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LECTURE NOTES

ON

CRUDE ASSAY

J M NAGPAL, J K DIMRI

RELIANCE INDUSTRIES LTD


JAMNAGAR

INTRODUCTION
Assay or evaluation of a crude oil involves assessing the crude oil for its characteristics including microconstituents present in it and yields and characteristics of the straight run petroleum products, which can be
obtained from the crude oil.

CRUDE OIL COMPOSITION (1,2)


Main bulk of a crude oil is hydrocarbons. Very simple structures (C3, C4, C5 hydrocarbons) to most complex
structures such as resins, poly-aromatics, asphaltenes and porphyrines etc. are present in a crude oil. Besides the
hydrocarbons, it consists of traces of compounds containing sulfur, nitrogen, oxygen and metals. Three main types
of hydrocarbons found in crude oils with their generic formulae are paraffins (CnH2n+2), naphthenes (CnH2n) and
aromatics (Cn Hn).

Branched as well as straight chain paraffins up to the carbon number of C120 and higher occur in a crude oil.
Naphthenes (saturated cyclic compounds) generally five or six member rings (monocyclic) or fused rings (polycyclic) structures are present in a crude oil. Aromatics are the unsaturated cyclic structures having lower hydrogen
to carbon ratios as compared to naphthenes. Aromatics are present as a single ring, biphenyl structures and fused
(multiple) ring structures. In the heavy ends of a crude oil, the fused rings are of very large structures with
molecular weights ranging from 1000 to 100000. Compounds containing sulphur, nitrogen, oxygen and metals are
present in traces but they have significant effect on the quality of products and feed stocks derived from a crude
oil. The elemental analysis of crude oils is in the following ranges:
Element

%wt.

83-87

11-14

~0-7

~0-1.0

~0-0.5

Metals

<0.1

The average elemental analysis of petroleum varies in a narrow range but the nature (quality and product potential)
of the crude oils from two different reservoirs is never the same. It is the relative difference in homologues series
of hydrocarbons (paraffin, naphthenes and aromatics) and the level of micro constituents, which are responsible for
the variations in the crude quality from different fields.

OBJECTIVE AND SCOPE OF CRUDE ASSAY

For an oil producer the crude assay data is important for its transportation and marketing/pricing of the crude oil in
the international market and a refiner needs the crude assay data for selection, grading and valorization. A detailed
crude assay is required for the design of a new refinery as well as for the expansion of an operating refinery. It is
not possible for a refinery to depend on a single crude supply these days. Refiners try several crudes and blend
them to their operating requirements. All such decisions are based on crude assays. Therefore, evaluation of the
crude oil becomes a priority to producers as well as refiners. However, depending on the objective of a crude
assay, its scope also may very (Table-1).

BASE AND CHARACTERISTICS OF CRUDE OIL

Characteristics of a crude oil, generally carried out, are given in Table-2. A crude oil consists of millions of
individual compounds. Although all the crudes contain substantially the same types hydrocarbons but their gross
properties and product potential are likely to change with the relative predominance of particular type of
hydrocarbons. Paraffinic base crudes consisting of predominantly paraffinic hydrocarbon are generally light
crudes with relatively higher distillate yields. On the other hand crude oils classified as naphthenic contain
predominantly cyclic structures and are generally heavy with lower yields of distillates. Crudes classified as
intermediate have approximate balance of both paraffinic and naphthenic (cyclic) type of hydrocarbons resulting in
more or less intermediate in product potential and quality of the products.

Several empirical correlations and approaches have been developed to classify the crude oils (2). Most commonly
used is a characterization factor method developed by UOP.

TB
Characterization factor (KUOP) = -------------------S
Where TB is mean average boiling point and S is specific gravity at 60/60F

KUOP
---------------

Base of crude oil


------------------------

> 12.1

Paraffinic

11.5-12.1

Intermediate

< 11.5

Naphthenic

The expected quality of crude oils as such, their products potentials and quality of the products with the base of the
crude oils are compared in Table-3 (3).

For assessing the nature of lighter ends of the crude oil, Reid vapor pressure and (RVP) and LPG potential by gas
liquid chromatography are carried out. Flow behavior of the crude oil, which is important for its transportation
through pipelines, is studied by determining viscosity at different temperatures (dynamic or kinematics at above
the pour points and plastic viscosity and yield stress through rotational viscometers below the pour point
temperatures). Rheological behavior of a waxy crude differs significantly from a low wax containing crude (Table4). Pour point and wax content (above ~ C16 paraffins) determinations also made to highlight the flow behavior of
a crude oil.

Characteristics such as asphaltene content, carbon residue and ash content give an idea of the nature of heavy ends
of a crude oil. Sulfur, nitrogen, metals and acidity are considered important quality parameters of a crude oil as
they deteriorate the quality of products and feed-stocks for secondary conversion processes. Cost intensive
processing is required in refineries to treat the distillates to bring down the levels of sulfur, nitrogen and metals.
These days, environmental concerns are forcing refiners to produce distillate fuels with ultra low sulfur contents.

Salt content (associated brine), water and sediment are the impurities in a crude oil. Presence of high salt content
is the main cause of overhead corrosion in distillation units and deterioration of the bottom product quality as well
as it is responsible for fouling of heat exchangers. Sediment and water occupy precious space in crude oil tanks
and increase the sludge as well as cause operational problems. Besides conventional fuels a detailed assay covers
potential of pure chemicals and other value added products and lube base stocks (Table : 5)

TBP ASSAY

True boiling point (TBP) distillation, consisting of a fractionating column with minimum 15 theoretical plates and
a provision for a reflux (5:1) (ASTM D2892) is a main tool for carrying out the TBP assay. Broad cuts from the
crude oil for a qualitative assessment in atmospheric range up to a temperature of ~ 400oC are also prepared in
TBP set up. The residue can be further distilled using a high vacuum still (Pot still, ASTM D5236) to prepare cuts
up to ~ 565oC

Typical crude assay data are given in tables 6 to 8. Table 6 gives the typical crude characteristics of different crude
oils.

In a TBP assay the crude oil is fractionated to prepare narrow cuts (2-6 %volume or weight intervals or 10 to 25oC
vapor temperature intervals). Yields of these cuts are assigned on cumulative weight and volume basis to prepare
TBP distillation curves (Figure-1). The narrow cuts can be analyzed for some key characteristics to study the
variation of properties with cut temperatures (Table 7). The data can be represented in more useful manner on mid
vol. / wt. % - property curves (differential curves) (Figure-2). The representation of additive properties on mid %
curves is more accurate and these curves can be used to find out the property of any width of fraction of
commercial interest.

Key properties of the broad cuts (prepared directly from the crude or by back blending of narrow cuts) can be
represented on property yield curves also. These curves are very useful in product optimization.
Broad cuts of commercial interest prepared directly from a crude oil are characterized in detail to study the yields
and quality of these products (Table-8).

ANALYTICAL DEVLOPMENTS
Advances in analytical techniques (Fig-3) have been of valuable support to crude and product analysis. Capillary
Gas Liquid Chromatography (GLC), Mass Spectrometry (MS), Nuclear Magnetic Resonance (NMR), Near Infra
Red (NIR), X-Ray Fluorescence (XRF), High Performance Chromatography (HPLC), Atomic Absorption
Spectroscopy (AAS) and Gel Permeation Chromatography (GPC) and other dedicated instrumental analytical
techniques can be used to generate the compositional parameters of petroleum products. The
compositional information can be used for computer simulations and design of processes units as well as to study
the feasibility of getting value added products from the crude oils in order to increase the profitability of a refinery.

CONCLUSION
A crude assay essentially comprises of crude characteristics, TBP assay and yield and characteristics of several
broad cuts in atmospheric and vacuum ranges. However, the scope of the crude assay varies with its required
application. Use of advanced analytical techniques can help in generating a detailed component-wise analysis or
hydrocarbon type analysis of the various cuts which is very useful in design of the refinery units. The crude assay
data is of immense importance to the crude producer as well as to the refiner.

REFERENCES

1.

Davies J.F. Crude Oil in Modern Petroleum Technology Edited by Alan G. Lucas John Wiley & Sons Ltd

2000.
2.

Nelson W.L. Evaluation of Oil Stocks in Petroleum Refining Engineering, Mc Graw Hill Book Company

Inc. 1949.
3.

Nelson W.L. Which Base of Crude Oil is Best? Part I, Oil & Gas Journal 1979, Jan8, p112

4.

Nagpal J M, Sharma R L Role of IIP in the Area of Crude Oil Evaluation and Product Analysis in

Challenges in Crude Oil Evaluation Edited by J M Nagpal, Tata Mc Graw Hill Publishing Company Limited, New
Delhi, 1995.

Table 1: Objective and Scope of Crude Assays

Type of Assay

Preliminary

Objective

Consistency of crude supply

Scope

Basic crude characteristics

Assay
Short Assay

Detailed Assay

- Absorption of a new crude in a fuel Crude characteristics, TBP distillation


refinery

data, key characteristics of straight run

- To study the change in crude quality

cuts in atmospheric range and long

over a period of time

residue

-Design data for a grassroot refinery

-Detailed characterization including


crude oil micro-constituents

-Product optimization

-TBP Assay in atmospheric and vacuum


range. Yield and characteristics of

-Selection and design of secondary

several broad cuts with variations in IBP

conversion units

and FBP
-Characteristics and composition of

-Expansion modification of units

specific cuts for process simulation and

-Value Addition feasibility

feed stock quality for secondary


processing, value addition and lube
manufacture

Table2. Characteristics of Crude Oil

Property

-Density /API

Type

Basic physico- chemical


properties

-Base of crude oil

- Reid Vapor Pressure

Significance

-Chemical nature of the crude reflected


-Density / API extensively used in weight /
Volume conversions

Light ends in crude oils

-LPG potential

- Dissolved Gas analysis


-Storage, handling of crude oil
-Pour point
-Viscosity

Flow properties of crude oil

-Waxy crude oils not suitable for lube


and bitumen manufacture

-Wax Content

-Asphaltene
-Carbon Residue

Heavy End Properties

Water Content
-Basic Sediment &
Water

-Reflect heavy hydracarbons in crude oils

- Ash reflects presence of inorganic matter

-Ash
-Sulphur
-Nitrogen
-Metals
-Acids
-Salt Content

-Transportation and handling crude oil

Micro- constituents

Significant effect on product and feedstock


quality

Impurities

- Process implications
-Need to be eliminated before processing
the crude oil

Table3: Correlation of Base of Crude Oil with Quality of Crude and Products

Crude /Product

Crude
Petroleum Naphtha
Petrochem./Fert.
BTX
Gasoline
Straight Run
Reformer feed
Thermal Crackate
Cat Crackate
Hydrocrackate
Kerosene
Jet Fuel

Superiority

Sp. Gravity

Yield
Yield
Oct. No.
Oct. No.
Oct. No.
Oct. No
Oct. No.
Smoke Point

P
low

I
Intermediate

Good
Best
Fair
High
Intermediate
Good
Low
Good
Fair
Little -----Little- Effect---------Effect-----V. Good
Good

N
High

Good
Low
V. Good
Best
Good
-----------Poor

Fair

Good

Cat Cracking

Ignition
Pour Point
Gasoline Yield

Good
Good

Fair
Fair
Fair

Good
-

Hydrocracking

Distillate Yield

Good

Fair

Carbon Black

Yield

Good

Lube oil, Automotive


Residual Fuel

VI
Pour Point
Pour Point

Best
-

Good
Good
Good

Best
Best

Asphalt

Ductility

Good

Best

Coke

Electrode Carbon

Fair

Best

Diesel Fuel

Freezing point

Base of Crude Oil

Table 4: Flow Characteristics of Crude Oils with Low and High Wax
Crude

Basrah Lt.

Mumbai High

Wax, %wt

3.5

10.9

Pour Point

-24

+30

Kin. Viscosity, cSt at 40 C

6.18

4.30

at 50 C

4.84

3.32

2.0
5.0
10.0
12.5

45.0
85.0
222.0
330.0

9.6
14.7
6.0
17.3

7.9
30.7
43.7
45.0

Yield Value, Dynes / cm2, at


32 C
24 C
18 C
16 C
Plastic Viscosity CP at
32 C
24 C
18 C
16 C

Table 5: Potential of Pure Chemicals and Other Value Addition Products


Stream
Naphtha

Value Added Products


-

Petrochemicals through
Olefins
Petrochemicals through
Olefins
Pure Chemicals (Pentane,
Hexanes, Heptane
SBP Solvents

Kerosene

n-Paraffins for LAB

Gas Oil

n-Paraffins for Synthetic Fatty Acids

VGO

Potential for Base Oils, Waxes

Deep Distillation Cuts

Microcrystaline Wax

Cut Temperature
(Approximate)
IBP -105C
60-140C
Optomised cut point from light
naphtha
Specific cut points depending on
grade in the range of IBP to
300C
175 -265C

550C+

TABLE : 6
CRUDE CHARACTERISATION
RESULT
Sr No

CRUDES
CHARACTERISTICS

Density,at 15C

Specific Gravity @
15.6/15.6C
Barrel factor
API Gravity
Pour Point
CCAI
RVP, at 38C
BS&W
Water content, (D & S)
Salt content
Total chloride
Ex H2S
Potential H2S
Total Sulphur
Asphaltenes
Carbon Residue (Micro)
Total Nitrogen
Filterable solids
TAN

3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25

26

27

Kinematic viscosity, @ 40C


V50
C/H ratio
Gross Calorific value
Kuop
ASTM Distillation D-86
IBP
5% vol. recovered at
10% vol. recovered at
20% vol. recovered at
30% vol. recovered at
40% vol. recovered at
50% vol. recovered at
60% vol. Recovered at
Recovery at 300C
TRACE METALS
Ni
V
Fe
Cu
Si
Light Hydrocarbon Analysis
n-C2, (Ethane)
n-C3, (Propane)
i -C4, (iso-Butane)
n-C4, (n-Butane)
i -C5, (iso-Pentane)
n-C5, (n-Pentane)

ZAFIRO

ARAB HY.

MARIB LT

EOCENE

kg/m3

872.2

890.8

802.6

940.3

--

0.8727

0.8913

0.8030

0.9

bbl/T
API
C

7.2
30.6
<-21
707.1
36
<0.05
<0.05
1.7
<1

7.8
44.6
<-27
771.35
50
0.02
<0.05
1.6
2.8
<1
0.098
0.9
1.0
555
5
0.03

6.70
18.9
<-24
822.6
10
0.1
0.05
8.7
9.1
16.0
4600
4.36
7.4
10.8
1350
38.0
0.29

UOM

Kpa
%vol
%vol
PTB
ppm
ppm
ppm
%wt
%wt
%wt
ppm
PTB
mg KOH
/gm
cSt
KJ/KG
-

0.28
0.2
2.8
2140
21
0.70

7.1
27.3
<-24
798.9
42
0.1
0.05
4.1
2
<1
8
3.00
5.9
8.1
1610
8
0.21

6.46
15.5
6.7
44910
11.8

21.06
21.9
6.7
43710
11.9

1.79
5.06
6.2
44989
12.2

109.5
28.0
7.0
42470
11.5

C
C
C
C
C
C
C
C
%vol

49
100
127
167
213
262
49

60
106
138
200
272
34

43
67
80
104
128
156
198
252
67

68.0
147.0
186.0
273.0
26.0

ppm
ppm
ppm
ppm
ppm

13.7
2.1
7.1
<0.01
5.6

20.3
69.1
0.7
<0.1

0.2
0.5
1.9
<0.01
<0.01

22.0
58.8
5.4
0.5
<0.1

% wt
% wt
% wt
% wt
% wt
% wt

0.01
0.15
0.14
0.56
0.61
0.63

0.02
0.27
0.15
0.78
0.55
1.00

<0.01
0.15
0.29
1.84
1.89
2.52

0.01
0.10
0.11
0.42
0.66
0.47

7.4

0.7372

125

3.0

10.4

0.7576

150

15.4

0.7760

175

4.3

19.7

0.7938

200

4.1

23.8

0.8136

225

4.2

28

0.8321

250

5.9

34

0.8441

275

5.8

39.8

0.8582

300

5.5

45.3

0.8644

325

5.3

50.6

0.8732

350

5.1

55.7

0.8902

370

4.1

59.8

0.9015

370C+

40.2

100.0

4.1
3.5
5.6
4.7
4.4
4.4
6.1
5.9
5.5
5.3
5.0
4.0

Kuop

3.5

Diesel Index

100

2.4

Aniline Point, C

0.6891

Smoke Point, mm

3.9

Pour Point,C

1.9

TAN, mg KOH/g

75

1.5

K.
Viscosity,cSt@40C

0.6275

Total Nitrogen ,ppm

2.0

Doctor test

1.1

1.35608

73.8

1.38490

4.8

12.2

9.4

60.4

1.40733

4.0

-ve

11.7

12.9

55.2

1.41886

0.010

2.8

-ve

11.7

18.5

50.8

1.42922

0.015

2.2

-ve

2.3

11.6

23.2

46.7

1.43870

0.03

3.7

-ve

3.5

0.01

24

50.0

56.9

11.6

27.6

42.3

1.44873

0.04

5.7

-ve

6.4

0.03

22

51.2

52.5

11.5

32.0

38.5

1.45833

0.06

6.1

-ve

8.1

0.04

<-24

20

55.2

50.5

11.5

38.1

36.1

1.46599

0.084

6.6

-ve

24.9

0.17

<-24

18

58.8

49.7

11.5

44.0

33.3

1.47465

0.15

8.1

-ve

69

2.58

0.35

<-24

15

60.6

46.9

11.5

49.5

32.1

1.47844

0.19

9.8

-ve

129

3.99

0.62

-21

65.2

47.9

11.6

54.8

30.5

1.48301

0.21

10.2

-ve

218

5.90

0.89

-9

69.2

47.7

11.6

59.8

27.4

1.49251

0.28

10.7

-ve

435

9.45

1.20

69.6

43.0

11.6

63.8

25.4

1.49918

0.33

15.0

-ve

769

15.60

1.39

12

70.4

40.3

11.6

1.4

112.5

2.9

94.0

5.3

Mercaptans,ppm

38

1.4

T.S ,%wt

0.5800

R.I @20C

0.9

API

Cumm wt%

0.9

Cumm vol%

wt%

15

vol %

Fractions, C

Density
@15C,Kg/M3

TABLE : 7 TBP DISTILLATION DATA AND CHARACTERISATION OF 25C TBP CUTS

TABLE : 8 CHARACTERISATION OF BROAD CUTS


Fractions C

Density @15C,Kg/L

15C

105-150C

150-165C

165-227C

227-270C

270-370C

370C+

370-390C

390-410C

410-565C

565C+

LPG

L.N

M.N

H.N.

L.K.

H.K.

L.D.

RCO

HD

LVGO

HVGO

V.R.

0.5800

0.7064

0.7671

0.7910

0.8193

0.8506

0.8794

0.9683

0.9190

0.9215

0.9442

1.0337

0.7066

0.7674

0.7913

0.8197

0.8510

0.8799

0.9689

0.9195

0.9220

0.9447

1.0343

68.8

52.9

47.3

41.1

34.8

29.3

14.5

22.4

22.0

18.3

5.3

-6

36

15

24

33

84

1.48645

Specific gravity
API

C5-105C

112.5

Pour Point, C
Refractive Index

1.3958

1.42429

1.43747

1.45176

1.46997

Freezing Point,C

<-60

<-60

-38

Smoke Point, mm

24

20

16

12

Flash Point,C

54

99

139

Saybolt colour

12

-2

R.V.P at 38C, PSI

7.53

1.06

0.32

Viscosity at 100F,cSt

0.74

0.84

1.20

2.41

6.93

47.05

Viscosity at 122F,cSt

0.65

0.73

1.02

1.97

4.95

25.63

130.40

Viscosity @100C,cSt

59.7

8024

Total sulphur,% wt

<0.01

0.01

0.03

0.05

0.11

0.24

0.48

0.34

0.36

0.38

0.64

Total Nitrogen, ppm

2.8

6.9

44.8

372

1119

2974

1.0

1.9

2.8

3.6

6.9

-ve

-ve

-ve

-ve

-ve

-ve

0.5

0.7

1.1

1.5

0.26

0.96

1.13

1.14

1.38

RSH , ppm
Doctor Test

Total chloride, ppm

0.2

0.3

0.4

TAN ,mgKOH /gm

<0.01

0.01

0.02

0.06

Copper strip corrosion

1A

1A

Cetane Index

27.3

34.8

41.2

50.3

Carbon residue,%wt

7.8

0.3

19.8

C5 insolubles, %wt

12.5

Aromatics, %vol (FIA)

16.1

28.6

Aromatics,wt %( UV)

14.92

16.46

Ni /V

32.4 / 5.7

90/ 17.8

53 /<0.01/ 51.8

TRACE METALS

Fe/ Cu /Si

18 /<0.01 / 31

BENZENE VOL%

0.9

Yield %wt on crude

0.9

6.5

8.1

2.4

10.9

9.7

21.2

40.3

0.1

0.6

26.8

12.8

yield %vol. on crude

1.3

8.0

9.2

2.7

11.6

9.9

21.0

36.3

0.1

0.6

24.8

10.8

15
38
75
105
124
150
175
200
222
250
275
300
325
350
370

0.9
2.0
3.9
7.4
10.4
15.4
19.7
23.8
28.0
34.0
39.8
45.3
50.6
55.7
59.8

1.4
2.9
5.3
9.4
12.9
18.5
23.2
27.6
32.0
38.1
44.0
49.5
54.8
59.8
63.8

275
300
325
350
370

275
300
325
350
370

2.58
3.99
5.9
9.45
15.60

41.1
46.8
52.2
57.3
61.8

41.1
46.8
52.2
57.3
61.8

-30
-21
-9
0
12

275
300
325
350
370

275
300
325
350
370

2.58
3.99
5.9
9.45
15.60

41.1
46.8
52.2
57.3
61.8

41.1
46.8
52.2
57.3
61.8

-30
-21
-9
0
12

Fig :3

Application of Instrumental Analytical Technique

GAS / LPG

GLC (Composition)
GLC(Composition,PIONA,Bz, Oxygenates)
NMR (PONA, C/H Ratio, Av. Mol Wt )

NAPHTHA /
GASOLINE
AAS
ICP
Metals

GLC
LPG Pot

IR (PONA )
SFC ( Olefins )
HPLC ( Olefins )
HPLC ( Hydrocarbon Types )
GLC (n-Paraffins )

KEROSENE

UV (Total Aromatics )
MASS(EI) (Naphthalenes)

HPLC ( Hydrocarbon types )

CRUDE OIL

UV

GAS OIL/ DIESEL

NMR
MASS (EI ) (Hydrocarbon Types)
MASS(EI) (Hydrocarbon Types )
HPLC (Aromatics )

VGO / LOBS
CRUDE BLENDING (ONLINE)
NMR / NIR

NMR (n -, iso - cyclo paraffins )


AAS/ICP (Metals )
UV ( Aromatic distribution )
IR ( Functional group )

MASS (FI/FD) (Av. Mol weight and distribution)

RESIDUE

AAS/ ICP (Metals )


NMR (Carbon type distribution, Av. Structure )