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Abstract
Organic deposition predominantly in the near well bore and in production tubing can create serious oilfield problems such as
flow restrictions, near wellbore damage, efficiency of crude processing units and etc. As the reservoir depleted over the time,
the solid deposition can lead to a steep decline in productivity of wells. The deposition of organic solids is one of many flow
assurance problems faced by operators in Malaysia. It has been observed that, after years of production, many fields in
Malaysia are suffering from organic solid deposition problem. This phenomenon is predominantly caused by changes in
temperature, pressure and composition/morphology of the crude oil over time. To perform organic deposit removal treatment
and prevention in the well, the nature of the solid should be characterized. If the deposit sample is organic mainly, it is
important to quantify the various organic fractions of the solid sample collected from the production facilities. This paper
explains how SARA analysis was modified to detect not only Macro-crystalline waxes (Saturates), asphaltene, aromatics and
resins but also micro-crystalline wax and naphthenates. The content of each of above component will affect the method of
treatment and the chemical formulation to treat the well. By knowing the composition of the solid sample along with Crudes
Colloidal instability index (CII), Pour point and Wax Appearance Temperature (WAT), a customized chemical formulation
can be designed. Lab studies were performed on solid samples collected from several wells to detect the flow assurance
related issues prior to design of chemical formulation. With the analysis of the production data, history matching, and etc, a
customized chemical formulation was developed to treat the wells. The proposed chemical formulation consists of 2 specially
designed pills which would be simultaneously injected to the wellbore, which generates heat and ester once comingles. The
heat melts the deposits while the ester disperses the melted solid. The initial studies of the treatment showed promising
results; moreover the field implementation was very successful and proven significant increase in production rate. This novel
system that combines both thermal and physical energy, evidenced to work effectively for wide range of organic
compositions. Implementation of this system made it possible to restart the production from those wells which were idle due
to extensive organic deposits. This technique was also often used to rejuvenate the old wells with low production rate. This
paper discusses the diagnostic process and successful implementation of the proposed treatment in several oil wells in
Malaysia.
Introduction
Deposition of organic particles during transportation, storage and processing of Crude oil is very common [1].Near wellbore
area and production tubings can suffer from serious damage due to solid deposition. Existence of solid organics along with
natural depletion can directly contribute to production decline. Organic solids caused flow assurance problem is one of the
major issues in mature fields. After many years of production natural driving forces are low. Therefore the production decline
is much expected. Probability of organic deposits in near- well bore region and in production tubing, can contribute to
production decline by causing flow constrain for reservoir fluids from wellbore to wellhead.
To address the flow assurance issues, nature of reservoir fluid and the key parameters affecting the stability of organic solids
should be well-understood .In hydrocarbon mixture, beside hydrocarbons, which are the predominant group, organic
compound of sulphur, nitrogen and oxygen and metal element consisting compound can be found [2].
SPE SPE-165912-MS
Petroleum constituents are classified under two major groups, volatiles (C6- fraction) and non-volatile (C6+ fraction). C6+
fraction are more complex compare to volatile group, in C6- fraction all components and even their isomers are well known
however when carbon number increases the possibility of multiple isomer combination increase too [2]. Due to this
complexity, the hydrocarbon mixtures are classified based on solubility class rather than their chemical class [3-4]. Another
reason is that: components like asphaltenes do not exist as purely identical molecules; therefore, it is more practical to define
them as a solubility class [5].
The non-volatile group is classified as paraffins (P), naphthenes (N), aromatics (A), resins (R), and asphaltenes (A).
Generally paraffins and naphthenes are reported under one group which is called saturates (S) [2]. Major oilfield problems
arise from deposition of saturates and asphaltene. The following section gives a brief overview about diagnosis of the organic
deposits.
Organic deposits diagnosis
The initial step for diagnosis and treatment of any solid deposit is to study the crude source of the sample. There are several
routine laboratory tests which are conducted on crude sample such as saturate, asphaltene , resin and aromatic (SARA)
analysis , Colloidal instability index (CII), Pour point, Wax Appearance Temperature (WAT), and rheology.
Dissolution Test
To test the nature of the sample, one of the routine tests is to examine the solubility of the sample in organic solvents, acid
and water. This is not a quantitative test however it is a helpful tool to examine the nature of the deposit sample. Samples
with predominant organic fractions are soluble in solvent while in-organic sample are dissolved in acids and clay in water.
This step is one of the initial steps to characterize the deposit sample. Since dissolution test is just an initial indication, it
should not be relied on without further analysis.
Volatility Test
To do any analysis and treatment, the volatile percentage of the sample is measured first. By heating the sample, the volatile
fraction (C6- fraction) will vaporize, remaining is the stable portion of the sample contains C6+ fraction.
SARA analysis
One method in characterizing crude oil is by separating it into smaller quantities or fractions, each of which has a different
composition from the rest. Each component would be defined based on its solubility in various solvents. Hence, the crude
oil is fractionated to four solubility classes (based on their solubility characteristics in polar and non-polar solvents). This
method, referred to collectively as SARA: saturates aromatics, resins, and asphaltenes. Saturates consist of non-polar
materials; and aromatics are more polarizable and have at least one aromatic rings [6]. Meanwhile, asphaltenes are known to
be the heaviest and the most polar fraction of petroleum. Although asphaltenes and resins are alike in molecular structure,
resins are less polar, less aromatic and have lower molar mass compared to asphaltenes [7]. SARA is performed on both
crude and solid sample.
Saturates
The petroleum wax consists of 2 primary groups: paraffin wax (C18-C36) and naphthenic hydrocarbons (C30-C60).
The difference in 2 groups is the structure of the crystals they forms, the crystal formed from paraffin waxes are
Macro-crystalline wax. Macro-crystalline waxes contain normal saturate alkanes with little iso-alkanes. This group
has the melting point of 60 C. On the other hand, microcrystalline waxes are formed from naphta. The branchedchain paraffins are the major portion of the microcrystalline wax, however long naphthenic chains along with
SPE SPE-165912-MS
aromatic paraffins play a role in crystal growth of the microcrystalline wax , their melting point reach to 90 C[810]. Compare to macro-crystalline wax, microcrystalline wax has finest crystals, it is darker in colour, more viscous
and denser.
In normal SARA practice, microcrystalline wax is un-detected most of the time or reported together with saturates.
However when it comes to flow assurance, the concentration of microcrystalline wax play an important role to
design a suitable treatment, due to its distinctive structure and characteristics .
In modified version of SARA analysis, to separate the microcrystalline wax, the remaining residues on filter paper
are washed and filtered using boiling solvent; this is due to the high difference in the melting point of macro and
microcrystalline wax.
Asphaltenes
Asphaltenes are one of important solubility classes of crude oil , they are highly polar and aromatic with high
molecular weight. They are brown or black in colour (depend on the solvent used for asphaltene extraction) .Under
initial reservoir conditions Asphaltene is stable however changes in fluid composition , pressure and temperature
which happen during production life of a well ,may lead to asphaltene precipitation and deposition. Asphaltene
deposition occurs in the reservoir, wellbore, production tubing and even can lead to catalyst poisoning in refineries.
Due to complicated nature of asphaltene and complexity of asphaltene precipitation mechanism, asphaltene removal
is very expensive and has an adverse impact on the profitability of the operation .Asphaltene and wax precipitation
happen simultaneously in most cases. Wax layers are covering deposited asphaltene which makes a barrier to access
asphaltene directly. Deposited asphaltenes on tubing walls provide wax with a suitable condition to crystallize and
co-deposit [12, 13].
Resins
Resins are surface active, poly-disperse, polar and have a range of aromaticity [13]. The stability of asphaltene much
depends on resins since resins affect asphaltene aggregation and precipitation. They can, affect the quantity of
precipitation from gravimetric analysis, and decrease the size of asphaltene aggregates [14]. It is known that resins
do not precipitate themselves; normally they precipitate along with asphaltenes.
Aromatic
Aromatic compounds are common in all crude oils. They contain at least one or two aromatic rings-structures
similar to benzene.The atoms are connected by aromatic double bonds; they are polar but not as polar as asphaltene
and resins. They are mostly found in lower boiling point fractions [15]
Naphthenates
According to API Standard, naphthenic acid includes saturates with single/or multiple fused cyclo-pentane rings
with carboxyl group attached either to an aliphatic side chain or to a cyclo-aliphatic ring [16]. Although Total Acid
number is used to measure naphthenic acid of the crude ; but other factors (e.g. Dissolved H2S, dissolved CO2,
hydrolysable salts , inorganic acids , surfactant or other production chemical enhancements ), will affect the TAN
[17].
Naphthenic acid forms acid salts in presence of alkali. These salts or soaps are the results of reaction of metal
cations and naphthenates anions. In some cases, formed bound can break by acidification [18] Formation of these
salts is one of the new issues in oilfields. Known like any other deposits, naphthenates are capable of blocking the
pipelines and tubings and as a result major product drop or even production shutdown is expected. Immature, heavy
SPE SPE-165912-MS
oils with high naphthenic acid content present most naphthenates deposits problem. Besides, naphthenates deposits
are mostly observed at oil/water cut-off point, that is due to the fact that naphthenic acids and divalent (Ca2+,
Fe2+ and Mg2+) or monovalent (Na+, K+) ions present in produced waters interact and lead to naphthenates deposits.
Heavy crude oils with high acid numbers mostly interact with divalent cations (i.e calcium naphthenates). On the
other hand, in light oils with low acid number the possibility of naphthenates formed with monovalent cations is
higher [19].
Naphthenates exist in crude oil have a very long chain with high molecular weight, in modified SARA analysis,
naphthenates are extracted by an organic solvent acidified with a carboxylic acid. The solution breaks the bond
between the cations and ions, so naphthenates are collected separately. After filtration of asphaltene components, the
residue on the filter paper is washed by the proper solution to extract naphthenates or after extraction of resins in
chromatography column, naphthenates are removed, if any left in the column.
Resins
Aromatics
Naphthenates
Micro-Crystalline wax
Modified SARA
Modified SARA
Asphaltene
Routine SARA
Saturates (macro-Crystalline
wax )
SPE SPE-165912-MS
Crude Sample
Solid Sample
SARA
SARA
CII
Pour Point
WAT
Melting point
Compatibility Test
TAN
Dissolution test
Free Water Content
Pack 1 + Pack 2
Ester + Heat
Treatment Application
The two pack formulation can be injected in different manners: they can be simultaneously injected into the well inside the
tubing or in the well inside the flow line or pipeline. In wells where there is communication between lower part of the
production tubing and annulus, or where another tube is provided inside the production tubing, one formulation can be
injected in the production tubing and the other in the annulus. Where coil tubing unit (CTU) is used one formulation can be
injected in the coil tube and the other in the annulus between the production tubing and coil tube in bottom of the coil tube. In
all cases the generated heat from the exothermic can be carried down in the well where high accumulation of organic
deposition exists.
Prior to injection of formulation, a mixture of organic solvent (pre-flush) is injected to prepare the deposit surface for a better
reaction with the 2 pack system. When 2 pack systems are injected, it is allowed to soak for 12-24 hours, the chemical system
is carried to the affected area with another formulation called post flush. When soaking period is over, the normal production
is resumed. By doing so, the dissolved and dispersed organic deposits are carried away from the treated areas. To reach
higher temperature, one or both formulation can be heated prior to their injection.
This system is applied using a unique modular technology consisting of 3-4 small pumps. Such modular approach is most
suitable for offshore as it eliminates requirement for barge and other heavy equipment for well applications. For severe
problems for example pipeline de-clogging, a CTU may be deployed to inject the chemicals with a higher pressure force.
This novel technology can be applied for cleaning the pipelines, tanks, vessels and etc.
SPE SPE-165912-MS
Original Crude
SPE SPE-165912-MS
Case Studies
Case A
Well A is a single string oil producer which produces from 3 pay zones. From Oct 2007 onward, only one of the zones is
actively producing. Production rate declined from 1100 bopd to 600 bopd, moreover high well bore skin was observed. To
overcome the deposition problem, mechanical deposit removal was performed once in every 7 days and each job was taking
3 days at the rate of 8 hours/day. Mostly, organic deposits were found around the upper side of tubing. To perform the wax
cutting job, not only high volume of specialty chemicals was required for soaking purposes, but also mechanical cutting left
waxy fragments on the tubing surface and the improved production was not able to sustain for long period.
To formulate the treatment, crude and deposit sample was collected from the well. Modified SARA was performed to
characterize the nature of samples. Crude analysis showed the existence of micro-crystalline wax and naphthenates. Low
asphaltene content and high CII indicate the instability of asphaltene; therefore the case presents the high possibility of wax
and asphaltene precipitation. Presence of naphthenates can lead to forming a tough and stable emulsion.
Table 1: SARA Analysis for Crude sample, Well A
SARA ANALYSIS
%
Volatiles
Saturates
Total Saturates
Asphaltenes (n-pentane insoluble)
Resins
Aromatics
Naphthenates
CII (colloidal instability index)
Sample basis
25.8
40.70
05.26
45.96
01.47
09.60
12.40
01.78
2.16
Besides crude analysis, deposit was tested too. Based on SARA results, sample is mostly consist of saturates, especially
Micro-Crystalline wax. Furthermore the high percentage of asphaltene precipitation was predicted due on high CII value. The
solid sample has high melting point (79.5 C) which can be due to high micro-crystalline wax.
Table 2: SARA Analysis for Deposit sample, Well A
SARA ANALYSIS
%
Volatiles
Saturates
Sample basis
8.09
22.4670
38.088
60.56
10.68
6.11
8.38
4.56
Based on the analysis results, well condition and production data, two pack thermo-chemical treatment systems was
proposed. High wax and asphaltene content of the deposit sample make it necessary to use a treatment which can melt and
disperse the organic deposit at the same time. Therefore the thermo-chemical treatment is the ideal solution for this case. To
confirm the performance of the treatment, dissolution test was performed. Dissolution test (solid sample with addition of
thermo-chemical solutions) showed high solvency effect while generated heat assisted to melt the sample , the temperature
was raised above the melting point therefore the organic sample was melted. Moreover the compatibility studies showed that
the formulation was completely compatible with crude oil and other well completion accessories.
The treatment was designed to be carried up to 2 ft behind the casing. Total of 52.5 bbl of chemicals was consumed; the well
test data showed 80% improvement in production. IPR showed noticeable improvement in production index (from 0.34 to
0.62). Significance of the treatment can be explained in term of financial aspect, the production was sustained for 12 months
without any mechanical cutting being required, in other word USD 100,000 was saved.
SPE SPE-165912-MS
Case B
Well B is consisting of three pay zones, with dual string oil producer. One of zones is produced through short string while the
other two zones are producing through the long string however Since March 2004, only one of the zones is producing
through the long string. Production declined from 2010 to 2012 production was dropped by almost 85%, and water cut
reached up to 62%.
Modified SARA analysis shows the sample is very rich in wax content. The high CII value suggests that instability of
asphaltene and high possibility of its precipitation.
Table 3: SARA Analysis for Crude sample, Well B
SARA ANALYSIS
%
Volatiles
Saturates
Total Saturates
Asphaltenes (n-pentane insoluble)
Resins
Aromatics
Naphthenates
CII (colloidal instability index)
Sample basis
32.40
51.38
6.876
58.26
4.30
15.89
18.43
1.32
1.86
Analysis shows that the deposit sample has high wax and asphaltene content, besides the existence of naphthenates may
assist the formation of a strong emulsion. Melting point of the deposit sample is in average range (55.6C).
Sample basis
70.94
9.4585
2.664
12.12
5.31
3.58
5.58
2.19
Like previous case two pack thermo-chemical treatment systems was found to be a suitable solution , high temperature
released during the treatment can easily melt the sample while the applied solvent can disperse the organic deposit and
provide the smooth flow. Dissolution and compatibility test were performed to test the efficiency of the treatment, results
indicated that the thermo-chemical system is effective in dissolving the deposit and also it is compatible with the crude and
completion accessories.
The application of the thermo-chemical had improved the production rate by 200 %( from 200 bopd to 600 bopd). IPR
analysis shows that the PI has increased from 0.11 to 0.40 and water cut reached to 42.4% from 61.6%.
Summary
To perform flow assurance treatment, sample analysis is very crucial to characterize the nature of the sample and
formulate a suitable treatment.
When dealing with organic deposition issues, SARA analysis would be helpful in separating the sample in to
different solubility fractions. Modified SARA analysis was developed to detect microcrystalline wax and
naphthenates which are overlooked in routine SARA procedure.
Treatment of deposits which contain micro-crystalline wax required higher temperature compare to macrocrystalline waxes, but thermal treatment will not be sufficient enough since asphaltenes and other organics will co
precipitate along with wax. The suitable treatment should be able to provide enough heat and as well act as a
surfactant to disperse the solid deposits.
SPE SPE-165912-MS
To treat the wells, pipeline and other production and processing facilities suffering from organic deposits specially
wax and asphaltene, a 2 pack system was developed. The thermo-chemical system will generate heat and ester
which can melt and disperse the sample to ensure a smooth flow. The chemical formulation can be altered by adding
certain additives to generate more heat in case it is required.
The formulated chemical is highly suitable for high saturates contents (>10%), high WAT, pour point temperatures
and CII of more than 0.9, besides it can act as an excellent demulsifier.
There are variety of methods for injecting the thermo-chemical system which makes it ideal for different condition
and facilities. Execution of the job only requires small equipment which makes it economically feasible in offshore
environment, considering the limitations and logistic issues.
Acknowledgement
The authors would like to thank Deleum Chemicals for their assistance and support. We also would like to express our
appreciation to PETRONAS for their supports and approval in publishing this work.
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11
Appendix A: CASE A
Table A1. Sample properties, well A
Case A
Wax appurtenance Temperature C (Crude)
Pour point C (Crude)
Melting point C (Solid )
55.4
36
79.5
12
SPE SPE-165912-MS
Appendix B: CASE B
Table B1: Sample properties, well A
Case B
Wax appurtenance Temperature C (Crude)
Pour point C (Crude)
Melting point C (Solid )
65.0
65.0
55.6
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13
In-Soluble
+Organic solvent acidified with a carboxylic
acid
Naphthenate
s
+Boiling Solvent
Microcrystalline
Wax
Soluble
+Maltenes feed to Chromatography Column
Saturates
+ Organic Solvent
Aromatics
+ Mixture of organic solvent and
Methanol
Resins
+Organic solvent acidified with a carboxylic
acid
Naphthenate
s