S in crude oil

3.07

3.26

3.61

3.91

4.0

S in crude Oil
(wt%)

residue (wt%)

Crude Oil Assay

detaileda
is assayCrude
which
ofpropertiesthereport describes
the
crude, as well as the major fractionswhole
into
which a crude is distilled at the refinery gasoline, naphtha, kerosene, jet fuel,
middle distillates, gas oils and resid
data the Typically,
crudea incontained
the fromgeneratedyieldsincludesassay
physical Distillate/resid& distillation
properties

Crude Oil

Evaluation Scheme

TBP Distillation

Naphtha
C5140C

Kero
140-240C

Gas oil
240-370C

Atm.Resid
+ 370C

Vac Gas Oil

370-540/600C

SR
+540-600C

ALL TESTS ARE CONDUCTED AS PER STANDARD TEST METHODS : ASTM/IP/IS

Combined TBP curves of

Basrah Light Crude oil
100.0
90.0
80.0

Yield %

70.0
60.0
50.0

%vol

40.0

%wt

30.0
20.0
10.0
0.0
0

100

400

300

200

Temperature, o C

500

600

Properties of Crude oil

Characteristics

Basrah Light Bomba

y High
0.8745
0.8200
30.3
41.0
-30
21

Arab mix

Kuwait

North Gujarat

0.8664
31.6
-24

0.8741
30.3
-27

0.8932
26.8
27

@40 oC
@50 oC
Water content, %wt
Salt content, ptb
Sulphur, %wt
TAN, mgKOH/gm
CCR, %wt
Wax, %wt
Asphaltene, %wt
ASTMDistillation
cracking
point, oC
Metal content, ppm

nil
10
3.1
5.9
1.2
2.6

3.4
nil
0.09
0.1
1.1
12.7
0.25

10.0
8.9
nil
L20
2.7
0.14
6.4
2.5
2.3

11.1
8.5
nil
2.0
2.8
0.14
5.4
6.0
2.5

65.6
31.4
4.1
200
0.08
1.93
2.5
5.9
0.05

339

372

322

335

367

Nickel/vanadium

4/23

4/33

61/L10

Density, gm/ml
API gravity
Pour point, oC
Kinematic Viscosity

Laboratory Distillation
ASTM D86
ASTM D1160
TBP Distillation ASTM D2892
High vacuum Distillation, ASTM D5236
Simulated Distillations based on gas
chromatography principle

Test methods- Density

Density is defined as the mass per unit volume of a
substance. (Units:g/mL or g/cm3 or kg/m3). Density is
.temperature-dependent
Density is measured using an Anton Parr DMA
48/Kyoto digital density meter, and following ASTM
method D 5002 - Density and Relative Density of
Crude Oils by Digital Density Analyzer (ASTM,
.1996a)
Density of crude oils : 0.83 to 0.90 g/ml. Densities
can be measured to 0.0001 g/ml with a repeatability
.of "0.0005 g/ml

API Gravity
API Gravity
API =(141.5/sp.gravity)-131.5
Light Crude Oil

31<
Mixed Based

22-31
Heavy crude

22>

API is a major factor for Crude pricing

BS&W
Base sediments and Water determined by Karl Fischer
titration using a Met Rohm 701 KF Automatic Titrator
(ASTM D 4377) or by Distillation method, ASTM D4006
Oils with significant water contents, (>5%), do not
. represent the properties of the "dry" oil
For 0.1%vol change, the cost implication
10 MMT purchase at ~$60/barrel For
US$420/MT x (0.1/100)x10 MMT
US$4.20 million~

Flash Point
There are several ASTM methods for measuring flash
points. The minimum flash point that can be determined
by method D93/IP34 is 10oC. Method D 56 is intended
for liquids with a viscosity less than 9.5 cSt at 25oC. The
flash points and fire points of lubricating oils can be
determined by ASTM method D 92/IP 36
Many fresh crude oils have flash points below 10oC
and/or viscosities above 9.5 cSt at 25oC

Pour Point
The pour point of an oil is the lowest temperature
at which the oil will just flow, under standard test
conditions. The pour point of the oils is therefore
an indication, and not an exact measure, of the
.temperature at which flow ceases
ASTM method D 97 - Standard Test Method for
Pour Point of Petroleum Oils (ASTM, 1996a) for
.pour point determinations
Heavy & waxy oil transportation is a challenge

Viscosity
There are several ASTM Standard Methods for measuring
viscositythe .oilsof ,theseOf only methods
D
TestStandard
Kinematic forMethod
andTransparent (theLiquids Opaque
445
Dynamic Viscosity) and D 4486 - Standard Test Method
for Kinematic Viscosity of Volatile and Reactive
Liquids,
will yield absolute viscosity measurements
(ASTM,
of Viscosity
.1996a)
of Calculation
methodstheseofBoth
of
use make
capillary
viscometerskinematic
producewill glass and
measurements in units of centistokes (cSt) only absolute
for oils
that exhibit Newtonian flow behavior (viscosity
.independent of the rate of shear)

Flow curve of waxy crude at different

temperatures
300

Deg C 60
40 Deg
C

Shear Stress (Pa)

250

Deg C 50
35 Deg
C

Deg C 45

200

150

100

50

0
0

100

300

200

She ar R ate (s-1 )

400

500

Factors Effecting the Selection of

Crude oil
:Choice of crude oil for a refinery depends on
Product mix
Product quality
Refinery configuration
Product treatment facilities
Refinery design spec- Metallurgy, desalter etc
Environment stipulation for pollution control
Pipeline design for inland refineries

Proper crude selection is necessary for

.optimisation of refinery margin

Refinery Constraints
Refinery Configuration
Refinery metallurgy
Catalyst
Down-stream treatment facilities
Pipeline design constraints

Opportunity
High S crude oil
High Acid crude oils
Beat the market by proper selection of
crude
Overcome refinery design constraints to
widen crude basket
Crude Blending Facility

MAJOR THRUST BY OIL REFINERY

1 Optimise crude mix
2 Widening crude basket
3 Ocean freight reduction
4 Demurrage control
5 Inventory control
6 Ocean Loss reduction
7 Reduce F&L

: High or Low sulfur

: Increased No. of crudes
: Higher Cargo size
: Minimise tanker waiting
: Min possible inventory
: Proper controls
: Proper design,operation

Gross product Worth of crude Oil

API
S, wt%
Price, /MT

32.4

32.6

32.7

0.079

0.081

0.13

Yield, wt fraction

GPW

Miri

Widuri

Cabinda

Miri

Widuri

Cabinda

0.9%
6.4%
8.0%
21.5%
42.5%
12.7%
8.0%

0.1%
1.5%
1.6%
7.7%
51.2%
29.9%
8.0%

1.5%
5.0%
5.4%
13.0%
45.0%
22.1%
8.0%

2.0
18.5
23.8
62.4
112.2
21.1

0.2
4.3
4.8
22.3
135.2
49.6

3.3
14.5
16.1
37.7
118.8
36.7

100.0%

100.0%

100.0%

239.95

216.46

227.03

7.28

7.28

7.28

32.96

29.73

31.19

Freight

1.2

0.75

Crude Price (Calc for Netback-Zero)

31.8

29.0

30.2

LPG
Naphtha
MS
Kero
Gasoil
Fuel oil
Fuel & Loss

220
289
298
290
264
166

Total
BPT
GPW, $/bbl

Landed Price, $/bbl

30.51

Gross Margin,$/bbl

2.45

ELEMENTS OF IMPORTED CRUDE

COST
COST ELEMENT

1 FOB

90%

2 OCEAN FREIGHT

3.9%

3 DAUGHTER VESSEL FREIGHT

0.8%

4 INSURANCE

0.05%

5 OCEAN LOSS

0.2%

6 PORT CHARGES

0.08%

7 CUSTOM DUTY

5.0%

8 DEMURRAGE

0.002%

9 ENTRY TAX

0.09%

TOTAL

100.0%

Gross product Worth of crude Oil

API
S, wt%
Price, /MT

32.4

32.6

32.7

0.079

0.081

0.13

Yield, wt fraction

GPW

Miri

Widuri

Cabinda

Miri

Widuri

Cabinda

0.9%
6.4%
8.0%
21.5%
42.5%
12.7%
8.0%

0.1%
1.5%
1.6%
7.7%
51.2%
29.9%
8.0%

1.5%
5.0%
5.4%
13.0%
45.0%
22.1%
8.0%

2.0
18.5
23.8
62.4
112.2
21.1

0.2
4.3
4.8
22.3
135.2
49.6

3.3
14.5
16.1
37.7
118.8
36.7

100.0%

100.0%

100.0%

239.95

216.46

227.03

7.28

7.28

7.28

32.96

29.73

31.19

Freight

1.2

0.75

Crude Price (Calc for Netback-Zero)

31.8

29.0

30.2

LPG
Naphtha
MS
Kero
Gasoil
Fuel oil
Fuel & Loss

220
289
298
290
264
166

Total
BPT
GPW, $/bbl

Landed Price, $/bbl

30.51

Gross Margin,$/bbl

2.45

Refining

39

Yield Structure of Various Crudes

40

TYPICAL REFINERY CONFIGURATION (MATHURA REFINERY)

FUEL GAS
SRU

AR
U

SR LPG
MERO
X

CRUD
E

PRU

STABILISER

SULPHUR

LP
G
PROPYLEN
E

NS
U

CCR
U

NAPTH
A
CAUSTI
C WASH

GASOLIN
E
MEROX

GCU

NAPTH
A

MS

DHDT
SK/ ATF
MERO
X

O
H
C
U

VD
U

FCC
U

LPG
MERO
X

VB
U

VB
N
MERO
X
BBU

AT
F
SK
HS
D

LD
O

FO
BITUME
N RFO

HP

Oil Products & Cut Points

42

Products
LPG
Naphtha
Petrol (BS-II/BSIII)
Kerosene
ATF

Fuel Oil (High S, Low S)

Fuel Oil (High or low Viscosity)

Diesel (BS-II/BS-III)
LOBS
Bitumen
RPC
Wax

LSHS
HPS

Petrochemical feed stock

LABFS
HPL Naphtha

Petrochemicals
pX, PTA
LAB etc

Yield Pattern of Crude Oils

Yield, %wt
LPG
Naphtha
Kerosene
Gas oil
VGO
Short resid

Basrah Bombay Arab mix Kuwait North Jodhpur

Light
High
Gujarat
crude
1.0
1.0
1.0
2.0
1.0
12.0
21.0
12.0
15.0
5.0
1.0
15.0
20.0
16.0
18.0
10.0
13.0
20.0
27.0
20.0
17.0
21.0
24.0
36.0
27.0
29.0
25.0
33.0
21.0
16.0
4.0
22.0
23.0
30.0
41.0

Properties of Naphtha
Characteristics

Basrah Bombay
Light
High

Density, gm/ml
Sulphur, ppm
RSH, ppm
Octane number
Aromatics, %wt

0.6912
175
33
9.5

0.7378
L0.01
nil
68.1
25.8

Kuwait

North
Gujarat

MS
Spec

0.6493 0.6958
0.06
L0.02
117
4.8
53.9
47.4
4.3

0.7407
L0.01
1
56.8
-

0.005
95
35

Arab
mix

Gasoline Specification
Euro I Euro II Euro III Euro IV
RON

95

95

95

95

Sulphur, Wt%

0.05

0.05

0.015

0.005

Benzene %wt

Aromatics %wt

42

35

Olefins,Wt%

18

Properties of Kero / ATF

Characteristics Basrah
Of SK/ATF from
Lt.
the Crude:

MH

Arab
mix

Density, gm/ml

0.783

0.7918

0.7902 0.787 0.7975

Smoke, mm

29

21

27

27

28

18

Sulphur, %wt

0.18

0.02

1.3

0.16

0.13

RSH, ppm

30

nil

8.8

12.9

<30

H2S, ppm

nil

nil

nil

3.9

nil

nil

<-60

-54

-59

-53

-47

-47

18.1

27.7

20.6

20

9.2

20

Freezing, C
Aromatics, %wt

KEC

NG

ATF
Spec

Properties of Gas oil

Characteristics

Basrah
Light

Density, gm/ml

0.8549

Mumbai
High

Arab
mix

KEC NG

Diesel
Spec

0.852 0.85 0.847

-6/18

-15

-18

-6

Sulphur, %wt

2.05

0.13

1.7

1.51 0.05

0.005

Cetane No.

48.8

59.5

54.9

56.8 60.6

53

Pour point, C

Distillation , T95, C

340

Diesel Specification
Euro I

Euro II

Euro III

EuroIV

Cetane Number

49

49

51

53

Sulphur,Wt%

0.2

0.05

0.035

0.005

Distillation T-95, oC

370

370

360

340

API classificationLOBS
SULPH VISCOSI
CLAS COMPOSITI UR
TY
S
ON
%
INDE
WT.
X
Group<90%
>0.03
95-120
I
Saturates
Group>90%
<0.03
95-120
II
Saturates
Group>90%
<0.03
>120
III
Saturates
GroupPoly alpha
IV
olefin
GroupOthers
V

THANK
!!! YOU