Processing high TAN crude: part I

T
he trend in crude oil supplies
after 150 years of petroleum
processing is towards heav-
ier, lower quality feedstocks.
According to ENI Group of Italy,
the ratio of heavy crude oil (API
1026) in the total crude oil slate
rose from 11% in 1995 to 14% in
2005, and the trend in recent years
has accelerated. So the oil refning
industry must increasingly face
the challenges presented by heavy,
low-quality crudes, cleaner produc-
tion standards, and the demand for
cleaner fuels and high-value petro-
chemical products.
Opportunity crude oil generally
refers to crude oils with a relatively
high metals and sulphur content,
and a high total acid number
(TAN) and density. High TAN or
acid content heavy crude oil is the
typical opportunity crude oil.
Usually, high TAN crude has the
following properties: a high acid
value, fewer light components, a
high density and viscosity, a high
gel-asphalt content, and high salts
and a heavy metals content, which
give rise to equipment corrosion
and severe problems with product
quality and environmental
protection.
The price of opportunity crude oil
is about 80% of the price of conven-
tional crude oil. The extra cost of
processing high TAN crude is in
the range $1.1510.73/bbl, but the
savings compared to conventional
crude processing are $43.5462.7/
bbl. The cost of crude accounts for
about 9095% of the total running
costs of refneries, so it is very
attractive for refneries to process
opportunity crude, especially high
TAN crude.
Huizhou, which is the frst refnery for processing 100% high TAN crude, started up
in 2009. This article describes the challenges of an opportunity crude operation
Wu QiNg
CNOOC
Huizou refnery
With an annual capacity of
12 million tonnes (240 000 b/d)
CNOOCs Huizhou refnery is the
frst large-scale refnery designed
for the full conversion of high TAN
crude. The refnery has done a
tremendous amount of work to
address the potential risks of
refning opportunity crude oil
and to achieve successful produc-
tion start-up and smooth operation.
The grassroots refnery started
operations in April 2009 and
currently all units are running
smoothly, with excellent product
quality achieved from a slate of
around a dozen high-acid crude
oils.
The frst part of this article deals
with specifc corrosion types and
environmental issues arising from
high TAN crude processing. Part
two will address operational issues
at Huizhou.
High TAN crude: resources,
properties and acid distribution
Usually, we use acid number to
distinguish the acidity of crude oil.
Acid crude oil means that the acid
number is >0.5mg KOH/g, and
high TAN crude means that the
acid number is >1.0mg KOH/g. For
high TAN crude, there are two
main types, according to sulphur
content: one is high TAN, low-
sulphur heavy crude, and the other
is high TAN, high-sulphur heavy
crude. The latter are produced in
Venezuela and California, while
high TAN, low-sulphur heavy
crudes are more common; there are
fve main oil felds in four conti-
nents producing this type of crude.
In Europe, it is mainly represented
in the North Sea and processed by
refneries in Europe and the Gulf of
Mexico. In the Americas, it is
mainly represented by Brazilian
www.digitalrening.com/article/1000524 PTQ Q4 2010 35
Year North Europe, kb/d America, kb/d West Africa, kb/d Far East, kb/d Total, kb/d
1998 510 910 100 770 2290
1999 580 1160 110 770 2620
2000 600 1415 170 770 2955
2001 630 1675 200 795 3300
2002 725 1815 255 795 3590
2003 765 1875 265 805 3710
2004 740 1935 475 805 3955
High TAN crude production, 19982004
Table 1
Cost of crude accounts
for about 9095%
of the total running
costs of refneries, so
it is very attractive for
refneries to process
opportunity crude
Marlim crude oil and is processed
in several continents. In Africa, it is
mainly represented by West African
Kuito and Sultan crudes and is
36 PTQ Q4 2010 www.digitalrening.com/article/1000524
processed in refneries in the US
and Asia. In Asia, it is mainly
represented by Bohai sea crudes
(for instance, Penglai crude) and is
processed mainly in China. Table 1
shows the output of high TAN
crudes in 19982004. Table 2 shows
the main properties of high TAN
Crude oil Liuhua Xinjiang pipleline Duli Hange Kuitu Penglai 19-3 Liaohe Duoba Malin Da blended
transfer crude oil
Density, g/cm
3
20C 0.9208 0.907 0.921 0.8829 0.9283 0.9276 0.9338 0.9309 0.9326 0.9
Solidifcation point, C -8 -17.5 10 <-20 <-20 -32 3 -13 -8.1 38
Viscosity, mm
2
/s50C 67.96 100.8 179.5 14.64 54.83 97.91 509.4 141.9 78.62 23.7
Residual carbon, % 6.7 4.75 7.61 5.28 6.54 6.11 8.98 5.47 6.78 7.7
Sulphur, % 0.243 0.131 0.221 0.661 0.691 0.32 0.2 0.16 0.68 0.11
N, ppm 2569 2235 2538 4439 3000 4700 18742300 3700 3370
Acid number, mgKOH/g 1.12 4.51 1.4 0.51 1.9 3.57 2.12 3.555.05 1.27 3.68
Asphalt, % 4.12 5.42 1.63 1.55 1.19
Resine, % 16.56 12.58* 19.14 12.19 28.34 17.7* 18.54* 19.87 16.98*
Wax, % 6.37 13.55 1.51 1.52 6 7.5 10.36 2.92
Metal analysis, ppm
Fe 2.45 12.51 7.89 14.16 11.02 6.92
Ni 5.68 9.8 36.61 8.41 41.96 31.34 46.6 7.1310.53 16.6 60.63
Cu 0.04 0.34 <0.03 <0.03 0.03 0.16
V 0.41 0.42 1.43 14.46 39.12 1.17 0.17 0.130.62 24.7 1.06
Ca 11.5 12.22 0.33 1.18 199.33 5.77
Mg 1.28 1.78 <0.03 0.47 2.42 0.62
Pb 0.12 1.55 <0.10 <0.10 0.18 <0.10
Na 8.24 8.34 1.02 13.63 _ 2.92 41.94
As <0.10 0.81 _ <0.10 <0.10
Salt, mgNaCl/L 67.8 15.6 9.8 38.2 130 3.2 179 17.4
Watson, K 11.7 12.25 11.85 11.9 11.65 11.85 12.2
Crude type Low Low Low Low Sulphur Sulphur Low Low Sulphur Low
sulphur sulphur sulphur sulphur contained contained sulphur sulphur contained sulphur
heavy naphthene heavy medium heavy heavy naphthenic heavy heavy medium
content medium content content content naphthene base content content content
medium base medium medium medium medium medium naphthenic paraffn
base base base base base base base base
Light yield, % 26.77 21.83 44.75 34.72 20.33 21.5
Total yield, % 63.92 51.19 72.07 67.1 54.18 48.1
Main properties of high TAN crude
Table 2
No. Boiling Occupation Density, Solidifcation Acid degree, Acid number, Watson, K
point range, C in crude oil,% (m/m) g/cm
3
(20C) point, C mgKOH/100mL mgKOH/g
Each fraction Total yield
1 <80 0.49 0.49 0.7288 3.77 11.3
2 80100 0.57 1.06 0.7389 1.26 - 11.7
3 100120 0.87 1.93 0.7536 1.89 11.7
4 120145 1.25 3.18 0.7723 6.29 11.6
5 145170 1.72 4.90 0.7947 24.53 11.5
6 170200 2.27 7.17 0.8247 63.96 11.3
7 200235 3.78 10.95 0.8516 116.6 1.2
8 235250 1.95 12.90 0.8671 230.7 11.2
9 250275 3.67 16.57 0.8766 304.5 11.2
10 275300 3.51 20.08 0.8791 395.9 11.3
11 300320 3.29 23.37 0.8776 471.4 11.5
12 320350 5.23 28.60 0.8946 470.6 11.5
13 350360 1.65 30.25 0.9036 <-40 6.19 11.5
14 360395 5.72 35.97 0.9096 -30 5.74 11.5
15 395425 5.67 41.64 0.9166 -14 4.34 11.6
16 425450 5.74 47.38 0.9342 -10 2.68 11.6
17 450475 6.27 53.65 0.9347 -6 2.26 11.7
18 475500 5.06 58.71 0.9347 2 3.23 11.8
19 500520 3.25 61.96 0.9323 6 3.94 12.0
20 520545 3.80 65.76 0.9352 24 4.16 12.1
21 >545 34.24 100

Detailed data for the different fractions of PL 19-3 crude
Table 3
crude, and the acid distribution of a
typical high TAN crude is shown in
Tables 3 and 4.
In general, the features of high
TAN crude are:
Higher acid number (for instance,
Penglai 19-3s acid value is
3.57 mgKOH/g, but most have
a comparatively low sulphur
content)
Lower API number (or higher
density, most of them higher
than 930 kg/m
3
) with higher viscos-
ity and higher asphalt and gel
content
Low solidifcation point
Higher nitrogen content
Higher content of heavy metals
Lower yield of light oil
distillates.

Problems of high TAN crude
processing
Table 5 lists the processing chal-
lenges posed by high TAN
properties and solutions to these
challenges.
Potential problems in processing
high TAN crude are set out in Table
6. Apart from the huge risks associ-
ated with high-temperature
corrosion, Huizhou refnerys crude
distillation unit has other problems
to contend with; for instance,
Table 5
www.digitalrening.com/article/1000524 PTQ Q4 2010 37
Sample name Acid degree/acid number, mgKOH/100mL/mgKOH/g
Penlai19-3 crude oil Cao FeiDian crude oil
Acid degree
Atmospheric overhead gasoline 0 0
Atm draw 1 228.69 2.05
Atm draw 2 404.44 22.82
Atm draw 3 553.77 149.98
Acid value
Vacuum draw 1 5.88 1.45
Vacuum draw 2 5.79 2.89
Vacuum draw 3 3.72 3.29
Vacuum draw 4 3.79 3.78
Typical acid number (or degree) of different draws from CDu for China offshore crudes
Table 4
Materials typical pollutants Process challenges Solutions
High content of flterable solids Fouling, foaming, desalting effciency, Storage tank dewatering, desalting (listed as process challenge), process
environmental protection scale inhibitor, wastewater treatment
High water content Desalting, product quality, corrosion, Storage tank dewatering, desalting (same as above), tower overhead
foaming, energy consumption corrosion control
High salt content Corrosion, fouling, desalting, catalyst Storage tank dewatering, desalting (same as above), tower overhead
poisoning corrosion control, process scale inhibitor
High content of organic chloride Corrosion, HDS catalyst poisoning Tower overhead corrosion control, HDS reactor bed treatment
High acid content Corrosion containing water and high Tower overhead corrosion control, high temperature corrosion control,
Total acid value naphthenic temperature material upgrading
acid value
High sulphur content H
2
S and Corrosion, product quality, Tower overhead corrosion control, H
2
S trapping agent
mercaptan transportation storage and safety
High metal load CaHg Fe Se Fouling, catalyst poisoning, product Remove impurities in desalting unit, process scale inhibitor,
quality, SH&E wastewater treatment
High content of Ni/V Catalyst poisoning, FCCU operation FCCU metal inactivation plan
Raw material poor compatibility Fouling, desalting, energy consumption Process scale inhibitor
Processing challenges and solutions with high TAN crude
Problem areas Problem description
Tank area Sump oil in tank increase
Tank volume decrease
Electric desalting tank Oil entrainment in drainage water
High water content in desalted crude oil
Emulsion layer thickness increase
Treatment capacity decrease
Tower overhead corrosion Tower overhead organic acid corrosion increase
Tower overhead salting increasing trend
Heat exchanger system Fouling trend increases in heat exchanger system
High energy consumption
Wastewater treatment system Higher solids, naphthenic acid, organic material
and other content in wastewater
Very diffcult to treat
Potential problems in processing high TAN crude
Table 6
Corrosion-infuencing factors
Temperature
Naphthenic acid corro-
sion is heavily infuenced by
temperature. Corrosion at low
temperatures is not signifcant but,
in the boiling state especially
in a high-temperature, anhydrous
environment corrosion is most
signifcant. Most high-temperature
naphthenic acid corrosion occurs in
the liquid phase, but if naphthenic
acid is condensed in the gas phase
then gas-phase corrosion may
occur and the extent of corrosion
will be infuenced by acid value.
In addition, the corrosion prod-
uct of a direct reaction between
high-temperature naphthenic acid
and metal surface or iron sulphate
membrane Fe(RCOO)
2
is oil
soluble. It can be easily dissociated
from the metal surface and carried
away by oil, so that a new bare
metal surface is exposed, resulting
in further corrosion. A metal surface
corroded by naphthenic acid is very
smooth and clean. Following long-
term contact with naphthenic acid,
the metal surface will form observ-
able corroded grooves or traces. (A
high-speed acid stream will form
directional, sharply grooved lines,
while a low-speed acid stream will
form corrosion pits with sharp
edges.) These signs distinguish this
type of corrosion from other types.
The following summarises the infu-
ence of temperature on naphthenic
acid corrosion:
<200C in anhydrous conditions,
no corrosion; but, in an aqueous
environment, corrosion will increase
with rising temperature
270~280C the acid boiling point,
resulting in the most serious
corrosion
350~400C as a result of the melt-
ing of FeS membrane, together with
the effects of elemental sulphur
dissociated from crude oil
sulphides, the corrosion of metal
equipment becomes violent,
enhanced by the interaction
between naphthenic acid, elemental
sulphur and H
2
S
>400C oil-derived acid is decom-
posed and corrosion is weakened;
www.digitalrening.com/article/1000524 PTQ Q4 2010 39
increased amounts of sump
oil, diffculties with wastewater
treatment, and constraining issues
in sole crude and mixed refning.
Figure 1 shows the locations of
these problems, including the crude
oil tanks, electric-desalting tank
heat exchanger system, overhead
system and wastewater treatment
system.
High-temperature naphthenic
acid corrosion
High-temperature naphthenic acid
corrosion mainly occurs at tempera-
tures above 200C, in particular
above 220C, affecting equipment
that has the closest contact with
naphthenic acid. The most seriously
affected component is the vacuum
distillation column system of the
atmospheric and vacuum distilla-
tion system, including the vacuum
heater, transfer line, vacuum draw
three, vacuum draw four, vacuum
tower feeding line and internal
structures.
High-temperature naphthenic
acid corrosion includes four main
steps:
Naphthenic acid molecules are
transferred to a metal surface
The molecules become adsorbed
onto the metal surface
The molecules react with surface
active centres
Corroded materials are desorbed.
Crude oil tank area
Electric-desalting tank
Electric-desalting drainage
Water
Heat exchanger system
Waste treatment system
Overhead
Figure 1 Main problems in Huizhou refnery
High-temperature
naphthenic
acid corrosion
mainly occurs at
temperatures above
200C, in particular
above 220C
where naphthenic acid is thermally
decomposed, there will be forma-
tion of low molecular mass organic
acid or CO
2
, which have an effect
on the corrosivity of condensate
water.
Flow velocity and fow regime
Corrosion is particularly heavy in
equipment elbows, tee joints and the
turbulent fow areas of pumps. The
included angle between media fow
direction and metal wall also heav-
ily infuences naphthenic acid
corrosion; a bigger angle will result
in a bigger impact force and hence
heavier corrosion. If the fows gas
content is higher than 60%, and the
gas streams speed is higher than
60m/s, the corrosion speed of some
equipment such as furnace tubes,
elbows and vacuum distillation
transfer lines may increase by about
two orders of magnitude. At certain
temperatures, there is a critical
velocity for some materials. If the
fow velocity is lower than this criti-
cal value, the naphthenic acid
corrosion rate will be very low. The
generally controlled fow velocity is:
For carbon steel: <25-30m/s
SUS316: <120m/s (no turbulent
fow).
Acid molecular weight and acid
distribution
Acid value does not directly refect
the rate of naphthenic acid corro-
sion; there is no proportional
relationship. Naphthenic acids of
light molecular weight need a lower
activation energy for their reaction
with metals; activity is higher at
low temperatures and corrosion is
heavier. Naphthenic acids of heav-
ier molecular weight need a higher
activation energy during their reac-
tion with metal, hence activity is
lower at low temperatures.
High acid crude oils from differ-
ent areas have differing acid
distributions, hence they have
differing corrosivities and differ-
ences in absolute corrosion speed.
Figure 2 shows the infuence of acid
molecular weight and distribution
on naphthenic acid corrosion.
Crude oil type
High acid crude oils from different
areas show differences in their
www.digitalrening.com/article/1000524 PTQ Q4 2010 41
acid distribution and corrosivity.
The corrosivity towards SS300
stainless steel, for example, of
Penglai 19-3 crude oil, Beijiang
crude oil and Lvda-10 is different
in each case; the infection point
temperature of these three high
acid crude oils is 300C, 300310C
and 310320C respectively, and
their corrosivities are decidedly
different. The speed of corrosion of
SS300 in these three oils at a
temperature of 330C is around
1mm/a, 0.4mm/a and 0.3mm/a
respectively.
Material
The corrosivity sequence (strong to
weak) for various alloy steels is as
follows: 20G, Cr5Mo, 0Cr13, Cr18-8,
00Cr17Ni14Mo2.
Other factors
Even with a very low sulphur
content, naphthenic acid is still
heavily corrosive because there is
no formation of a protective
sulphide flm, but sulphur can
reportedly reduce corrosion at a
content level of 23%.
Low-temperature corrosion issues
resulting from electric desalting
diffculties
High acid crude oils are generally of
higher density and viscosity; in
particular, they have a higher
content of asphalt and gel, which
results in increased diffculties in
electric desalting. Furthermore,
naphthenic acids and their salts are
strongly emulsible, which may bring
added diffculties to crude oil
Temperature, C
2
4
6
8
10
12
14
0
260 280 300
C
o
r
r
o
s
i
o
n

r
a
t
e
,

m
m
/
a
450 524
360 450
235 360
Figure 2 235360C, 360450C and 450524C distillate corrosion rate for carbon steel
Temperature, C
100
500
400
300
200
0
20 30 80 70 60 50 40 90 100
m
p
y
500 ppm HAc
400 ppm HAc
200 ppm HAc
100 ppm HAc
50 ppm HAc
No HAc
Figure 3 Infuence of acetic acid concentration on corrosion of X-65 steel
desalting, making it more diffcult to
meet deep desalting requirements so
that the low temperature part of the
distillation unit overhead (120) will
be heavily corroded.
H
2
S-HCl-H
2
O-type corrosion
Corrosion in low-temperature areas
follows the same mechanism as in
atmospheric and vacuum distilla-
tion low-temperature corrosion.
After crude oil desalting and dewa-
tering, non-organic salts, including
calcium chloride, magnesium chlo-
ride and sodium chloride, remain
in crude oil. Organic chlorides
added in some oil felds during
deep extraction may form HCl in
certain conditions, giving rise to
corrosion mainly in the primary
tower overhead and atmospheric
tower overhead (top fve trays), in
the tower overhead condensate
cooling system of the distillation
unit, and in the vacuum tower
overhead. The main infuencing
factors are chloride content and pH
value. A low chloride concentration
will result in slight corrosion, while
a high content will result in heavy
corrosion. A low pH value will
result in heavier corriosion, while a
higher pH value (>8.0) will result
in fouling of the condensing
system.
Acetic acid corrosion
Acetic acid added during high acid
crude oil extraction, or acetic (and
formic) acid derived from the crude
oil itself, presents a big problem.
Atmospheric top corrosion and
wastewater treatment problems are
caused mainly by acetic acid, which
is added to solve the naphthenate
problem in Chinas offshore
produced oil. Figure 3 shows the
corrosion effects of different concen-
trations of acetic acid in water on
X-65 steel.
Corrosion resulting from high
nitrogen content
High acid crude oil has a relatively
high nitrogen content, which gives
rise to three main types of
corrosion:
H
2
S-HCN-H
2
O-type corrosion This
type of corrosion occurs on the
catalytic cracking tower overhead
below the temperature range 40
50C. Its damage to carbon steel
includes even reduction in wall
thickness, hydrogen blistering and
sulphide stress corrosion cracking.
The effect on austenitic stainless
steel is sulphide stress corrosion
cracking
NO
x
-SO
x
-H
2
O-type corrosion During
catalytic cracking catalyst regenera-
tion, nitride will be converted to
NO
x
, and will result in NO
x
-SO
x
-
H
2
O-type corrosion in the
low-temperature area of the cata-
lytic cracking regenerator and
tertiary cyclone when wet weather
or wet ambient conditions reach
nitric acid dew point. This is the
main cause of accidents in the cata-
lytic cracking unit regenerator of
Chinese refneries
Pipeline blocking and corrosion due
to fouling This results from the
accumulation of ammonium chlo-
ride and ammonium hydrogen
sulphide in the hydrogenation low-
pressure air cooler. After
hydrogenation of raw materials, the
elemental nitrogen in a nitrogen-
containing compound is converted
to ammonium. HCl and H
2
S react
with ammonia in the distillates heat
exchanger to form NH
4
Cl and
NH
4
HS. These salts have low solu-
bilities and will accumulate on
equipment surfaces, resulting in
blockages in the hydrogenation
high- and low-pressure air coolers,
heat exchangers and pipelines,
42 PTQ Q4 2010 www.digitalrening.com/article/1000524
5 l0 l5
14.31
14.67
15.35
16.12
17.00
18.16
24.67
26.25 27.78
28.29
31.07
13.23
8.61
6.36
5.41
20 25 30 35
Time, min
l0
20
30
40
50
60
70
80
90
l00
0
0
e
c
n
a
d
n
u
b
a

e
v
i
t
a
l
e
P
9.56
13.61
Figure 4 Salty drainage water acidic organic content total ion spectrum (TIC)
4 8 6 l0 l2
4.60
5.45
6.25 7.63
9.56
11.47
11.61
11.96
12.97
14.86
16.29
18.04
19.57 20.69
11.23 9.17
l4 l6 l8 20 22
Time, min
l0
20
30
40
50
60
70
80
90
l00
0
e
c
n
a
d
n
u
b
a

e
v
i
t
a
l
e
P
7.69
Figure 5 Salty drainage water alkaline organic content total ion stream spectrum (TIC)
leading to further corrosion under
fouling.
High salt content and metal content
High metals content in crude oil,
especially calcium, nickel and vana-
dium, will mainly infuence
secondary processing units such as
catalytic cracking and hydrogena-
tion, and will result in catalyst
poisoning and/or permanent inac-
tivation, catalyst bed blocking and
high-temperature heat exchanger
fouling and coking. If the residuum
is used as fuel oil, then corrosion of
furnace tubes and heavy ash accu-
mulation on furnace tube surfaces
will occur, with negative effects on
heat effciency and operational
safety.
Envrionmental protection
Wastewater treatment presents a big
headache in high acid crude oil
processing. Highly acidic organic
substances (representing 90% of total
extractable organic content) can be
extracted from wastewater. Acidic
organic substances from various
wastewater sources are different. By
calculation, naphthenic acids contri-
bution to COD in the fnal outlet is
above 30%, with molecular weights
around 300 (basically C
18
naphthenic
acids). Figures 4 and 5 show
analysis results for organic materials
in wastewater using different
treatments.
Conclusion
Producing clean fuel or high-value
petrochemical products from heavy,
low-quality crude oils is a big chal-
lenge for oil refners. Characteristics
of high acid crude oil include high
acid value, fewer light components,
high density and viscosity, high gel
and asphalt content, and high salts
and metals content, which may
result in serious corrosion of equip-
ment, and concerns with product
quality, environmental protection
and processibility.
CNOOCs Huizhou refnery is a
full conversion site exclusively
processing high acid heavy crude
oil at an annual rate of 12 million
tonnes. Just one year on from
production startup, the refnery has
achieved a high standard of
performance in electric desalting,
high- and low-temperature corro-
sion control, and the processing and
treatment of kerosene and diesel,
wax oil and residuum.
Wu Qing is the Chief Engineer of Huizhou
refnery, Guangdong, China, part of the Refning
and Marketing Group of China National
Offshore Oil Corporation (CNOOC).
Email: wuqing@cnooc.com.cn
www.digitalrening.com/article/1000524 PTQ Q4 2010 43
Producing clean
fuel or high-value
petrochemical
products from heavy,
low-quality crude oils
is a big challenge for
oil refners

LiNKS
More articles from the following
categories:
Corrosion/Fouling Control
Heavy/Sour Crudes