Light crude oil treatment

T
he development of sour light crude oils or
condensates in certain areas of the world,
such as Kazakhstan and Qatar, has created
a problem in storage and transportation to crude
oil refning centres where these oils are fraction-
ated and converted to fuel products and
petrochemicals.
Crude oils contain all kinds of sulphur
compounds, both inorganic as in the case of H
2
S,
and organic as in the case of mercaptans and
thiophenes. Both H
2
S and mercaptans are highly
odorous and volatile sulphur compounds and, in
the case of H
2
S, its presence raises major safety
considerations since it is a poison to animal life
as well as humans. When crude oils are light
(above 40 API gravity) and contain volatile
sulphur in suffcient quantities, these oils require
either treatment to remove the noxious sulphur
in order to allow their storage and transporta-
tion, or the use of more costly and sophisticated
facilities along with special safety and environ-
mental handling procedures.
The typical crude oil production facility
employs a processing scheme that includes oil
and gas separation followed by desalting of the
oil, stabilisation, and fnally storage in atmos-
pheric tanks. In the case of light crude oils or
condensate from sour felds, the fnal stabilised
crude oil could contain several hundred ppm of
H2S and several thousand ppm of mercaptans,
forcing these facilities to further prepare the oil
for safe and non-odorous storage and transpor-
tation that mitigate any releases of poisonous
H
2
S and highly odorous mercaptans.
Many countries prohibit the storage or trans-
portation of these sour crude oils within their
territories unless certain specifcations for H
2
S
and mercaptans are met. Pipelines impose simi-
Felipe Suarez and Herbert Wizig Merichem Chemicals & Renery Services LLC
Liu Youchao China National Petroleum Corporation
Jack Zhang Jackson International Inc
lar specifcations as they not only transport these
oils, but also provide intermediate storage at
their terminals. Waterborne vessels also limit
the level of volatile sulphur that they will permit
while transporting crude oils.
Historically, oil producers have used various
schemes to mitigate the problem. These schemes
include processing facilities for stripping H
2
S
and mercaptan, pressurised storage facilities and
alternate higher-cost transportation options such
as rail in lieu of lower cost pipeline transport.
With ever-stricter safety and environmental
regulations, storage facilities have become
extremely costly. It was not until recently that
producers began searching for a chemical treat-
ing process, such as caustic treating, for a more
attractive option to solve their sour oil storage
and transportation dilemma.
Project objectives
In March 2002, CNPC-AMG, in Aktyubinsk,
Kazakhstan, approached Merichem with a need
to treat a six million tons/year crude oil stream
already in production. Up to that time, a portion
of the crude oil had been transported to a refn-
ery in Orsk, Russia, via pipeline at depressed
pricing and the rest by rail to Russia and other
Central Asian countries via rail tank cars at an
average cost of US$23.4/ton. The new require-
ment to treat the oil was an increase in
production coupled with the construction of a
new oil pipeline that would reduce oil transpor-
tation costs to US$8.5/ton and open new
markets for CNPC-AMG, provided that they
could reduce the volatile sulphur to meet the
following specifcations:
H
2
S (1ppm/wt)
C
1
and C
2
mercaptans (<10ppm/wt)
www.digitalrening.com/article/1000760 PTQ Q4 2004 1
A review of caustic treating technologies useful in the removal of volatile
sulphur from sour light crudes
C
1
, C
2
and C
3
mercaptans (<30ppm/wt).
Design basis
The characteristics of the raw crude oil produced
by CNPC are shown in Table 1. As the table
shows, the oil not only has the sulphur impuri-
ties already mentioned but also contains two
additional caustic extractable impurities, CO2
and naphthenic acids (the latter is measured as
feed acidity in mg KOH/g).
Carbon dioxide in itself does not present a
major diffculty in treating the crude oil but its
presence does affect chemical usage as this acid
gas is also caustic extractable. Fortunately, for
CNPC-AMG the CO
2
levels of 40ppm/wt are
minimal and do not result in large caustic usage.
However, the reaction of carbon dioxide with
caustic and the presence of magnesium and
calcium chlorides along with H
2
S in the crude
must be carefully considered in the design to
avoid precipitation of salts, which could affect
process performance and equipment reliability.
The naphthenic acid content of the crude,
while relatively low, must also be carefully
considered in the design because of several
factors. First, naphthenic acids react with caustic
to form soaps, which in conventional mixer
settler treating systems will tend to form emul-
sions and cause foaming, making the process
2 PTQ Q4 2004 www.digitalrening.com/article/1000760
inoperable at times. Second, naphthenic acids
also react with magnesium and calcium to form
metal carboxylate salts, which can precipitate
and/or plug the treating equipment.
Finally, naphthenic acids will interfere with
the oxidation of mercaptans as they consume
alkalinity needed for the mercaptan sweetening
process. In order to remove this frst set of
impurities, which can be categorised as strong
acids, Merichem licensed and supplied CNPC-
AMG its proprietary Napfning process.
The removal of H
2
S, CO
2
and naphthenic acids
would only take the producer of the crude oil
part of the way to preparing the crude oil for
storage and transportation because mercaptans
would still be present. Mercaptans are highly
volatile organic sulphur compounds, which are
only slightly acidic and very diffcult to remove
with caustic unless the caustic solution is main-
tained in a fresh condition (low spending and
high alkalinity).
Mercaptans are also extremely odorous and
removal to low levels is mandatory in most fuel
products produced for industrial and consumer
use. For example, in most industrialised coun-
tries the historical motor gasoline specifcations
for mercaptan is the qualitative Doctor test
which almost always requires below 10ppm
mercaptan and sometimes as low as 2ppm for
passing as Doctor negative.
The Zhanazol crude oil contains approximately
659ppm/wt of C
1
C
2
mercaptan measured as
sulphur. There are other heavier mercaptans in
the crude oil but fortunately the lighter (lower
molecular weight) C
1
C
3
mercaptan species,
which represent 469ppm of the total, are the
most odorous and thus the ones targeted for
removal. In order to successfully remove these
light mercaptans without creating very large
chemical (caustic) usage and operating costs, the
economics dictate that the process employed be
regenerative, allowing the caustic solution to
remain fairly fresh, as earlier stated. For mercap-
tan removal, Merichem designed and licensed to
CNPC-AMG its proprietary Mericat technology.
Once treating is accomplished, the producer
must then deal with the effuents produced in
the treating unit, which in this case only consists
of the spent caustic effuent leaving the
Napfning and Mericat treating stages. This
stream must be handled or disposed of in an
environmentally acceptable manner. For treat-
Design basis
Chargestock Light crude oil
Flow rate, bpsd
Maximum 67800
Design 56500
Normal 56500
Minimum 28250
Molecular wt 110
Specic gravity @ 15C 0.81
IBP-EP C CH4-398
Water content wt% 0.5
Inlet impurities
Acid number, MgKOH/g 0.05
H
2
S, ppm (wt) 30
CO
2
, ppm (wt) 40
Total mercaptans as S, ppm (wt) 659
C
1
-C
3
Mercaptans as S, ppm (wt) 469
Methyl mercaptan as S 49
Ethyl mercaptan as S 249
Propyl mercaptan as S 171
C
4
-C
5
Mercaptans as S, ppm (wt) 190
Table 1
2 PTQ Q4 2004 www.digitalrening.com/article/1000760
ment of this stream, Merichem
designed and licensed its
proprietary Mericon process.
Process solution
In the summer of 2002, CNPC-
AMG issued a letter of intent to
Merichem to license its tech-
nologies and to purchase the
proprietary equipment in order
to have the facility in operation
by the end of 2002, a project
duration of less than six
months. The fast track delivery
and startup of the facility was
necessary because it had to
coincide with the completion of
the new crude oil pipeline to
Kenkiak, where the Zhanazol
crude oil would ultimately be
transported via another pipe-
line to the Caspian Sea for
ultimate shipping to the Black
Sea and Mediterranean
markets.
The contract involved supply-
ing CNPC-AMG with the basic
engineering design and propri-
etary equipment consisting of
the Fiber-Film Contactors,
process strainers and other
special equipment, the operat-
ing and maintenance manuals and the startup
services. In addition, Merichem also supplied
the process vessels fabricated by its sub-contrac-
tors in Ekaterinburg, Russia.
CNPC-AMG, using the East China Design
Institute as its engineering contractor, was
responsible for the detailed design of the plant,
procurement of all other materials and equip-
ment, installation, erection and interconnection
of the facility. The facility applied a combination
of US, Russian and Kazakhstan standards for
design of equipment, materials of construction
and methods of construction as well as safety
and environmental standards.
Process description
The Napfning system as illustrated in Figure 1
(following page) is designed to remove strong
acids with a weak caustic solution (3-5wt%
NaOH) in accordance to the following reactions:
www.digitalrening.com/article/1000760 PTQ Q4 2004 3
H
2
S + 2NaOH Na
2
S + 2H
2
O
Hydrogen sulphide
CO
2
+ 2NaOH Na
2
CO
3
+ 2H
2
O
Carbon dioxide
RCOOH + NaOH RCOONa + H
2
O
Naphthenic acids
The fashed and desalted crude oil supplied via
pumps P-1 and 2 from the existing production
facilities frst passes through a pair of hydrocar-
bon strainers (BS-1 and 2) to remove any scale,
rust or other solid matter that could interfere
with the proper functions of the system.
The crude oil then enters the Napfning stage
Fiber-Film Contactor (FFC-1) where it comes
into contact with a mixed fresh and recycled
caustic solution. The total caustic rate is approx-
imately equal to 10% by volume of the crude oil
rate. The actual make up caustic rate includes
LC
PC
PC
AC
PC
PC
AC
PC
PC
V-2 V-1
LC
P-3&4
P-5&6
P-1&2
Water
Oxidation air
Treated
light
crude
Naphthenic/sulp h idic
caustic to
spent caustic tank
Plant air
Untreated
light
crude oil
Fresh
caustic
(continuous)
BS-3&4
BS-1&2
Naphthenic acid extraction Mercaptan oxidation
BS-5&6
Catalyst
Figure 1 Napning/Mericat schematic ow diagram
fresh caustic being injected from the facilitys
fresh caustic supply system and cascaded from
the downstream Mericat mercaptan sweetening
system.
The total fresh caustic makeup rate is set after
a laboratory analysis of the circulating caustic
solution to determine its spending level (or
free alkalinity). Actual usage is directly propor-
tional to the total sum of H
2
S, CO
2
and
naphthenic acids contaminants contained in the
feed crude oil. The design caustic spending level
of the Napfning stage is 60%. The spent caustic
is removed from the bottom of the separator
vessel (V-1) on level control to the spent caustic
tank.
The previously mentioned Fiber-Film
Contactor (Figure 2) is a proprietary mass trans-
fer device licensed by Merichem consisting of a
cylinder packed with metallic fbres that provide
the surface area required for mass transfer to
take place. The fbres, being hydrophilic, attract
the aqueous (caustic) phase and provide the
surface on which the hydrocarbon (crude oil)
and aqueous (caustic) phases are in continuous
contact as both phases fow co-currently down-
ward though the contactor.
The caustic extractable impurities pass from
the hydrocarbon to the caustic phase where they
are removed from the system with the spent
caustic. The mass transfer mechanism is
non-dispersive, which is distinctly different from
the conventional mixing/settling approach,
where caustic droplets are formed for mass
transfer purposes. This results in a nearly perfect
separation of phases and avoids the formation of
emulsions, caustic carry-over with the crude oil
and hydrocarbon carry-under with the caustic as
would be experienced in mixer/settler processes.
The need for costly water washes to clean up
the treated product for caustic entrainment is
eliminated as well as losses of caustic with the
hydrocarbon product or losses of hydrocarbon
with the spent caustic leaving the system.
Mercaptans, being a weak acid, are not
removed to any signifcant level in the Napfning
system. Any mercaptans extracted when the
caustic solution is at its highest level of free
alkalinity are displaced back into the crude as
the more acidic impurities are extracted into the
caustic solution and the caustic spending
increases. The product leaving the system will
then require further treating in the second
Mericat stage previously shown in Figure 1.
The partially treated crude oil enters the
Mericat system where mercaptans are extracted
and oxidised in accordance to the following
reactions:
RSH + NaOH RSNa + H
2

Extraction
2RSNa+1 O
2
+H
2
O catalyst RSSR+2NaOH
2 --------- Oxidation
2RSH + 1 O
2
+ H
2
O catalyst RSSR + H
2
O
2 --------- Combined
It should be noted that the combined reaction
illustrates a 100% regeneration of the caustic,
which fulflls the prior mentioned requirement
that the caustic solution must not be signif-
cantly spent in order to extract the mercaptans
with caustic. The RSSR (disulphide oil) by-prod-
uct will re-enter the treated crude oil product
and leave with the fnal product.
The crude oil entering the Mericat stage is frst
contacted with air in a specially designed air
sparger (SP-1) to dissolve the oxygen needed for
the oxidation reaction to take place. The crude
oil containing the dissolved oxygen enters the
Fiber-Film Contactor (FFC-2) where it comes
into contact with a combined fresh caustic and
re-cycled caustic solution containing a dissolved
4 PTQ Q4 2004 www.digitalrening.com/article/1000760
Clear
hydrocarbon
phase in
Hydrocarbon
phase in
Aqueous
phase in
Clear
aqueous
phase out
FIBER-FILM
Contactor
Figure 2 Fiber-Film Contactor
oxidation catalyst. The latter promotes the
mercaptan oxidation reaction mentioned earlier.
Catalyst additions are made on a batch or
continuous basis depending on requirements
and plant preference.
As the crude oil and caustic/catalyst solution
fow co-currently downward through the contac-
tor mercaptans are converted to disulphdes,
which re-enter the crude oil phase. The treated
crude oil, free of H
2
S, naphthenic acids and C
1

C
3
mercaptans, passes on to product tankage on
pressure control. Since H
2
S is no longer present
and mercaptans have been converted to much
less volatile/odorous compounds, the treated
crude oil can then be stored in conventional
facilities and transported via truck, railcar and,
more importantly, the lower cost pipeline to its
fnal end user.
Operating performance
On 17 February 2003 the Napfning/ Mericat
system was started up by CNPC-AMG. Despite
the extremely accelerated project schedule,
which consisted of a total of eight months from
contract execution to mechanical completion,
the crude oil treating system successfully started
up and has been running on-specifcation and
onstream continuously ever since.
Some of the key results obtained since the
startup are listed as follows:
The system has processed an average of 11500
tonnes/day of crude oil. Additional throughput
will be processed once oil feld production is
expanded
The crude oil product has been successfully
transferred via the new Kenkiak pipeline to its
market destination, fulflling one of the most
important economic objectives of the project
The system has operated with a 100%
onstream service factor since startup
Fresh caustic consumption as 100% NaOH has
averaged 4.28 tonnes/day versus a design rate
(adjusted to crude oil throughput) of 4.13
tonnes/day. This represents 104% of the design
expectations
Spent caustic production has averaged 7.9m
3
/
hr versus an adjusted design rate of 5.26m
3
/hr.
This indicates that in addition to the H
2
S, CO
2

and naphthenic acids, the caustic is also picking
up free water contained in the desalted crude
entering the caustic treating unit
The raw crude oil H
2
S content has ranged from
20~90ppm/wt, 300~2000 ppm/wt for C
1
and C
2

mercaptans respectively; and 400~2500ppm/wt
C
1
, C
2
and C
3
mercaptans, fgures which are
waved far away from the design basis
Product H
2
S content has averaged 0ppm/wt,
0ppm/wt for C
1
and C
2
mercaptans respectively,
and 10ppm/wt C
1
, C
2
and C
3
mercaptans, fgures
which are well below design requirements of
1ppm/wt, 10ppm/wt and 30ppm/wt,
respectively.
The summary of the operating cost variables
based on design light crude fow rate and impu-
rity levels are contained in Table 2.
Some of the problems faced during the opera-
tion can be summarised as follows:
The hydraulic throughput of the facilities has
been restricted by some bottle-necks in the pipe-
lines feeding the Napfning/Mericat system.
CNPC-AMG is in the process of debottlenecking
these pipelines in order to achieve the full
processing potential of the facilities as the oil
production in the feld continues to increase
The spent caustic currently being produced
has been plugging existing disposal facilities due
to its high salt content. The proprietary Mericon
system, which will be used for treatment of this
effuent, is expected to eliminate this problem.
Future plans
CNPC-AMG is planning to increase crude oil
production in the near future and will be consid-
ering additional processing facilities that will
allow them to transport and market the Zhanazol
crude oil to far away places like mainland China.
A new 1300km pipeline is planned for comple-
tion by 2006.
In order to improve its environmental abate-
ment programmes and eliminate the problems
www.digitalrening.com/article/1000760 PTQ Q4 2004 5 4 PTQ Q4 2004 www.digitalrening.com/article/1000760
Operating cost variables
Crude oil Crude oil
Napning Mericat
Fresh NaOH, kg 2.2 million*
Spent caustic, m
3
65821*
Oxidation air, m
3
/h 562
Oxidation catalyst, kg 1134
Electricity, kWh 231779 296162
Operating labour, MH 300 300
Maintenance labour, MH 150 150
*Combined caustic use for Napning and Mericat
Table 2
associated with spent caustic disposal, CNPC-
AMG is planning the implementation of the
previously mentioned Mericon spent caustic
neutralisation process in the near future (Figure
3). The basic engineering and licensing of this
technology has already been completed.
The processing scheme consists of a low pH
neutralisation of the spent caustic followed by
H2S stripping and then a re-neutralisation of the
neutralised aqueous material to a neutral pH.
The goal is to achieve near
total removal of reactive
sulphur compounds;
sodium sulphide (Na2S),
sodium hydrosulphide
(NaHS) and sodium
mercaptide (RSNa). This
will allow the safe and
non-odorous handling of
the material in the plant
effuent treating systems.
In addition, the spent
caustic neutralisation
system will also provide for
removal of organic acids,
primarily naphthenic acids
that are extracted by the
caustic solution. The
systems spent caustic feed
and treated spent caustic
specifcations are shown in
Table 3.
Investment justication
The investment made by CNPC-AMG for caustic
treating the Zhanazol crude oil has been a very
successful and proftable project. The caustic
treatment of light crude oil for removal of light
volatile sulphur compounds is not only techni-
cally feasible with the appropriate technology,
but also extremely attractive from an economic
standpoint and environmentally sound when a
well-designed effuent caustic treating
unit is made part of the project.
Oil producers should avoid the use of
conventional mixing/settling caustic
treating processes that will create emul-
sions as crude oils have a strong
propensity to emulsify when contacted
with a caustic solution.
Napning, Mericat, Mericon, Fiber-Film Contactor
and Mericon are trademarked technologies owned by
Merichem Chemicals and Renery Services LLC.
Felipe Suarez is vice president of Merichem Chemicals
& Renery Services LLC, responsible for the process
technology and caustic management services
business units. He holds a BS in chemical engineering
from Louisiana State University and is a registered
professional engineer in Louisiana.
E-mail: fsuarez@merichem.com
6 PTQ Q4 2004 www.digitalrening.com/article/1000760
Fuel gas
Solvent
Sulp h uric
acid
Water
Spent
caustic
feed
PC
FC
FC
LC
FC
FC
FC
LC
LC
Offgas to
sulp h ur plant
Fresh
caustic
Neutralised
brine to
WWTP
Acid oils to
storage tank
NC
Cooler
Figure 3 Mericon schematic ow diagram
Spent caustic data
Caustic type Mixed naphthenic and sulphidic
Standard density or gravity @ 15C 1.01
Operating density or gravity @ 45C 1014kg/m
3
Flow rates @ 15C Design 20.0m
3
/h
Normal 18.0m
3
/h
Spent caustic specications Composition, wt%
Water 97.76
NaSH
Na
2
S 0.31
NaSR
Free NaOH 1.26
NaOR
NaOOCR 0.46
Na
2
CO
3
0.22
Hydrocarbon oil Trace
Treated brine specications, max: Product specications
pH 6.08.5
Na
2
S as sulphur <10ppm wt
Mericon spent caustic specications
Table 3
6 PTQ Q4 2004 www.digitalrening.com/article/1000760
Herbert Wizig is assistant director of marketing for the process
technology division of Merichem Chemicals & Renery Services
LLC. He holds a BS in chemical engineering from the University
of Texas and MS in chemical engineering from Georgia Institute of
Technology, Atlanta.
E-mail: hwizig@merichem.com
Liu Youchao is chief process engineer for CNPC-AMG in
Kazakhstan, in charge of project management and new process
application. He is a member of the China Petroleum Society with
more than 20 years experience in the petroleum industry.
Jack Zhang is vice president of Jackson International Inc, Beijing
ofce. Jackson International is the sole representative of
Merichem technology and service in China. He graduated from
the chemical engineering department of Dalian University of
Science and Technology in 1987.
Email: jack.zhang@jackson-international.com
www.digitalrening.com/article/1000760 PTQ Q4 2004 7

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