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ON
CRUDE ASSAY
J M NAGPAL, J K DIMRI
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.
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.
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).
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
---------------
> 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.
Type of Assay
Preliminary
Objective
Scope
Assay
Short Assay
Detailed Assay
residue
-Product optimization
conversion units
and FBP
-Characteristics and composition of
Property
-Density /API
Type
Significance
-LPG potential
-Wax Content
-Asphaltene
-Carbon Residue
Water Content
-Basic Sediment &
Water
-Ash
-Sulphur
-Nitrogen
-Metals
-Acids
-Salt Content
Micro- constituents
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
VI
Pour Point
Pour Point
Best
-
Good
Good
Good
Best
Best
Asphalt
Ductility
Good
Best
Coke
Electrode Carbon
Fair
Best
Diesel Fuel
Freezing point
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
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
Petrochemicals through
Olefins
Petrochemicals through
Olefins
Pure Chemicals (Pentane,
Hexanes, Heptane
SBP Solvents
Kerosene
Gas Oil
VGO
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
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
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
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
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
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
0.2
0.3
0.4
<0.01
0.01
0.02
0.06
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
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
0.9
6.5
8.1
2.4
10.9
9.7
21.2
40.3
0.1
0.6
26.8
12.8
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
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)
CRUDE OIL
UV
NMR
MASS (EI ) (Hydrocarbon Types)
MASS(EI) (Hydrocarbon Types )
HPLC (Aromatics )
VGO / LOBS
CRUDE BLENDING (ONLINE)
NMR / NIR
RESIDUE