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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

Process Chemistry Process Chemistry


COST VOLUME
Maximising Production Potential
(with existing facilities)




Russell Hollamby & Guus Nuis







The copyright of this document is vested in Shell International Exploration and Production B.V., The Hague, The
Netherlands. All rights reserved. Neither the whole nor any part of this document may be reproduced, stored in any
retrieval system or transmitted in any form or by any means (electronic, mechanical, reprographic, recording or otherwise)
without the prior written consent of the copyright owner.


2000 SHELL INTERNATIONAL EXPLORATION AND PRODUCTION B.V.,
RESEARCH AND TECHNICAL SERVICES, RIJSWIJK

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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

Contents


Objectives and Introduction

1. Emulsion Treatment
1.1 Dehydration
1.2 Sludge
1.3 Deoiling

2. Organic Deposits
2.1 Gas Hydrates
2.2 Waxy Crude
2.3 Asphaltenes

3. Drag Reducers

4. Inorganic Scales
4.1 Oil Field Water Scales

5. Bacteria and Biocides

6. Corrosion

7. HSE Aspects
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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
















































Produced by:

Nuis Exploration & Production Services V.o.F.
Zijdelaan 25
2594 BW Den Haag
Netherlands
telephone: 0031 70 3850764
facsimile: 0031 70 5851048
email: nugget01@xs4all.nl

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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS



Objectives and Introduction


Session Objectives Session Objectives
At the end of the Session the Participants will be able to:
List the Main Technical Challenges (Chemistry Specific) for
Processing Produced Hydrocarbons and Effluents.
List the Main Influencing Factors on the Formation of
Emulsions and Deposits.
Describe the Process for Formulating, Applying and
Monitoring a Chemical Treatment.
List the Key Elements in Assessing the Economics of a
Chemical Treatment.
Identify the main HSE aspects for Process Chemistry.


The objectives of this booklet are that, after reading the various sections and
completing the exercises, you will be able to:

name the different types of deposits and emulsions that may form or be present,
in hydrocarbons
explain what makes deposits come out of solution and what makes
emulsions occur
explain the potential problems that may arise in production facilities from deposits
and emulsions
explain how the potential production problems associated with deposits and
emulsions may be prevented and/or resolved
describe the process for formulating, applying and monitoring a chemical
treatment
list the key elements in assessing the economics of a chemical treatment
explain the term drag reduction
name a range of drag reducing agents and explain how they work
explain how and why drag reducers are used in a production environment.
identify the main HSE aspects for Process Chemistry

Overview
Crude oil and gas are naturally occurring substance which emerge from the well with
a considerable range and variation of both physical properties and chemical
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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
constituents. Some of these emerge as a direct result of the production processes
involved in extraction and transportation. Many of these physical properties and
chemical constituents do not cause problems in the upstream or refining processes.
Others may, however, have a negative impact on costs, quality, safety, the ability of
a well to continue to produce and the ability of the refinery to handle the output. It is
essential, therefore, that production staff have a clear understanding of the relevant
physical properties and chemicals, their potential impact on operations and, of equal
if not greater importance, how the associated problems may be avoided and/or
overcome.

Process Treatment Chemicals Process Treatment Chemicals
Product Quality
DeHydration (Oil, Gas)
DeOiling
Pour Point Depressants
Sulphide Scavengers
Sludge Disposal
Processing Potential
Wax Inhibitors
Asphaltene Inhibitors
Hydrate Inhibitors
Oxygen Scavengers
Corrosion Inhibitors
Scale Inhibitors
Friction Reducers
Estimated Group Expenditure on Process Chemicals
Demulsifying US$ 22 MM Scale US$ 8 MM
Deposits US$ 20 MM Other US$ 5 MM
Corrosion US$ 11 MM HSE Related US$ 5 MM
(1994 - WOCANA)


Process Chemicals can be sub-divided over a number of different processes in
which these chemicals are being applied. The types of chemicals used in the left
column are mainly aimed to improve the quality of the stream to be treated.
Dehydration chemicals will assist reducing the water (and salt) content in the crude
to the quality level required for export. Pourpoint reducers assist reducing the
temperature at which wax deposits from the crude stream, while sulphide
scavengers reduce the H
2
S content in the production stream, etc. In some cases like
for deoilers and sludge disposal chemicals, the product quality is more of an
environmental quality.

In the right hand column, chemicals applied are aimed more at improving the
production- or process potential in the field and/or the facilities. A wax inhibitor for
instance, could avoid deposition of wax in the production facilities without directly
improving the crude quality. Asphaltene and Hydrate inhibitors, allow undisturbed
flow of hydrocarbons while producing under normally deposit forming conditions.
Their application, however, does not have any impact on the sales aspects of the
produced hydrocarbons.

The application of chemicals has a number of disadvantages which should be taken
into consideration before any process chemical is introduced.
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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
chemicals can be rather expensive
applying chemicals can be Labour intensive
chemicals often have a negative impact on the environment when disposed

Chemical Costs - Gabon Chemical Costs - Gabon
CHEMICALS
50%
WELLS
11%
STATIONS
14%
MANPOWER
13%
MISC
12%
OPCO - OPEX Breakdown
RABI - OPEX Breakdown
CHEMICALS
18%
MATERIALS
12%
SERVICES
35%
MANPOWER
8%
SALARY
27%
1994 Data


The cost of chemicals as a percentage of total Opex varies between Operating Units.
Above Viewgraph shows that for Gabon (1994 data), chemicals take 18% of the total
Opex. From the bottom Viewgraph, depicting the split of Opex for the Rabi field in
Gabon, clearly shows that the fraction of the total operating expenditure required for
process chemistry, can vary widely in and between OUs. The reason for these
differences is often the differences in production streams and conditions, but can
also be attributed by the design of the production facilities.


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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Chemical Cost - Expro Chemical Cost - Expro
Total Expenditure on Treatment Chemicals - US$ 8.3 million.
Unit Cost of Chemical Treatment - US$ 0.051 / BOE.
1994 Data
0
500
1000
1500
2000
2500
3000
3500
E
x
p
e
n
d
i
t
u
r
e

-

U
S
$
'
0
0
0
Scale Inhibition (P)
Corrosion Inhibition
Demulsifier
Oxygen Scavenging
Dehydration
Biocide (P)
Hydrate Inhibition
Anti-Foam (P)
Doiling
Anti-Foam (I)
H2S Scavenging
Biocide (I)
Anti-Foulant
Freezing Depression
Filtration
Scale Inhibition (I)
Flow Improvement
38%
16%
12%
10%
9%
6%
91%
<2%

The Viewgraph above demonstrates the variation in chemical cost that can exist in a
certain OU. In this case Shell Expro UK in 1994 spent 91% of her chemical cost to
only six of the in total 17 different categories of chemicals in use. Scale inhibition
ranks first which is caused by scaling as result of sulphate containing sea water
injection in a calcium bearing formation.
In most OUs scale inhibition takes only a minor part of the OU Opex, while
demulsifier cost is normally higher.


Chemical Selection Chemical Selection
Chemical Treatment is the Third Line of Defense
Avoid.
Mechanically Treat.
Only Then Use Chemicals!
Identify the Problem
Ascertain Specific Cause/s (Temp., Press., Energy, Chemistry).
Determine Reason for Cause/s to Occur at that Point in the Process.
Assess Remedial Action Target
100% solution or a proportion.
Identify Candidate Chemicals
Computer Modelling if Available.
Literature, Service Company, RTS/ARC Searches.
Laboratory Screening (OPCO, RTS/ARC, Service Company Laboratories).
Field Trial & Evaluation
Routine Sampling and Evaluation of Performance.


Application of process chemicals can be costly, operationally manpower intensive,
and cause a negative impact on the environment. For these reasons, chemicals
should only be applied as the third line of defence.
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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Always first try to avoid using chemicals by for instance changing operational
conditions.
If problems cannot be resolved with these changes, then mechanical treatment may
be a solution.
Only if above attempts do not result in a sufficient improvement in the production
problems, chemicals can be used.

In order to select the most effective chemical, first the problem at hand has to be fully
identified. Therefore samples and measurements have to be taken and analysed by
an experienced process chemist who has a good understanding of the production
processes and equipment. Once the cause(s) have been identified, the required
minimum improvement has to be established to form the target for the process
chemicals to be tested.
Candidate chemicals will now have to be identified and, to assist the Process
Chemist, use can be made of computer modelling (if available), literature searches,
or assistance from research (RTS/ARC) or from chemical companies. After initial
screening and testing, a full field trial and evaluation thereof is very important to
make sure that the finally selected product will work under the actual production
conditions and variations thereof.

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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

1. Emulsion Treatment

Emulsion treatment can be subdivided into three groups of hydrocarbon water
processes.
The first process is called dehydration whereby water is removed from oil or gas.
The main reasons for dehydration are the following:
Requirement of refineries which demand a specific (maximum) water content in
the crude
High water cut of crude oil require larger pipeline size and pump capacity and thus
higher transport costs
The presence of water in crude enhances the likeliness of corrosion in the
production facilities.

Deoiling is the opposite process whereby remaining (dispersed) oil will be removed
from the remaining water phase following dehydration.
The reasons for removal of the oil are mainly the following:
environmental, where the water is disposed into the sea or other surface waters
where the water is (re-)injected oil removal is often required to reduce formation
damage and reduction of injectivity
For high oil in water contents, the removal of the oil can be economically
attractive.

Sludge is an emulsion stabilised by a high solids content and not possible to be
broken by normal dehydration techniques.
Their removal from the dehydration and deoiling process is important to avoid
upsetting these processes. Environmentally acceptable disposal options are
sometimes difficult to find and often annular injection is the most acceptable method.

Hydrocarbon-Water Processing Hydrocarbon-Water Processing
DeHydration.
Water Removal from Oil or Gas.
Refinery Requirements (0.5-1.0%v) or End User Requirements.
Reduced Transportation Cost.
Minimise Corosion Problems.
DeOiling.
Oil or Gas Removal from Water.
Environmental Impact.
Formation Damage.
Loss of Revenue.
Sludge.
Removal of Residual Emulsion with Entrained Solid Debris.
Interference with Dehydration.
Environmental Impact.


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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

1.1. Dehydration

Oil Processing Emulsions
An Emulsion is a Stable System of Two Immiscible Liquids,
with One Phase Finely Dispersed in the Other.
Dispersion
Mechanical
Energy
Water
Emulsification
Chemical
Stabilisers
Calcium
Stearate
Sodium
Stearate
Non-Polar Tail
CH
3
-(CH
2
)
16
CH
3
-(CH
2
)
16
Ca
++
C
O
O
-
C
O
-
O
Polar Head Non-Polar Tail
CH
3
-(CH
2
)
16
Na
+
C
-
O
O
Polar Head

Oil

In many cases, water is co-produced with oil production and part or all of the water
produced may be in the form of an emulsion with the oil phase. An emulsion is a
semi-stable dispersion of one liquid (dispersed phase) in another liquid (continuous
phase). The formation of an emulsion requires:
the presence of two immiscible liquids
mechanical energy to disperse one liquid as small droplets in the' other liquid
the presence of compounds to stabilise the emulsion, delaying phase separation.

Two types of emulsion can occur:

Water in oil (W/O) emulsion (or normal emulsion)
Oil in water (O/N emulsion (or reverse emulsion).

In the first case the oil is the continuous phase and the water is the dispersed phase,
with the opposite being true in the second case. The removal of water from a water
in oil emulsion is called dehydration. The removal of oil from an oil in water emulsion
is called de-oiling.

When one fluid is dispersed in another, the interfacial area is increased. Dispersion,
therefore, requires energy. The amount of energy required is a function of the
interfacial tension between the liquids and the increase in interfacial area. The
presence of surfactants, compounds which are partly
attracted by both liquids, reduces the interfacial tension and in doing so facilitates
emulsification.

A common example of this phenomenon is a soap molecule. This has a polar "head",
which will dissolve in water out of preference, and a non-polar "tail", which prefers to
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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
stay in the oil phase. In crude oil, asphaltenes, naphthenic acids and intermediate
wet solids, among others, will act in the same way to stabilise emulsions.

Maximum Stable Droplet Size
The Maximum Stable Droplet Size is a Function of the Mixing
Intensity ( = P / t).
D
max
= 0.725
1

.4

c
.6
D
max
= Maximum Droplet Size (m)

c
= Mixing Intensity (erg/g.sec)
= Interfacial Tension (dyne/cm)
= S.G. of Continuous Phase
Hinze-Clay Relationship
10
1
10
2
10
3
10
4
10
5
10
0
Dmax
(m)
10
1
10
2
10
3
10
4
10
5
10
6
10
7
10
8
10
9
(erg/g.sec)
= 1
= 5
= 30
Energy for Dispersion = Interfacial Tension x Interfacial Area.


An important parameter for emulsion stability is the size of the emulsion droplets. As
can be seen from the above figure the stable size of the emulsion phase droplets
decrease at increasing energy levels.
The smaller the droplets the more difficult it is to break or destabilise the emulsion
and separate the water from the oil. This emulsion stability is often further assisted
by the presence of stabilising chemicals in the produced crude as was discussed
above.

Emulsion Droplet Size
Droplet Size is Dependant Upon System Energy and the
Density and Viscosity of the Continuous Liquid Phase.
0
10
20
30
0
10
20
30
0
10
20
30
1 2 3 4 5 6 7 8 9 10
Droplet Size - m
1 2 3 4 5 6 7 8 9 10
Droplet Size - m
Vol% Vol% Vol%
1 2 3 4 5 6 7 8 9 10
Droplet Size - m
Gas Lift (18% Water) Beam Pump (29% Water) Beam Pump (84% Water)


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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Potential Emulsification Areas
Increase in Velocity
or Turbulence.
Typical Mixing
Intensity Values:
Choke - 10
9
Valve - 10
7
Pump - 10
6
Pipeline - 10
2
Sample Point - 10
6
1
2
3
4
5
Surface Pumps
Beans, Valves
Artificial Lift
Perforations
Formation
1
2
3
4
5


Originally in the reservoir, the oil and water phases, having stayed at rest in the
formation for millions of years, are fully separated in the formation pore structure.
When production starts, the oil and when the water cut exceeds connate water
saturation, also the water, starts moving from the formation into the wellbore, up the
tubing, across the bean valve into the flow line, etc.
Over the total distance of their travel from reservoir to the export tanks, the oil and
water is subjected to shear forces and different mixing intensity levels.
As result stable emulsions can be formed stabilised by the emulsifiers.

Formation-Perforation Region
Shear Around Wellbore Emulsification Field
SW Ampa
(Brunei)
Rahab
(Oman)
Lab Study
@ 30 cm @ 15 cm
0.8 - 4.0 E
4
1.3 - 6.5 E
4
40 - 120 65-185
>2000
>1100
sec
-1
sec
-1
The Emulsion Forming Tendancy in the Formation and at the
Perforations can be Modelled Using the Shear Rate.
8k
4V
Kozenys Formula : Shear Rate =


Laboratory modelling can be used to establish the likeliness of emulsion forming
conditions in the formation and at the perforations in the wellbore.
The so-called dynamic coalescer ( a fan viscosity meter type equipment) has been
developed to submit live crude and water mixes to similar shear conditions as
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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
observed downhole. It is important to note that presence of gas and the actual
pressure cannot be simulated. For calculating the actual shear rate at the wellbore
Kozenys formula can be used.

Shear rate = 4v/(8kf)

v = linear velocity (m/s),
k = formation permeability (m),
f = porosity (fraction).

Example: A well produces 100 m
3
/d ,the total perforation surface area is 1m
3
, while
the permeability is 1Darcy and the porosity is 0,3. What is the average shear rate at
the perforations?

Velocity 100 m
3
/d => 100/(24*3600) = 1,1 * 10
-3
m/s

Shear rate = (4* 1,1 * 10
-3
) / ( 8* 10
-10
* 0,3) = 284 s
-1

The dynamic coalescer can be used to subject oil and water mixes to the calculated
shear in order to find out whether formation of stable emulsions under these
conditions are likely. Further the effectiveness of selected demulsifiers can be
screened.


Gravity Separation
Buoyant Force: F
b
=1/6 * gd
3
(
w
-
o
)
Most important parameter is droplet diameter (d)
Drag Force: F
D
=1/8 * * C
D
* d
2
*
w
* v
2
where v = gd
2
* (
w
-
o
)
18
Density difference (
w
-
o
) between oil and water phase
Cannot be influenced
Can be influenced
Viscosity of continuous phase also important for separation


Oil and water can be separated because of their difference in density. If the density
of the droplets of the dispersed phase is lower than the continuous phase, they are
rising upwards while in the other case (e.g. water in oil), the droplets are falling.
The basic equations describing this motion are the buoyant force:

F
b
=1/6 g d
3
(
w
-
o
)

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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
F
b
= buoyant force, N
g = gravity, m/s
2

d = diameter of droplet, m

w
= density of water, kg/m
3

o
= density of oil, kg/m
3


and the drag force:

F
D
= /8 C
D
d
2

w
v
2


F
D
= drag force, N
C
D
= drag coefficient
v = droplet velocity relative to continuous phase, m/s

Equating F
b
with F
D
and assuming a Reynolds number Re = (
w
vd / ) below one,
so that the equation C
D
= 24/Re is valid, the terminal velocity of a spherical ,
dispersed phase droplet, will give Stokes Law (next Viewgraph).

The only parameter which can be influenced is the droplet size by subjecting the
emulsion to more or less mixing energy (shear). This influencing starts already at the
plant design phase where high shear conditions are avoided where possible.

Separation is Primarily by Settling:
Stokes Law
Variables: Droplet Size (d), Viscosity (
c
), Gravity (g), Density().
Influencing Factors: Turbulence.
Dehydration
.g.d
2
V=
18
c
Velocity (ft/hr) of a 200 m Water Droplet in Various Gravity Crudes
Crude API 12 16 33
40 oC 0.01 0.1 7
65 oC 0.12 0.18 10
90 oC 0.28 0.45 18


In Stokes Law the variables are the droplet size, the viscosity of the continuous
phase, and the density difference between the phases.
At static (or very low shear) conditions (i.e. in a dehydration tank) the droplet
diameter being squared in the equation, the effect on phase separation velocity
(dehydration) is very significant.
The example on the view-graph demonstrates the effect of the viscosity on the
settling velocity of water droplets in oil at various temperatures.
As the temperature rises, the viscosity drops and settling velocity increases.
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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
The higher the API (or gravity number) of the crude the lower the viscosity of crude
oil is.
For a similar water droplet of half the above diameter (or 100 m), these velocities
would be a factor four lower.
The above table also demonstrates the effects of API gravity and temperature on the
dehydration velocity.
The higher the API number (or the lighter the crude) the faster the droplet velocity.
This is caused by two factors; first the lighter the oil phase, the larger the density
difference between the oil and the water phase. The second reason is that the
viscosity of lighter crudes (the continuous phase) is lower thus allowing less drag and
faster separation.
Increasing the temperature during the dehydration process also results in a lower
viscosity of the oil and enhances the droplet velocity.
For this reason heating is sometimes applied to enhance dewatering of emulsion.
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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Sedimenting & Coalescing
Closely Packed & No Coalescing
Good Separation
Interference
Continuous Dehydration
The Working Layer Promotes Active Coalescence
Dry Oil
Emulsion
Water


In continuous dehydration tanks the feed stream is entered below the oil water
interface. The oil droplets have to move through the (brown) emulsion layer in the
middle where they meet other small oil droplets. As demulsifier has been injected
upstream the feed emulsion is destabilised and droplets can easily coalesce into
larger ones improving the separation velocity. The density of the water droplets
mixed with oil is also lighter than pure water and will enter the water rich emulsion
layer allowing these droplets to grow in size and fall into the clean water layer.
In case of stable emulsion the interface is very closely packed with a higher
apparent viscosity making it more difficult for the oil and water droplets to enter the
middle emulsion layer. As result coalescence will be hindered as no free interaction
between the droplets will be possible.
Stable emulsions can be formed and grow in size as result of the presence of for
instance stabilising agents such as emulsifiers, silt, rust particles, etc.
For this reason the emulsion layer has to be removed from the tank at regular time
intervals and treated with heat and/or chemicals to be broken into clean oil and
water.

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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
DeHydration Demulsifier Action
Rupture the Emulsion Skin
and Coalesce the Droplets
to Increase Size.
Destabilise the Skin.
Adsorb at the Interface.
Displace the Emulsifier
Alter the Emulsifier
Promote Coalescence to
Increase the Droplet Size.
Chemical Must be Fully
Dispersed in the Stream
Before the Mechanical
Separation Equipment.
0 100 200 TCM 2227/8


The above view-graph shows a microphotograph of water droplets in an oil phase.
Emulsifier chemical molecules, present in the production stream, position themselves
along the interface between the water and the oil phase, creating a kind of difficult to
penetrate skin stabilising the emulsion. Addition of Demulsifier chemicals counteract
the effect of the emulsifier and reduces the interfacial tension or the energy required
for the droplets to coalesce into larger ones. The results is that the skin (of
emulsifying agents) around the droplets is ruptured allowing easier access to the
cohesional forces of other droplets. To be able to work optimally, it is important that
these chemicals are applied as far upstream in the production stream as possible to
allow time for the chemical molecules to place themselves around the water droplets
and promote coalescence. This process can be totally upset when excessive shear
is applied to the feed stream whereby all liquids and chemicals are mixed up again.
It is therefore important to avoid large pressure drops and/or the use of high shear
pumping systems before the oil and water phases are separated dehydrated).

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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Chemical Application
0
10
20
30
40
50
60
70
80
90
100
0 4 8 12 16 20 24
Free Water, %v
Time, hrs
Inject Demulsifier at the Earliest Possible Point.
Allow Coalescence Before Entering the Separation Tank
Downhole
Wellhead
None


As discussed above, for optimal application of dehydration chemicals these products
have to be injected as far upstream the system as operationally possible. Preventing
stable emulsions to be formed is the most important criterion.
Downhole injection of the chemical would theoretically be the best option as it could
also enhance the production rate of the well because of the lower viscosity of the
produced fluids as well as giving more time for the chemical to avoid or destabilise
stable emulsions.
In practice however, injection downhole may not be practicable as this would require
intensive operator attention. In some cases, it may be possible to select one or two
notoriously stable emulsion producing wells for downhole injection in stead of
injecting at the production manifold of that particular field.

A new option currently under development by RTS in Rijswijk is the squeeze
injection of demulsifier chemical downhole say once a year in stead of continuous
injection and similar to the injection of scale inhibitors. Slow release chemicals are
injected in the formation rather than applying continuous injection.
Chemical Selection
Identify the Problem.
Representative Samples Throughout Process Stream.
Evaluate Mixing Intensity Distribution.
Eliminate Mitigating Factors Where Possible.
Lengths of Pipeline Instead of Valves to Reduce Pressure.
Compatibility Testing with other Treatment Chemicals.
Ionic - Cationic Reactions.
Bottle Test with Chemicals.
Quick Elimination of Non-Candidates.
Due to Complexity of the Process it is Still the Most Effective Method.
Evaluate Best Candidates for Temperature Sensitivity.
Select on Cost-Performance Basis.
Field Test
Minimum of 3 Months to Allow System to Stabilise and to Monitor Sensitivities.
Routine, Representative Sampling Throughout the Field Trial.


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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Where stable emulsion, hindering the dehydration process are encountered,
dehydration chemicals may be required to enhance the separation process.
To identify which chemicals will be required and at what location, a comprehensive
sampling and analysis programme has to be conducted to find out where the
problems do occur. It could also be that somewhere in the system conditions do
generate sufficient mixing energy to stabilise emulsions, and could be avoided easily
by simple engineering modifications. In these cases, making these modifications and
if economically feasible, would always be preferred above using chemicals.

If this is not the case and chemicals will be required, an extensive screening of
products has to be conducted using the so-called bottle test.
This test in which a large number of products can be screened will allow for a quick
elimination of non-performers. Life crude-water mixes without chemical are used for
this screening test. 100 ml bottles are filled with a carefully homogenised mixture to
which a certain concentration of one of the demulsifiers under test is added. These
bottles are monitored for their oil-water separation performance against time, the so-
called settling profile. The faster the oil and water separate into clean oil and water
phases without sediment or stable interface, the better the performance of the
product.
Apart from obtaining a dry or water free crude, for environmental reasons also the
water quality (i.e. oil in water content, etc.) becomes ever more important.

Until now it is still not possible to select suitable products based on the chemical
composition of the to be treated production stream and physical testing of products
will continue to be required.

After this first screening, a number of products will have to be tested further for their
performance under different operating temperature conditions and variations in
production streams.
After this second phase screening and economic evaluation, one or two promising
products are being selected for a full field trial. During these field trials which typically
last three months, all the different parameters such as fluctuations in production
rates, temperature, dosing rates, compatibility with other chemicals such as
corrosion inhibitors, but also the effect of stimulation activities in the field, etc. can be
monitored.
Based on the outcome of these trials, during which period an extensive sampling
programme has to be followed, the most cost effective product can be selected.

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PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Demulsifier Chemicals
Anionics
Sulphated Oils, Sulphonated Oils
Cationics
Quaternary Ammonium Compounds and Amines
Nonionics


Demulsifier chemicals can be divided into three main groups being the anionics
which have a negative charge on the molecule, the cationics with a positive charge,
and the nonionics who are neutral.
Depending on the emulsion stabilisation chemicals present in the feed stream,
chemical mixtures of one of these classes are used to destabilise the oil and water
emulsion.
Thereby ionic chemicals of the opposite side can never be mixed as they react with
each other and negate each others effect. This also applies if a for instance
cationic chemical is used for corrosion inhibition. In this case no anionic chemical
can be used as a demulsifier this would result in counteracting the effect of both
chemicals and precipitation products.

Non-ionic chemicals being neutral in electrical charge however, can be mixed with
either anionic or cationic chemicals.

Nowadays chemical mixes are rather complex and can exist of a large number of
products with varying molecular length. No method has at yet be found to predict
with sufficient accuracy, the effectiveness of these chemicals.
Trial and error product screening is up to now the only method of selecting an
optimal product.


20
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
SAMPLING PROGRAMME
When?
New Developments or Extentions
De-bottlenecking of Existing Facilities
Troubleshooting
Routine
Sampling Aspects
Offshore or Onshore Development
Is it a Complete New Development?
Is Crude Light/Heavy/Waxy/Asphaltenic?


Sampling programmes are important tools to prevent or solve dehydration problems.
For a new field development, up front information is required of the production
stream to anticipate potential emulsion/dehydration problems. During production
testing, of exploration wells, only limited information can be collected about the
dehydration characteristics of this new stream.
The settling profile can be measured on life crude samples which allows early
information on potential separation problems. Already a start can then be made in
selecting some potential demulsifier products which could be used once the field
starts producing.

De-bottlenecking of facilities means that somewhere in the production facilities the
conditions are such that they are the limiting factor for the maximum throughput of
the plant. A careful analysis and investigation of the settling performance at various
locations in the facilities is required to find the limiting factor.

For trouble-shooting of existing facilities, can be conducted to find the location in the
production system normally functioning satisfactorily, now causing the dehydration
problem. Changed operating- or other process conditions need to be found. Once
identified and understood, the best option for restoring proper functioning can be
identified, either technically, or by using/changing chemicals.

Routine sampling is conducted to ensure that changes in dehydration performance
are readily identified to allow timely action to rectify the changed condition before it
results in dehydration upsets. Routine sampling therefore requires regular sampling
at all critical locations in the field and the production facilities while maintaining
statistical records for analysis.
21
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

Aspects of importance for a sampling programme, include the location of the field,
onshore/offshore, the complexity of the operation, the physical properties of the
individual crude streams and their compatibility, etc.
A complete new development, where no- or very limited data are available, will
require another sampling approach compared to a field already in production for
many years.
The properties of the crude also are important for a good sampling programme,
necessitating sometimes different sampling methods to make sure a representative
sample is taken.

Sampling for Emulsions
Sample Collection Must Not Alter the Sample Condition.
Typical Mixing Intensity
Values:
Choke - 10
9
Valve - 10
7
Pump - 10
6
Pipeline - 10
2
Sample Point - 10
6
1
2
3
4
5
Surface Pumps
Beans, Valves
Artificial Lift
Perforations
Formation
1
2
3
4
5



At many locations in the production system the produced fluids are subjected to
mixing energy levels as shown above. As result the oil and water are mixed and
could form more or less stable emulsions. When sampling to identify potential
dehydration problems in the field, it is important that the samples taken reflect the
actual situation around the sampling point.
Therefore a proper sampling technique and equipment is required.


22
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Sampling
Sample Collection Must Acquire a Representative Sample.
The Whole Flow Stream Should be Sampled without Creating extra Shear.
Recommended Sampling System


A crude sample for dehydration performance testing has to be representative of the
actual stream in that part of the production process system under investigation.
The oil, water and gas phase in the flow line can be segregated and care has to be
taken that all these phases are represented in the sample.
Above picture shows a sampling system where, via an adjustable insert a sample
can be taken across the height of the pipeline. Another option is that the insert is
provided with a number of holes to take care of representative samples.
To minimise pressure drop and thus mixing energy across the sampling bottle inlet, a
large size valve has to be installed and fully opened to minimise the inlet restriction.

Temperature Effect
Temperature can Significantly Affect Dehydration Chemical
Performance.
0
5
10
15
20
25
0 30 60 90 120 150 180 210 240
0
5
10
15
20
25
0 30 60 90 120 150 180 210 240
0
5
10
15
20
25
0 30 60 90 120 150 180 210 240
Static Time - Minutes
Test Temp: 70
o
C
Only Product A Gave Separation
Residual
Water
%
Test Temp: 60
o
C Test Temp: 80
o
C
A
B
C


Demulsifier chemicals, due to their complex chemical mixtures, may be significantly
affected in dehydration performance by variations in temperature. Climatic changes
in temperature will also affect the temperature at which crude streams are processed
23
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
and have a significant impact on the dry crude quality. In desert locations ambient
temperature differences of over 50
o
C are not uncommon, and result in significant
variations of the production stream temperature. When screening for alternative
demulsifier products, the temperature sensitivity of these products has to be taken
into consideration. Before starting a new screening exercise, the maximum and
minimum expected crude stream temperature has to be measured. These minimum
and maximum temperatures can then be applied during the static settling
performance bottle tests. The above picture shows their performance on a certain
crude stream varying in temperature from 60 to 80
o
C. At 60
o
C, only product A
showed some separation, while no separation was achieved with the other two
demulsifiers.
At 70
o
C, all three products gave separation, product A showed an average
performance of the three chemical products. At 80
o
C, the performance of all three
products improved but chemical A was the least effective product.
Where temperatures fluctuate from 60 to 80
o
C, product A would be the best choice,
whereas with temperatures between 70 and 80
o
C, product C would be the best
product. Where no incompatibilities do exist between the tested chemicals another
option may be to change of chemical product to optimise the dehydration for the
various seasonal temperatures.

The Ghost Field Problem
The Ghost Field Produces from 50 Wells; Each Delivering
about 160 m
3
/day
Oil-Water Separation and the Export Crude and Disposal
Water Quality have become an Increasing Problem since the
First Formation Water Breakthrough.
Several Remedial Actions have been Implemented but the
Problem Persists.
As a Team Assigned to Investigate the Problem:
Analyse the Treatment Process and Flow of Fluids.
Identify the Potential Problem Areas.
Recommend Changes.
Consider the Various Change Options : Economics versus Benefits


24
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
The Ghost Field Schematic
Atmospheric
FWKO
Gas
Dehydration Plant
FTHP
1650 kPa
Field
Manifold
50 wells
1500 kPa
Field Station
Gas
4 Flowline
2000 m
Gaslift
7 Csg
3.5 Tbg
1500 m
FBHP
25,500 kPa
10 m
500 mD
20% Por.
SSV
Chemical
Injection
240 m
3
/d
Water
6,400 m3
Dynamic
Dehyd.
Tank
20m
4800 m3
Dynamic
Dehyd.
Tank
10m
320 m
3
/d
Freshwater
3200 m
3
/d
Water
800 m
3
/d
Water
12 Flowline
1000 m
Gas
Separator
675 kPa

160 m
3
/d
4100 m
3
/d
Oil



25
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

1.2. SLUDGE


Sludge
A Substance Left Over from the DeHydration Process.
Irreversible Emulsion with Entrained Solids and Debris.
Appearance is Highly Viscous with the Components Very
Finely Divided.
If Not Removed Results in:
Poorer Dehydration Performance
Tank Dropout SRB Growth
Components:
Water, Oil,
Sand, Silt, Clay, (Heavy Metals)
Wax, Asphaltenes, Scale
Corrosion Products, Bacteria


Together with the oil and water, other components from the reservoir such as clay,
silt, sand, but also wax, asphaltenes or scale can be co-produced. Operations such
as well acidisation and back production, apart from the spent acid, often also results
in large amounts of the above products to be released in the production system.
From the well and the production facilities, rust, paint, or bacterial debris, can be
transported into the production system.
These products often have a stabilising effect on oil and water emulsion systems and
hinder the destabilisation process of the demulsifier in a dehydration system.
As result, a stable, tight and highly viscous emulsion layer (called sludge) builds up
and cause a deterioration of the treated oil and water quality.
Also, the use of an ineffective dehydration chemical can result in the build up of tight
emulsion in the treatment facilities.

Carry-over of some of the sludge into the static dehydration-, export crude-, and
water treatment systems will occur and a sludge layer will also build up in the bottom
of these tanks.
Draining of the static dehydration and export tanks to remove water and stable
emulsion is applied to avoid excessive build up and to allow full utilisation of these
tanks. Normally the water is drained via a closed drain system to the water treatment
facilities while the sludge is often routed back into the incoming feed stream.
Due to the stability of these sludges, the amount of this product continues to grow
and further burden the dehydration process.

To minimise disturbances to dehydration and prevent sludge build-up in the facilities,
the stabilised emulsion will have to be removed from the oil-water interface at regular
time intervals. In continuous dehydration systems the sludge can be taken from the
interface via a separate line, while for batch operated systems sludge can be drained
after first draining the free water phase.

26
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Heat treatment is often applied to destabilise sludge, sometimes combined with
special dehydration chemicals or acid such as acetic acid.

Oily Water
Treatment
Export
Crude
Heat
Treatm.
Batch
Dehydration
FWKO
Sludge
Dehydration System
Sludge Build-up
Feed
Stream
Emulsion
Break Tank


Above picture shows a (very simplified) typical dehydration facility where sludge is
generated at various locations in the system. The feed stream enters the Free Water
Knock-Out (FWKO) tank with a relatively short residence time, to remove mainly free
water. The inlet is located just below the emulsion layer to take advantage of this
working or coalescence layer. If this layer grows too much or becomes too tight to
optimally function, a part has to be removed and treated via a heater treater. From
the FWKO tank, the crude stream is transferred into batch dehydration tanks with a
longer residence time, where the oil and water separation will be completed. Also in
these tanks stable emulsion can build up which has to be removed at regular
intervals to allow continued optimal functioning of these tanks.
In the heater treater the unbroken emulsion is heated to enhance the separation into
oil and water. Sometimes chemicals can be added. From the heater treater, the
emulsion will be transferred into an emulsion break tank to allow full separation.
If unbroken emulsion (sludge) remains from this tank, it has to be disposed of to
prevent it to recirculate through the treatment facilities and worsen the situation.

27
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Disposal
Burial
Road Surfacing
Direct Application
Injection into Asphalt Plants.
Solidification with Calcium Silicate (Dresser)
(Re-)Injection into wellbore or reservoir
(Controlled) Land Farming
Natural Evaporation
Bacterial Degradation
Sludge Disposal
Spiking in Crude Stream
Mechanical Removal for Biological Degradation or Disposa
Incineration


Sludge can be removed from the dehydration system via direct spiking in the crude
stream, mechanical removal or incineration. Spiking into the crude stream can only
be allowed if crude quality criteria are not exceeded. Spiking the sludge into the
crude results in transferring the disposal problem to the refinery and is therefore not
the environmentally preferred way of handling.
Another option is incineration where the emulsion can be injected in an incinerator.
Often when tanks have to be opened for maintenance sludge and bottom sediments
are often removed mechanically and have to be disposed of.
Depending on the composition (heavy metals and toxic organic materials) of the
sludge and environmental legislation in place, various options are available.
These include:
Burial (only allowed where no leaching of chemicals can occur)
Road surfacing (either via direct application or by mixing in asphalt)
Solidification to prevent leaching
Land farming in contained areas where toxic materials evaporate and/or degrade
naturally.

Sometimes sludge can be used as addition to the fuel for cement kilns which
temperature is high enough to fully decompose the material in an environmentally
acceptable manner.
28
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS


1.3. Deoiling

DeOiling Chemicals
Aid Mechanical Separation: Gravitational or Filtration
Increase Droplet Size
Skin Rupture & Coalescence
Quarternary Ammonium Compounds to Displace Emulsifying Agents
Insensitive to Dehydration Demulsifiers
Relatively Expensive (~$0.01/m
3
)
Toxic
Agglomeration
Polyacrylamide
Insensitive to Dehydration Demulsifiers
Relatively Inexpensive (~$0.004/m
3
)
Sensitive to Overtreatment (maximum 5 ppm)
Generally Non-Toxic (Must Not Have Free Acrylic Acid)


The water separated from the oil in the dehydration process always contains some
oil. As the water has to be disposed off either as an effluent into the sea or other
surface waters, or will be (re-)injected into a reservoir, the oil content has to be
reduced to meet environmental- or technical requirements.

Most of this oil can be normally removed from the water using mechanical
equipment, such as tilted plate interceptors (TPI), Dispersed or dissolved gas
floatation units, hydrocyclones, (ultra) filtration units or centrifuges. The selection of
the equipment is mainly based on three criteria namely, final oil concentration, oil
droplet size and available space. In particular (ultra- or membrane) filtration units and
centrifuges are capable of removing very small oil droplets and reduce the oil content
to below 10 ppm.

Often, in production facilities equipment is installed which cannot meet the required
outlet oil in water content. This can be caused either by having the wrong equipment
installed for the particular produced water stream, or as result of tightening of
environmental legislation.

In these cases, chemicals could be used to enhance the performance of the
equipment.
It is very important to realise that when chemicals are added, the main part of that
chemical will be disposed together with the water. Therefore, in the selection of a
deoiler chemical, the environmental acceptability is a very important factor.

Typical deoiler chemicals act in a similar way on oil in water emulsion as demulsifiers
on water in oil emulsions and in this case rupture the rigid skin around the oil
droplets allowing coalescence to take place. They are therefore often called reverse
emulsion breakers.
29
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Quaternary ammonium compounds are cationic or positively charged thereby
displacing the emulsifier at the oilskin. These chemicals can only be added in the
system after the dehydration process has been completed as they counteract
demulsifiers which are mostly anionic.

Another later developed group of deoiler chemicals are the so-called agglomeration
products, mainly organic polymer products. These products with high molecular
weight, have a charge density (positive or negative) independent of the pH of the
water. This charge density will neutralise the opposite, often negative charge of the
oil droplet and destabilise it.
The advantage of the use of polymers is that they are virtually insensitive to
dehydration demulsifiers and do not cause incompatibility problems. Also compared
to the above reverse emulsifiers they are relatively less expensive, and more
importantly virtually non-toxic.


30
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

2. Organic Deposits

In this chapter the organic deposits hydrates, waxes and asphaltenes will be
discussed.
Hydrates are crystalline compounds of water stabilised by certain guest hydrocarbon
molecules including methane, ethane and propane. Their main importance is that
these crystals can be formed during the production of water containing gas
sometimes at temperatures well above zero degrees centigrade, the normal freezing
point of water.

Waxes are chemical compounds consisting of long aliphatic (linear) hydrocarbon
molecules, which depending on the chemical composition of the oil and the
temperature, will form wax crystals.

Asphaltenes, are complex mixes of hydrocarbon compounds which are dispersed in
crude oils. Once destabilised, also these chemicals can form deposits which is
mainly pressure dependent. Destabilisation and subsequent deposition mainly
occurs when the (above bubble point) pressure of a compressible crude is reduced
resulting in a reduced solubility of the asphaltenes.

Hydrocarbon Processing Deposits
Hydrocarbon Based Deposits
Hydrates
Crystalline Water and Hydrocarbon Compounds.
Wax
Paraffinic, Alkane, Component of Crude Oils.
Asphaltenes
Natural Compounds Dispersed in Crude Oils.

Aqueous Based Deposits


Aqueous Based Deposits Aqueous Based Deposits

Scale
Scale Scale
Inorganic Chemical Deposits.
Inorganic Chemical Deposits. Inorganic Chemical Deposits.
31
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

2.1. Gas Hydrates


Gas Hydrates
Gas Hydrates are (ICE) Crystals Formed by a Framework of
Water Molecules, Reinforced by Guest Molecules.
The Most Common Guest Molecules are:
Methane (.7H20), Ethane (.8H20), Propane (.18H20), CO
2
, H
2
S and N
2
Carbon Dioxide Hydrogen Sulphide
Freezing Point Rises with Increased Pressure.
H
Guest
Molecule
O


Gas hydrates are crystalline compounds formed by a framework of water molecules,
reinforced by guest molecules. Under suitable conditions, water molecules may form
structures as a result of hydrogen bonding. These structures are thermodynamically
unstable. However, if guest molecules are available to fill the cavities in the water
framework, stable compounds will be formed. Suitable guest molecules relevant to
the oil industry include small hydrocarbon molecules such as methane, ethane,
propane and isobutane, as well as other gases such as carbon dioxide and hydrogen
sulphide. The size of the water lattice structure can vary, the final arrangement being
dependant on the precise availability of guest molecules. These hydrate lattices
when formed in production systems may grow to the extent that they can plug lines
or pieces of equipment. They can be found in the liquid as well as the gas phase
and, because of their damaging consequences, great care is taken to avoid their
formation in production systems.

Hydrates can be formed in oil and gas production and transport facilities and may
cause severe problems. A (normal) pre-requisite for hydrate formation is the
presence of free liquid water. High pressures and low temperatures are also
beneficial to the promotion of hydrate formation.

Impact of hydrate crystallisation
Hydrate ice crystals are generally softer than normal ice and as such will not
normally cause damage to tubing, flow line, or vessels. However, in some cases the
crystals are harder and cause erosion or destroy sensitive parts in the production
facilities. In particular attention has to be given to the damage which can be caused
to measuring devices such as orifices and pressure differential membranes.
32
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
In larger quantities, the crystals tend to lump together and cause blockages in the
system, for instance in the wellbore, the tubing or flowlines causing interruption of
the gas flow.

Impact of Hydrate Crystallisation
Particles.
Hard Hydrate Crystals can:
Cause Erosion of Metal Components.
Destroy Inlet Scrubber Screens.
Impact on Measuring Device Integrity.
Blockages.
Hydrate Formation can
Plug Producing Zone
Block Tubing
Block Flowlines.
Block Measuring Device Inlets.



Hydrate Formation
At temperatures well above 0
o
C, water molecules are moving freely from each other,
called the Brownian movement of molecules. When temperatures are approaching
the normal freezing point of water, these movements are becoming slower and the
water molecules tend to group themselves in a more stable structure. This is done
via the so-called Hydrogen Bonding in which the Hydrogen atoms from the water
molecules are forming a loose bond with the Oxygen atom of another water
molecule. In this way clusters of water molecules are being formed where the
hydrogen bonds move from one molecule to another. During these changes in
hydrogen bonding, also the formation of unstable crystal like lattices may occur.

In the presence of certain Guest Molecules which have a size to nicely fit in the
cavity of a lattice of water molecules, the total structure can thereby be stabilised
such to form a hydrate crystal. As result hydrate ice crystals can be formed well
above the pure water freezing point.

33
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Cluster Model of Freezing Water
H
O
O
O
O
O
O
O
O
O
O
O
H
H
H
H
H
H
H
H
H
H
H
H
H H
H
H
H
H
H
H
O
H
H
H
H
H
H
H
H
H
H
H
H
H
H H
H
H
H
H H
H
H
H
H
H
H
H
H H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
O
O
O
O
O
O
O
O
O
O O
O
O
O
O
O
O O
O
O
O
Regions of Low
Thermal Energy
Flickering Clusters due to Hydrogen Bonding


Factors affecting hydrate formation
Although solids, like true ice, hydrates have different structural characteristics. Two
hydrate structures are often encountered in oil and gas production operations.
Firstly, the simplest of all crystalline cavity structures can be formed by a pentagonal
dodecahedral of 20 water molecules linked together by hydrogen bonds (see below).
This structure has 12 regular pentagonal (five-ring) faces.
The almost spherical cavity inside this structure can accommodate small molecules
such as methane, ethane and hydrogen sulphide.

A Simple Lattice of Water Molecules A Simple Lattice of Water Molecules
40 Hydrogen-Bond
Linkages
20 Oxygen
Atoms

34
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS


As a result of minor deformations, other structures containing cavities can be formed
besides the regular pentagonal-dodecahedron ones. Typical examples, like the
fourteen and the sixteen face cavity structure are shown on the figure below left and
right of the twelve face structure. The larger the cavity the larger molecules the
molecules it can contain, including propane, isobutane and carbon dioxide. The
hydrogen bonding structure of the hydrate is weak and will collapse unless it is
supported by molecules occupying the cavities. This explains why propane and
butane, which only can fill the larger cavities, form very unstable hydrates- as they
do not fill enough cavities to support the weak lattice structure. Molecules larger than
butane are too big to form hydrates as they cannot fit into the cavities. In fact they
tend to inhibit hydrate formation because the crystal tries to form around it.

The number of guest molecules that can enter the cavities is dependant upon
temperature and pressure (pressure distorts the lattice, and hence the cavity shape).
Not all the voids may be filled, and hence hydrate structure tend to be varied.


Typical Gas Hydrate Structures Typical Gas Hydrate Structures
5A
14 faces
12 Faces
16 Faces
Ethane Methane Propane


The existence of single guest molecule stabilised hydrate crystals would not cause a
problem in production facilities are their physical size is very small (+/_ 0.50 nm.)
However, like normal ice, the crystal particles do tend to group themselves in typical
three dimensional crystal shapes as shown above. As such their size increases to
that extend that blockages of the flow system can occur
35
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Packing of Hydrate Basic Units Packing of Hydrate Basic Units


General conditions for hydrate formation
Hydrate formation in natural gas can, as follows from the above, only be formed in
the presence of water. Its formation is mainly dependant on pressure and hydrates
can be formed both in the gas and liquid phase of the gas (left of the hydrate line in
the picture below). At lower pressures, the temperature also has an effect on hydrate
formation, but significantly decreases when pressure increases.

General Conditions for Hydrate Forming
Dew Point
Line
Bubble Point
Line
Hydrate
Curve
P
T
Critical
Point



The next picture shows the hydrate forming conditions for pure Propane (C
3
H
8
).
36
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
The line in red indicates the hydrate curve while the blue line is the Propane vapour
pressure curve. The pink area indicates the total area where hydrates can be
formed. Below the water freezing point of 0
o
C, both ice and hydrate are present,
while above this temperature only hydrate ice can be formed. At temperatures above
0
o
C, the pressures required for hydrates formation increases steeply, while above
the vapour pressure line, hydrate formation becomes virtually independent of
pressure.

Hydrate Forming Conditions for Propane
0.05
0.1
0.5
1.0 Pressure
MPa
Temperature
o
C 10 5 0 -5 -10 -15 -20
Hydrate
+
Water
Liquid
Propane
+
Water
Vapour
+
Water
Vapour
+
Ice
Hydrate
+
Ice
Propane
Vapour Pressure
Curve


The same type of curves do also exist for other low molecular weight natural gas
components including Methane (CH
4
), Ethane (C
2
H
6
), Butane (C
4
H
10
), Hydrogen
Sulphide (H
2
S) and Carbon Dioxide (CO
2)
and can be used for hydrate formation
prediction modelling.
In the earlier models, like the Hercules model developed by KSEPL (former RTS),
only simple predictions for gas mixtures could be made based on equilibrium
conditions. They however, did not reflect the kinetics of hydrate formation and
decomposition.

37
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Prediction
Old Hydrate Prediction Software: Hercules (EP 51181).
New Software Package: STFLASH (OP97-20206)
More Accurate Over a Wider Operating Window.
Allows Multiple Phases and Tolerant to CO2.

Sensitive to CO
2
and Condensate.
A new software tool, STFLASH developed by Research and Technology Centre
Amsterdam (RTCA) however, is a thermodynamic model, capable of obtaining
quantitative results for the following categories:

Removal of water from the mixture below the level of saturation (with respect to
hydrate formation)
Control of thermodynamic conditions, i.e., temperature and pressure
Addition of inhibitor (i.e., Glycol or Methanol), shifting the equilibrium.

The addition of a new type of inhibitor, called growth modifier, cannot as yet be
predicted with the model.

The latest version (version 4.0) of the STFLASH software has recently been
released with a user manual, report OP97-20206. Further information can be
obtained from ORTET/26.

38
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Prevention
Freewater is Necessary for Hydrate Formation
Dehydrate the Gas
The Water Must Freeze to Form Hydrates
Depress the Freezing Point.
Anti-Freeze: Methanol or Glycol.
Glycol, being easily recoverable, is the preferred preventative measure.
Methanol, being faster acting, is the preferred remedial treatment.
Ammonia and Salts (NaCl, CaCl2).
Salt solutions can be corrosive.
Heat the Gas / Insulate Pipeline.
Inhibit Crystal Growth
Modify the Crystal Shape.
Negate Crystal-Crystal Bonding.


Hydrate Prevention
Prevention is always the preferred option and is also applicable to the formation of
gas hydrates. As water is always required in order to form an hydrate, dehydration
(or water removal) of the gas could be an attractive option. Dehydration in the oil and
gas industry is mostly conducted using glycol contactors and would be no option for
downhole application. In most cases hydrates, when present form either downhole or
upstream the gas processing facilities.

Anti-Freezes
Do Not React with gas hydrates but dilute the liquid water phase thereby shifting
the hydrate curve to lower temperatures by 0,8 degrees per mole % of particles
dissolved in the Water
H y d r a t e M e l t i n g P o i n t
0
2 0
4 0
6 0
8 0
1 0 0
1 2 0
1 4 0
1 6 0
0 5 1 0 1 5 2 0
T e m p e r a t u r e ( o C )
P
r
e
s
s
u
r
e

(
b
a
r
)
N o A n t i f r e e ze
A n t i f r e e ze

39
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
A second option is to depress the freezing point for hydrates. This can be done by
the addition of chemicals such as Methanol or Glycol and is used very often when
hydrate formation is predicted. These chemicals do not react with the hydrate
structure itself but merely function by diluting the water phase thereby shifting the
freezing point to lower levels (see figure above).

Glycols, due to their higher boiling points compared to water, can more easily be
recovered from the gas in gas dehydration systems, and is therefore the preferred
product as a preventative measure.
Methanol however, due to its lower viscosity, acts faster and is mostly used for
remedial applications when hydrates already have been formed. Examples in the
figure below show that the selection of the product can also be dependant on other
conditions such as the location of the hydrate plug in the production system.

When Hydrates Are Formed
MeOH Glycol
+
Water
Water
HYDRATE PLUG HEAT HEAT
BACK PRESSURE
SYSTEM PRESSURE
SLOW FAST


Other chemicals which depress the hydrate freezing point are salts such as common
kitchen salt (NaCl) or Ammonium Chloride (NH
4
Cl). Despite of being cheap products,
their disadvantages are the relatively large quantities required and their corrosivity
to carbon steel.

Heating is a third option to prevent hydrate formation. This option is often applied in
gas sales systems where the lines around the pressure reduction system are
insulated and electrically heated.

The last option for hydrate formation prevention is by crystal growth prevention.
This can be achieved in two ways namely:
40
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Crystal shape modification in which the crystal is reshaped into a more
amorphous appearance. In this case by its non-crystalline shape the hydrate
cannot easily adhere to flowlines etc. (see picture of amorphous crystal)

Amorphous Hydrate Growth



The second type of growth preventers are the so-called crystal-crystal bond
negating products. As the word says it does interfere with the growth of crystals by
positioning around the single crystal lattice, resulting in only very fine (and
harmless) hydrate particles to be formed.

An example of the latter type chemical is the Shell developed product Armoblen 802.
This product was successfully tested by Statoil in Norway in 1995.
A disadvantage of this product, although being very effective in preventing large
hydrate crystals to form, is that it is non-biodegradable. As part of the chemical ends
up in the water phase of the production system and has to be disposed of, it is
subjected to strict environmental limitations with regards the acceptable disposal
option. Particularly in Europe, the only possible solution could be to re-inject the
contaminated water into the formation.

Shell Hydrate Inhibitor
Initial Material - Armoblen 802
Non-biodegradable Prototype
Successfully field trialed by Statoil, May 1995.
Line operating at 4.5
o
Subcooling Hydrated up in about 2-3 hours.
With 0.25% Inhibitor Operated for Days Without Problems.
Tested Down to 10
o
Subcooling without Hydrate Formation.
Tested Down to 13
o
Subcooling Shutdown/Restart.
Ref. AMGR 96.202
Limitations
So Far Tested to 20% Water Cut; However Statoil Claim Up To 40% OK.
Non-Biodegradable; However Can be Reclaimed in Glycol Regeneration
Unit or Neutralised in a Simple Sewage Treatment Plant.
Future Developments
Biodegradable Version Ready for Field Trial.
Test Upper Limits of Operating Range.


As result, a new product has been developed by RTCA recently, which is
biodegradable. The product called ACER 96S44, is now available via Akzo/Nobel (at
test quantities) and is claimed to be 50% degraded within 28 days while product
toxicity is lost in five days. A successful test was conducted by Shell Expro UK in the
Sean field with a BS&W of 30%.
41
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Another test planned in Norway, was cancelled as no approval from the Norwegian
authorities could be obtained for reasons of the short term toxicity of the product.
Akzo conducted an environmental risk analysis which showed any effect of the
product to disappear within 5 days. Norwegian authorities still reject application as
they do not wish to set a precedent for application elsewhere in Europe.

Shell Hydrate Inhibitor
New Biodegradable Product is ACER 96S44 (AKZO/NOBEL)
50% Biodegradable in 28 days
Successfully tested by Expro in Sean Field (30% BS&W)
Product Toxicity was Lost in 5 days
Statoil Trial: No approval from Norway Authorities yet
Advantages of ACER 96S44:
+/- 8 times Cheaper than Methanol
Safer (Not flammable)
Requires less Storage Space


The figure above shows the advantages of the new type inhibitor compared to the
regular glycol and methanol.

Testing of Hydrate inhibitor products
In order to develop improved hydrate inhibitors, RTCA has developed a Hydrate test
loop in which wet gas can be subjected to actual temperature and pressure as
encountered in the field. In these tests the conditions under which hydrates are being
formed can be established. Another important function if this test loop is to test the
effectiveness of hydrate inhibitors. So, before an expensive field trial is to be carried
out, first the product can be tested in the laboratory.

Hydrate Test Loop - Amsterdam


Recently, Statoil developed their own test loop for hydrate formation testing.
A transparent loop is filled with gas, condensate and water and cooled to the
required temperature. During this cooling process the loop is rotated with a velocity
of 1 m/s, while a camera is fixed to the loop such that it is level with the
gas/condensate interface. While rotating, the liquids are moving and mixing with the
gas to enhance contact. The video camera records the movements of the liquids in
the loop while rotating. The formation of hydrates and its effect on the flow of the
liquids can be followed instantaneously.
42
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Also this loop can be used to test the effectiveness of hydrate inhibitors and has the
advantages of being more simple and visibly showing the effect of inhibitor products
on the onset of hydrate formation.


STATOIL Hydrate Wheel Test Unit
1 m/s
Camera
Condensate
Water
Gas



Laboratory Grown Hydrate Crystal


Apart from the Armoblen and the later biodegradable Acer product, other inhibitors
are available on the market.
One of these, an initial BP product, was proved to be fully ineffective in reducing the
onset of hydrate formation. This product was removed from the market by BP and
replaced by a former Shell product THI. This product is discarded by Shell as a poor
performer but claimed by BP to allow 10
o
sub cooling. It was tested by Statoil and
found to be hydrated up in two hours only.

BP conducted a field trial in the Hyde West Sole field with 12
o
sub cooling, where
over one year they reported only minor hydrate forming problems. Another, more
important problem reported was the formation of severe emulsions resulting from
incompatibility of the product with demulsifier used in the field.
For this reason BP also plan to conduct a trial with the Acer product in the Villages
field.
For pipelines in marginal hydrate forming conditions THI may be a suitable product
as in this case no crystals are formed at all, therefore needing no condensate flushes
to disperse crystals.
43
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
This product has the advantage of already being commercially available and it is
currently planned to be used as first fill in the Shell Expro UK ETAP field.



Other Hydrate Inhibitors
Initial BP Inhibitor
Proven to be Fully Ineffective (i.e. 0 performance) and Dropped by BP.
Current BP Inhibitor - THI
Previous Shell Development Discarded as a Poor Performer.
Claimed to Perform up to 10
o
Subcooling.
Tested By Statoil at Tommeliten
Ineffective, Hydrated Up in 2 hours.
BP Field Trial in the Hyde West Sole Field (12
o
Subcooling).
Only Minor Hydrate Problems Reported.
Severe Emulsions Reported.
Want to Field Trial Acer in Villages Field.



44
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS


2.2. Waxy Crude

World-wide approximately 1500 different types of crude have been distinguished,
although no two crudes are found to have exactly the same composition. Of these,
between 10 and 20% are found to be waxy. A strict definition of what constitutes a
problematic, waxy, crude is not possible because this is not related to any one
single property of the crude. The paraffin waxes present in a crude are the saturated
hydrocarbons, with. both straight chain -, CH3-(CH2)
n
-CH3, and branched-molecules
being present. Methane, is the simplest saturated hydrocarbon, and being a gas
under all operating conditions, can not be classified as a paraffin wax. In general, the
higher molecular weight compounds have higher melting points and so can generally
be considered to be more "waxy, although an increased amount of branching in a
molecule reduces this effect.

Whether wax is observed to crystallise under field conditions will depend
considerably on local circumstances. Production rates, temperature and flow
conditions, presence of other hydrocarbons, asphaltenes, resins and water content
are all factors which may have a bearing upon this. Thus the paraffin wax which
crystallises will vary in composition for each individual case. Operating at low
temperatures is likely to induce crystallisation for smaller, lower melting point
molecules (although the higher melting molecules will precipitate as well), than
operating at higher temperatures.

Wax Wax
Wax is the Paraffinic, or Alkane, Part of a Crude.
Deposits Usually Include Other Heavy Hydrocarbons, Asphaltenes and Resins.
Crystallisation is Temperature Sensitive.
Pressure has a Much Smaller Effect.
Crystals can be Either Plate or Needle Like.
These Interact Resulting in a 3-Dimension Structure.
B
u
b
b
le
p
o
in
t
-lin
e
Temperature
P
r
e
s
s
u
r
e


The Figure above shows a typical plot for the conditions under which wax will
deposit. Wax deposition is mainly temperature dependant, while pressure only has a
minor effect.
45
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Wax crystals can have different crystal structures depending on the hydrocarbon
composition. The structures are three dimensional and can easily adhere to rough
metal surfaces.

Impact of Wax Crystallisation
Increase in Crude Viscosity.
Higher Pressure Drops (Higher Pump Input Energy).
Reduced Throughput.
Gellation
Very High Restart Pressures.
Deposition on Metal Components.
Increased Wall Roughness Inducing Turbulence.
Partial Blockage Reducing Flow Area.
Impaired Safety Device Functionality.
Solidification in Pipelines.
Arrest of Flow ( )
Pipe
Wall
Cool
Cool


Wax deposition can have the following impact on hydrocarbon production.

Increase in Crude viscosity as result from the presence of solid wax particles in
the oil. This increase of viscosity will result in higher pump pressures and reduced
throughput through the production system.
The solid wax particles due to their 3 dimensional structure have the tendency to
adhere to each other thereby growing in size. This process, called gelation,
proceeds more rapidly in stagnant or low energy flowlines where the initially brittle
structures would easily be broken. In case flow has been interrupted for some
time, these wax crystal structures are building up in time. At the time of restart,
high pump pressures are required to break these gels.
As at the flow-line walls, under laminar flow conditions the shear rate is lower than
in the centre of the flow line. Wax crystals can more easily adhere themselves at
the rough metal pipe walls without being sheared into pieces. Over time the wax
particles are growing into more strong crystal structures, thereby reducing the flow
area and result in increased pump pressure and lower throughput. Another aspect
is that devices such as safety relief valves may become blocked and result in
safety hazards.
In extreme cases the total pipeline can become blocked by the deposition of wax.
This is the case when the shear stress and yield strength exceed the pump
capacity.



46
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Wax Deposition
The onset of wax deposition depends on the chemical composition of the crude; a
high concentration of high molecular weight n-alkanes (e.g. C40+) often is the
forebode of wax related problems. This onset is mainly influenced by the crude
temperature and in a lesser degree the pressure. The temperature at which the first
crystals appear is called the wax Appearance Temperature (WAT).

Wax Deposition
Drop in temperature below Wax-Appearance Temperature (WAT)
Drop in pressure (& temperature)
Beware of high proportion of n-alkanes e.g. C40+ => high WAT


Wax Terminology
In its original composition all the constituents of a crude will remain completely
dissolved when the temperature is high enough. On cooling, a temperature will
eventually be reached at which wax crystals form. The temperature at which the first
wax crystals form, and are in equilibrium with the wax that remains dissolved, is
defined as The Wax Appearance Temperature (WAT). Above this temperature all the
wax will eventually dissolve: below this temperature increasingly quantities of wax
will crystallise.

The best way to approximate the WAT is through the determination of the cloud point
of the crude oil. The cloud point is defined as the temperature at which the first wax
crystals are formed. This temperature may be determined by direct microscopic
observation of the crude. However, due to the problems inherent in physically
observing wax crystals in dark, non-transparent crudes, other means of measuring
the cloud point have been developed. For example, the Bondi cloud point is obtained
by recording the rate of cooling of a crude, the cloud point being marked by a drop in
the rate of cooling induced by the onset of wax crystallisation. Due to the effect of
supercooling, whereby crystallisation does not actually begin until below the critical
wax solubility temperature, the cloud point in this method is obtained by extrapolating
the cooling rate after crystallisation has been initiated, back to the cooling rate before
crystallisation. In this way the super-cooling effect is eliminated as an error in the
determination. Even so, due to the slow crystallisation rate of wax, this method also
has its drawbacks. As a result of these problems the measured cloud point may be
significantly (10-20
o
C) below the actual WAT.

Pour Point
Another way of characterising a waxy crude is by measuring its pour point,
the temperature below which, flow of crude ceases.

Paraffin crystals can, after sufficient wax has crystallised, form a three-
dimensional structure. This structure may become sufficiently strong to
prevent flow of the crude. The strength of this structure will depend on
47
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
several external factors such as shear effects and thermal history. More than
one type of pour point can therefore be defined. The minimum pour point
of a crude is defined as that obtained when the crude has been heated to
104
o
C prior to the pour point determination. The maximum pour point is
obtained when the crude is heated to at least 46
o
C, or to 9
o
C above the
expected pour point. The minimum temperature required to obtain the minimum
pourpoint is called the Inversion point.
If a repeat pour point were to be carried out on a sample, it is likely that a
higher pour point than originally observed would be recorded the second
time. Two factors would contribute to this phenomenon. Firstly some light
components may have been lost by evaporation during the initial determination and
hence the wax content of the crude may be expected to
be higher for the sample for the second determination. Furthermore, when
the gelled crude is re-heated the lighter paraffins within the crystal structure will
dissolve first. The large crystal structure disintegrates leaving a large number of
crystal fragments which, if they are not completely dissolved in the heating process,
will act as crystallisation nuclei. Thus, it is likely that in the second determination,
there will be more crystal nuclei to seed crystal growth, resulting in a higher pour
point being obtained.

In practice the apparent pour point is sometimes used. This is measured by
conducting a pour point test under ambient conditions, without any thermal pre-
treatment.


Wax Terminology
Cloud Point (= Wax Appearance Temperature)
Temperature at which the First Wax Crystal Forms.
Difficult to Determine in an Opaque Medium.
Cooling Rate Dependant.
Pour Point
Temperature at which Crude will No Longer Flow.
Measured in 3
o
C Decrements.
Generally 10-40
o
C Below the Cloud Point.
Strongly Dependant on Thermal History.
ASTM Minimum Pour Point - Monotonic Cooling from 104
o
C.
ASTM Maximum Pour Point - Reheated to 46
o
C then Re-cooled.
Inversion Point
Temperature at which All Crystals are Re-dissolved.
Some Crudes have an Inversion Point Below 46
o
C.


The figure below lists a number of crudes where crude density and wax content are
related to their pourpoint. This table indicates that at lower wax levels, relative lower
pour points are observed. At increased wax content above 10%, the pourpoint
48
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
rapidly increases to temperatures between 20 and 30
o
C. No direct relation has been
observed between the crude density and its pourpoint.

Pour Point - Wax Content
Crude Density Wax Content Pour Point
kg/m
3
%wt (Shell)
o
C ASTMD97
Arabian Light 854 4 -36
Kuwait 870 4 -21
Basrah 855 4 -12
Forties 839 4 0
Low Wax Content Oils
Cabinda 868 10 21
Gamba 868 12 33
Shengli 908 12 27
Sarir 847 16 24
Beatrice 832 16 27
Bombay High 832 16 33
Taching 864 20 33
High Wax Content Oils
The Pour Point May be Independent of the Wax Content.


The following figure shows the pourpoint behaviour for crudes with different wax
content. The crude samples are cooled from reservoir temperature to determine their
initial cloud point. Thereafter the crude samples are reheated above their inversion
temperature and cooled again to the cloud point. Finally, the samples are reheated
to 46
o
C and re-cooled again, now to obtain the maximum cloud point. The results are
listed in the table for these crudes and indicate no significant difference between
minimum and maximum cloud point for low wax contents, where higher wax
containing crudes show a higher maximum pourpoint.

49
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Pour Point Behaviour
The Pour Point is Dependant Upon the Thermal History.
Crude Wax Content Pour Point
Minimum Maximum
%wt (Shell)
o
C ASTMD97
Boscan 0 18 18
Kuwait 4 -21 -21
Shengli 12 18 27
Gamba 12 18 33
Sarir 16 9 24
Beatrice 16 9 27
Bombay High 16 24 33
X X
X X X
X X
X X
X X X
X X
X X
X X X
X X
- -
- - -
- -
Cloud Point
Min. Pour Point
Max. Pour Point
Undissolved Crystals
Seed New Crystals
Inversion Point
Reservoir
Conditions
Temp


Mixing of crudes is sometimes applied to avoid wax deposition problems. In these
cases, a crude with known wax deposition problems is mixed with a low wax crude
with a lower pourpoint as shown in the figure below. As result of this mixing the wax
content of the waxy stream is diluted and likely to reduce its pourpoint to lower

Mixing Crudes
Mixing Crudes with Different Pour Points Will Not Necessarily
Result in a Pour Point Between the Two.
Example:
Pour Points: Min. Max. Inversion
Crude A 12
o
C & 18
o
C 31
o
C
Crude B 21
o
C & 54
o
C 65
o
C
Mixed Above 65
o
C 15
o
C
Mixed Below 65
o
C 30
o
C
Tests Must Always be Carried Out, at Operating Conditions,
to Determine the Actual Impact.


temperatures. Laboratory testing under actual field conditions is a requirement as
there is no linear relation between wax content of a crude mix and its minimum and
50
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
maximum pour point. In these tests the actual temperature at which the crudes are
mixed is an important parameter and may have a significant impact on the resulting
mix pour point. At temperatures below the inversion point, a significant higher
pourpoint will be the result if compared to mixing the two crude streams above this
inversion temperature.

Waxy Crude Viscosity Behaviour
Most pure liquids have a viscosity profile which is independent of the shear rate
(i.e. display Newtonian characteristics). The formula to describe Newtonian viscosity
behaviour is as follows:

Newtonian fluid:
t =

a
y

If, however, solids are present which interact with each other, the viscosity profile
becomes more complex.
A crude which contains wax crystals will have a shear rate which depends upon
viscosity and a residual yield strength (
y
) at zero velocity. This can be understood
by the formation of loose wax crystal structures which hold the liquid together. Once
the main structure is broken, the fluid can start flowing. By exerting higher shear
(energy) to the liquid, also the smaller crystal structures will be broken, resulting in
an apparent reduction of the fluids viscosity.

Several models are available to describe non-Newtonian fluids. The mathematical
expressions representing the most common of these non-Newtonian viscosity
profiles are shown below:

Bingham equation:
=
y
+
p
y

Herschel Buckley equation (extended Power Law equation):
=
y
+ky
n


where:
= shear stress
y
= yield strength

p
= plastic viscosity
a
= apparent viscosity
y = shear rate k = consistency index
n = flow behaviour index

Fluids which have a viscosity behaviour similar to the Bingham equation, virtually
Newtonian, apart from the yield strength, which has to be overcome before the fluid
will start flowing. In the Herschel Buckley equation, however, in addition to the yield
strength, also a further shear thinning effect at increased shear rate is apparent.

By increasing the temperature of the waxy crude, where the crystals start melting, it
will be clear that the viscosity behaviour will slowly return to a Newtonian pattern.


51
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Waxy Crude Viscosity
Wax Crystallisation Has a Major Impact on Crude Rheology.
Above the Cloud Point the Crude is Newtonian.
Below the Cloud Point the Rheology of a Waxy Crude
Becomes Shear Rate Dependant with a Yield Strength.
Generally Waxy Crude Rheology can be Described with the
Herschel Buckley equation.
=
y
+ ky
n
= shear stress,
y
= yield strength, y = shear rate
k = consistency index, n = flow behaviour index
Waxy Crudes Become Increasingly More Thixotropic with
Further Reductions in Temperatures.


Crude Rheology Crude Rheology
0
10
20
30
40
50
60
70
80
90
100
0 200 400 600
Shear rate (sec
-1
)
V
i
s
c
o
s
i
t
y

(
M
p
a
s
)


Wax Prediction
Over the years a number of wax prediction software tools have been developed to
assist, the engineer and the operator in the design and optimal operation of the
production facilities with minimal negative impact of the waxy nature of the crude to
be produced and processed. Like for all other software prediction tools, the accuracy
of the input data are of paramount importance in obtaining reliable prediction results.
These data are collected by conducting laboratory tests under as much as possible
actual field conditions on fresh crude samples. Proper sampling and analysis is
important; two laboratories capable of conducting proper sampling and analysis are
52
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Core Laboratories, with laboratories in all major oil production regions, and Oil field
Chemical Technology (OCT), which is located in Aberdeen.

The first prediction model, Waxline , used mainly by process engineers, is a
relatively simple software tool, which can predict temperature and pressure drop for
waxy crude flow in a pipe line. It is part of the Engineering department Engineering
Office System (EOS) software package.

A second model developed by Shell Oil is called Waxdep, which in addition to
Waxline can also predict the pipeline restart pressure.

Crude Shear Stress Crude Shear Stress
Restart measurement after shut in
0
2
4
6
8
10
0 10 20 30
Time (min)
L
i
n
e

p
r
e
s
s
u
r
e

(
p
s
i
)
Build up of
Wax


The data required as input for these models include the isobaric temperature profile
of the crude (at operating pressure). In particular Waxdep also needs test-loop data
on wax build-up as function of shear as input to predict the restart pressure for a
particular production system.
This test loop was build by Oil field Production Analyst (OPA), but is now also used
by Nowsco.

A third model, ParaSim, recently developed by Atomic Energy Association (AEA).,
can be used for the prediction of wax deposition in multi-phase lines.

53
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Wax Prediction
Software Packages:
WAXLINE
Predicts Temperature and Pressure Drops for Waxy Crude Flow in a Pipeline
WAXDEP (ShellOil)
Can also calculate Pipeline Restart Pressure
Data required: Isobaric Temperature Profile (at Operating Pressure)
Testloop data on Wax build-up as function of Shear
Laboratories: Corelab and Oilfield Production Analyst (OPA)
ParaSim from AEA for Multi-Phase Lines





Apart from the above models, use is made of other models and techniques such as
Compack and Wellwax, to predict wax deposition inside the well. Compack is a
thermodynamic model which uses compositional data to fit equations of state and
validate predicted versus actual cloud point. The objective is to predict the well
temperature for a wax deposition free operation. For Wellwax, High Temperature
Gas Chromatography is used for wax samples extracted from core samples.

54
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

The importance of fresh, live crude samples, is demonstrated in the figure below.
It compares the wax appearance temperature of dead crude with that of a fresh
live crude sample. In this case a difference of some 5
o
C was observed in WAT
between the two crude samples (data from mtg. on asphaltenes and wax between
Shell Oil and Shell Expro 10-11 June 1997).

LABORATORY MEASUREMENTS
Wax Appearance
F
i
l
t
e
r

p
r
e
s
s
u
r
e

d
i
f
f
e
r
e
n
t
i
a
l

/

p
s
i
Crude temperature /C
Pressurised Crude Samples
0
2
4
6
8
10
12
14
16
0 10 20 30 40
Live Crude
Dead Crude
Wax appearance







When the temperature at the wall of a pipeline is below the cloud point of the crude,
wax deposition is likely. A wax layer of increasing thickness, increasing the thermal
insulation, will form, until an equilibrium situation will occur. In the equilibrium
situation, the rate of erosion of wax as result of shear forces is equal to the
deposition rate. In this situation the wall thickness may be reduced considerably.
This in turn will reduce the pipe capacity and increase the energy required for
pumping.

55
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
0
2
4
6
0 100 200 300 400
Wall Shear rate sec
-1
W
a
x

d
e
p
o
s
i
t
i
o
n

(
m
l
/
l
i
t
r
e

c
r
u
d
e
)
Wax Deposition
Measured on Live Crude
Approximate
Wax
shear strength
LABORATORY MEASUREMENTS


Wax Inhibition
Prevention of wax deposition by taking measures is always preferred to tackling the
problems after wax has deposited in the production system. Options to design out
wax problems by inhibition include the following:

Dilution of the wax content
Operating within optimal conditions
Chemical additives
Magnets?

Dilution of the wax content
Dilution of the wax content can be conducted in varies ways.
One method is by blending the waxy crude with another crude stream with a higher
cloud point. Proper sampling and laboratory testing has to be carried out to ensure
the mixture to be non-waxing under actual operating conditions.
Mixing the crude with solvents such as naphtha or kerosene also has been used in
the past. This method requiring large volumes of the solvent is expensive and
logistically unattractive..
Sea water has also been used for diluting the wax content and to create an oil in
water emulsion. The effects are a significant lower fluid viscosity and due to the
system being water wet, no wax deposition. The disadvantages, however, are that
the large amount of water has to be removed, biocides and corrosion inhibitors have

56
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Wax Inhibition
Inhibition.
Dilution of the Wax Content.
Operate Within Optimal Conditions.
Keep Temperature Above Cloud Point.
Induce Turbulence to Erode Pipe Wall Deposits.
Chemical Additives.
Shells SWIM (Shell Wax Interaction Modifier).
Generally Used to Reduce the Pour Point.
Shell SWIM 11-T Can Reduce Wax Deposition for Some Crudes.
Must be Thoroughly Tested Before Application.
Must be Added to the Crude Stream Before It Cools Below Its Cloud Point.
Shell SWIM Will Not Remove Already Deposited Wax.
Magnets ?


to be added to control corrosion, and more difficult dehydration of the emulsified
crude. It is also important to realise that by mixing the crude with sea water, the
temperature of this mix drops resulting in wax depositing inside the oil droplets.


Operating within optimal limits
Two options are available to control wax deposition in the production system which
are:

keeping the temperature above the cloud point of the crude
using turbulence to avoid build up of wax on the pipe walls
coating of pipe walls

Temperature above the cloud point
This can be achieved in a number of ways including insulation of pipelines or tubing,
or applying heat. Where insulation would be sufficient to prevent deposition, this
should be the preferred option. Also the use of heat exchange systems where heat is
generated somewhere in the production system could be an attractive method to
avoid cooling of the pipe wall below the crudes cloud point.

The second option of using turbulence can also be applied to avoid wax building up
in the system. The disadvantages of this technique include the following:

Initial wax deposition will always occur along the pipe wall and after for instance a
shut down, severe start up problems may be experienced including a total blocked
pipe line.
To create turbulence in a system, extra pump pressure may be required costing
additional energy.
57
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Turbulence in a system of oil and water, may cause a destabilisation of the
dehydration system and cause stable emulsions.

Coating of pipe walls
Coating of tubing down hole or pipe lines at surface, is sometimes applied to
minimise wax build up.
The principle thought behind this is that by smoothing the pipe wall, wax crystals
have more difficulty to adhere themselves, thereby delaying a wax layer to build up.

Chemical additives
Like with the use of all other chemicals, using wax inhibitors, should be the last resort
in combating wax drop out in the production system. An example of these products is
Shells SWIM which is the abbreviation for Shell Wax Interaction Modifier. The
product is generally used to reduce the pour point of a crude system.
It has been proved to reduce wax deposition for some crudes, but is not the solution
for every waxy crude stream. Therefore, before applying any chemical additive to
prevent wax, a thorough testing programme is required to test its (cost)effectiveness
and the dosing level of the product.
It is important to realise that Shell SWIM will not remove any wax already deposited.

The figure below shows how the chemical interacts with wax molecules, preventing
unlimited crystal growth and by smoothing the molecular structure such to minimise
adherence to the pipe wall. The actual temperature for the onset of wax crystals is
not altered, only the growth is affected and the crude viscosity will not increase
dramatically.

Wax Modifier Action
Pipe
Wall
Cool Cool
Pipe
Wall
Cool Cool
+
Normal Crystal Growth
Crystals Form Network.
Increase Viscosity
Adhere to Pipe Wall
Shell Wax Interaction Modifier
Modified Growth
Crystals Isolated.
Pass Through System


Magnets
58
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Magnets have been claimed many times in literature, to inhibit the growth of wax
crystals. However, scientific proof or a clear definition of how it works has not been
given as yet, and often initial promising test results could not be duplicated.
Based on this, it is very doubtful whether magnets have a measurable effect on wax
deposition.

Wax Removal
If, in spite of all prediction, prevention and mitigation actions, wax still is depositing
on pipe walls or in tanks/vessels, remedial actions have to be taken to remove this
material before it causes too large operational problems.
A number of techniques/methods are available for the removal of wax from the well
bore, pipe lines, etc.
These techniques/methods include the following:

Mechanical removal by scraping or pigging
Thermal removal via heating with stream or electrical
Dilution by dissolving in (hot) oil
Chemical dissolvers

Mechanical Removal
Mechanical removal by scraping is often applied to remove wax from down hole
tubing. Even when applying inhibitors like SWIM, it can still be necessary to run
scrapers down hole at regular intervals. Often economics related to crude deferral,
scraping frequency and scraping is used to find the optimal approach.
Pigging is often applied in flow and pipe lines. The selection of the most suitable type
of pig is important to remove as much as possible wax without running the chance of
getting the line blocked by a stuck pig.

Thermal removal
Heating is also regularly applied to remove wax deposition in the tubing. Mobile
steam generation is used, while also electrical heating can be applied. The
importance of this technique is that its frequency is tuned such that it is most cost
effective.
An alternative way of thermal removal is by utilising in situ heat generating chemicals
like NH
4
NO
3
with NaNO
2
which forms when mixed in the presence of water, NaNO
3
+
Heat. Placement problems are the main reason why this technique has not been
used recently.

Dilution
Dilution with hot oil can also be applied to resolve the crystallised wax from the
tubing, by heating the deposit well over its cloud point.
As in this case a liquid is injected via the wellhead into the well bore, extreme care
has to be taken that this wax enriched hot mixture does not enter the formation to re-
solidify. If this would occur, a relatively simple problem would be made worse by
impairing the well, requiring stimulation or hydraulic fracturing to start production
again.


Chemical solvents and surfactants
59
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Chemicals have been developed which are claimed to dissolve wax deposits. In
practice, however, these products do not perform as claimed. Also, often large
volumes of these (expensive) products and long soak times are required, resulting in
extra production deferral. Testing is always required before deciding on actual
treatment with these products.

Wax Removal
Removal.
Mechanical.
Scraping.
Pigging.
Thermal.
Steam/Electrical Heating.
Dilution.
(Hot) Oil Flushing.
Chemicals.
Mutual Solvents and Surfactants.
Effectiveness is Dubious and Must be Tested Beforehand.
Shell SWIM Will Not Remove Crystalline Wax.
Reference:
EP-64010 General Aspects of the Transport of High Pour Point Waxy Crude Through Pipelines.



60
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
New Developments
Wax problems in a number of Operating Units such as Shell Gabon, result in very
high chemical expenses, still combined with loss of production. These costs and
production losses warrant extra research in the development of better tools/products.
For this reason, and as part of the initiative by RTS in Rijswijk to improve
performance via the Installation of Jewel research projects, the idea of designer
bugs was developed.
These designer bugs, in the case of wax deposition should be bio-engineered such
that they would decompose-, or eat the wax crystals thereby avoiding serious wax
deposition and even remove wax layers already formed. One of such products
recently developed is Para-bac which is claimed to perform as described above. This
product is currently being evaluated by Thornton Research Centre for its
effectiveness.
As these bacteria prefer Oxygen free environments, a possible application area may
be the under water (anaerobic) storage cells in Draugen, which crude has a WAT of
31
o
C.

Apart from using these products in storage tanks, etc. their main use will be to
prevent wax growth in tubing and flow lines. Therefore these products could be
applied by annular injection, or alternatively, by squeeze injection into the formation.

Designer Bugs
Wax: New Developments
Para-Bac
Can also Remove Wax
Claims: Promotes Wax Degradation
Application Options:
Annular Injection
Reservoir Squeeze
Product evaluation by Thornton





61
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS


2.3. Asphaltenes


Asphaltenes are usually arbitrarily defined as that fraction of a crude oil which is
soluble in toluene, but not in n-heptane. As such the asphaltenes embraces a
complex mixture of components. They comprise a peptised dispersion of high and
lower molecular weight aromatic molecules (molecular weight usually between 1,000
and 10,000) which are polar (and as such usually contain hetero-atoms such as

Asphaltenes
Asphaltenes are a Complex Natural Component of Crudes.
They are the Constituents of Crude that are Not Soluble in Heptane/Pentane.
They Exist as Peptised Micelles Dispersed in the Crude Oil.
Resins and Aromatics Peptise (Disperse) the Micelles in the Aliphatic Oil.
Destabilising the Dispersants will Result in Asphaltene Flocculation.
Dispersion is Pressure Sensitive; Temperature has a Smaller Impact.
Central Part of
the Asphaltenes
High Molecular Weight
& Aromatic Compounds
Low Molecular Weight
Aromatic Compounds
Mixed Aromatic
Napthenic Compounds
Mixed Napthenic
Aliphatic Compounds
Predominantly
Aliphatic Compounds


nitrogen, sulphur, etc., for an example, see the figure on the next page ). Once
destabilised, these molecules have a tendency to aggregate, a property which
produces their insolubility in n-alkanes. However, in crude oil systems they are
normally associated with resins, which are molecules similar in nature to the
asphaltenes, but they are less polar and have strong solubility in the n-alkanes. The
resins association with the asphaltenes reduces the aggregation and thus enables
the solubility of the asphaltenes.

Research into the development of a model to predict the behaviour of asphaltenes in
crudes has followed two separate paths. One school of thought considers the
asphaltenes as particles present in the crude as a colloidal suspension. The colloids
exist as micelles (diameter 3-40 nm ), which are stabilised by large molecules (the
resins) adsorbed on their surface. Removal of the resin leads to the deposition of the
asphaltene. The theory implies an irreversibility in the process. Under this model the
phase behaviour is described by colloidal science techniques, e.g. electro-kinetics
and adsorption.

62
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Hirschberg has approached the problem by looking at asphaltenes as molecules in
the liquid phase, which may or may not form a solid phase, manifested as a deposit
or floc, depending on the thermodynamics of the situation. The key difference this
model has with the colloidal theory is that it implies that a reversible phase change
occurs in the deposition of asphaltenes.

S
CH3
S
CH3
CH3
CH3
CH3
N
S
N
CH3
CH3
CH3
Asphaltene Molecule


The molecular model implies that kinetic effects are extremely important in
asphaltene deposition. This is clear because deposition is usually seen to be
extremely fast whereas re-dissolution is extremely slow (weeks?). Deposits, once
formed, are extremely difficult to remove, and indeed re-dissolution may prove totally
impossible.

This latter point appears to be better explained by the colloidal theory but overall the
evidence either way is inconclusive. The models however are not necessarily
mutually exclusive and it may be that both models present elements of the truth.
63
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

Asphaltene concentrations in crude oils vary greatly - from virtual absence up to
50% in some heavy oils. Deposition of these compounds is a problem which has
plagued the industry world wide for a great number of years, though occurrence of
such problems has not always been seen to be a direct function of the asphaltene
content of the crudes in question. In contrast to the conditions which induce wax
deposition, temperature is found to have a relatively small effect on asphaltene
solubility; pressure and crude composition are much more critical factors.


Major Solubility Fractions of Crude Oil


The occurrence of asphaltene deposition problems in oil fields world wide is found to
bear little relation to the asphaltene content of the crudes in question. Crudes
containing very high concentrations of asphaltenes may produce trouble free for
years, whilst other crudes with asphaltene content as low as 0.2% can give
deposition problems from day one.

For example Venezuela's Boscan field, whose crude has a 17.2% asphaltene
content, was able to produce with no initial deposition. In contrast, the nearby Mata-
Acema crudes, which contained from 0.4-9.8% asphaltenes, had a history of
deposition problems. In laboratory tests the Boscan crude was shown to be resistant
to electro-deposition of asphaltenes, whereas the Mata-Acema crude did show
deposition under the same conditions. However, addition of Boscan crude to the
Mata-Acema crude resulted in the prevention of deposition in the Mata-Acema
crude. It was clear, therefore. that the Boscan crude contained some agent which
was able to work against asphaltene deposition. This agent turns out to be the
resins.

Thus, the asphaltene content of the crude is seen to play a lesser role in the
flocculation process than the amount of peptizing agents present, i.e. the resins.
64
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

There is a theory that the two metals nickel and vanadium, which are found to be
present in significant concentrations in many crude oils, may also be somehow
implicated in the mechanism for asphaltene deposition.
These elements are found to be present in asphaltene deposits in much greater
concentrations than they are in the crude itself. They do have a tendency to form
organometallic complexes with the asphaltene molecules and will tend to impart
electrical charge to the molecule; this may have a significant impact on the solubility
of the asphaltene in the main body of the crude and hence influence its deposition.

Destabilisation and thus asphaltene drop out for a particular crude can occur by a
drop in pressure above the bubble point. This pressure drop causes an expansion of
the oil leading to oversaturation of the crude with asphaltenes.
Temperature plays only a minor role in the deposition of asphaltenes.

By mixing of crudes with totally different chemical composition, and the presence of
asphaltenes, may cause oversaturation of asphaltenes in the mix and, resultingly, in
deposition.

Highly compressible oil, a high undersaturation in a gas reservoir and a low
asphaltene content, are all possible forebodes for the likeliness of asphaltene
deposition tendency.


Causes of Asphaltene Dropout
Drop in Pressure above Bubble Point
Some Dependence Upon Temperature
Mixing Incompatible Crudes or Condensates
Beware of: Light Oil (Compressible)
High Undersaturation in (Gas) Reservoir
Low Asphaltene Content (< 2%)


As described earlier, deposition of asphaltenes can occur rapidly, in contrary to its
dissolution, which, if at all possible, is very slow.

Once formed, the deposition of asphaltenes in the near well bore region (e.g.
perforation and inflow area, will severely impair the inflow of hydrocarbons into the
well. The use of solvents, dispersants, or even hydraulic fracturing, may become
necessary to improve inflow.
65
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

Like for wax deposits, asphaltene deposits in the production tubing will restrict inflow
and cause operational and safety hazards to operating equipment such as gas lift,
and safety valves .

In surface facilities, deposit particles due to their polar nature can form the nuclei for
emulsion droplets, thereby stabilising these emulsions. Further, plugging of oil/gas
processing equipment can result in deterioration of the treatment processes, or even
result in safety hazards.

Impact of Asphaltene Deposition
Slowly Reversible Process
Reservoir
Near Well Bore Drop Out of Asphaltene Flocs Can Severely Impair Inflow
Performance.
Tubing
Deposits can Restrict Tubing Diameter Reducing Outflow Performance.
Deposits can Foul Operating Equipment; GLVs, SSSVs and such.
Surface Facilities
Can Stabilise Emulsions.
Plugging First Stage Gas Separator; can lead to Pressure Build-up.
Plugging Compressor Inlets; leading to Starving.
Solids Disposal Problem


The figure below thus shows the asphaltene solubility versus applied pressure for a
given temperature and GOR. The shape of the plot is generally similar for each type
of crude oil, although the asphaltene content will naturally vary for each crude. From
the Figure, it can be seen that above the bubble point (P
b
), asphaltene solubility
decreases with decreasing pressure. This effect is due to the expansion of the oil
(compressibility). At a certain critical pressure (P
c
, the crude becomes saturated with
asphaltenes. Below this pressure, asphaltene: will precipitate until the bubble point
P
b
is reached, at which point there will be minimum solubility. As the pressure is
reduced further below P
b
, more of the asphaltenes will go back into solution, the
unfavourable effect of compressibility being increasingly compensated for by
degassing. However, as stated above, the rate at which re-dissolution occurs may be
slow relative to crude residence time in the system.

However, for deposits to be formed, the following aspects are of importance:

The asphaltene peptised micelle dispersion must be destabilised to allow
flocculation
The precipitation kinetics should be fast enough to form the deposits in time
66
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Once the flocs are being formed, they should grow into agglomerates to cause
plugging.
Due to the normally soft nature of the deposits and easy erosion, a high velocity in
the production system would prevent larger particles to be formed.
The build up of deposits can only occur when the wetting conditions are
favourable for the particles to adhere themselves to the metal walls.



Asphaltene Dispersion is Pressure Dependant
Asphaltene Dispersion Must Be Destabilised.
Precipitation Kinetics Must Be Favourable.
Crystals Must Agglomerate.
Velocity of Flowing Stream Must Allow Deposition.
Wetting Conditions Must Allow Adsorption.
Asphaltene Deposition - Production
Dispersion Line
Pb Pc Pr
Asphaltene Content
Of Reservoir Crude
Asphaltene
Content
(%w)
Pressure
Precipitated
Dissolved
Dispersed
Pb = Bubble Point
Pc = Critical Pressure
Pb = Reservoir Pressure


Asphaltene Deposition - Well Activities
Destabilisation of asphaltene micelles can be caused by a number of well activities
including:

High shear pumps.
The asphaltene-resin relationship is seen to be critical to the solubility of
asphaltenes.
In high shear environments, the micellar structure of the dispersion becomes
distorted, whereby the resins can become separated from the asphaltene molecules.
Once the destabilised crude enters a low energy zone in the production system
asphaltene particles can start dropping out of solution

Well Stimulation and EOR
Also when applying stimulation, the balance between resin and asphaltene is likely to
become distorted and have an impact on asphaltene deposition. The same is also
valid for injection of carbon dioxide, water, and steam flooding programmes. They all
can initiate asphaltene deposition where no problems had been previously
encountered.

67
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
When well stimulation is being applied in a reservoir where asphaltenes are likely to
become destabilised, deposition thereof can be prevented by separating the crude
from the stimulation chemicals by using a pre-flush of an asphaltene compatible
fluid.

Asphaltene Deposition - Well Activities
Asphaltene Micelles Can be Destabilised by:
Shear
High Shear Pumps Which Have a Lower Pressure Region Downstream.
Well Stimulation
Changes in pH.
Aromatic Solvents.
Surfactants.
EOR
CO2 Flooding
Change the pH and Cause Localised Joules-Thompson Cooling.
Steam Flooding
Localised Temperature and Pressure Change.
Prevention
Isolate the Natural Crude from the Treatment with a Pre-flush.


For the prediction of asphaltene deposition, a PVT sample is required of the crude
taken under reservoir conditions (above the bubble point). Apart form measuring the

Prediction
Asphaltene Dispersion versus Pressure and Temperature
can be Profiled in the Lab.
Field Test Unit Available Which Detects Asphaltene Dropout.
Also can Determine Wax Crystallisation Properties and Crude Viscosities.
PUMP A PUMP B
Pressure sensor
Filter unit
Stirred piston reservoir
Temperature
control
Data
capture

68
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

asphaltene content, In a PVT laboratory a pressure and temperature profile can be
determined by slowly changing the pressure in a PVT chamber with a see through
window where the transparency of the sample can be measured. This test has to be
repeated at various temperatures before a full profile can be obtained.

Another method is to make use of a special asphaltene field test unit.
A crude sample is transferred (at reservoir pressure) in the test unit shown below
and pumped though a filter unit equipped with a pressure sensor. The temperature is
kept constant while at slowly decreasing pressure. When the pressure has reached
where the asphaltene solubility is exceeded, particles will start dropping out of the
crude and slowly plug the filter. This plugging will result in an increase in the
pressure differential over the filter which can be monitored against the absolute test
pressure (see the figure below).

Asphaltene Detection
Precipitate
Formation
Test Direction
Pressure - psi
D
i
f
f
e
r
e
n
t
i
a
l

P
r
e
s
s
u
r
e
0
1
2
3
4
5
6
7
8
9
10
1500 2000 2500 3000 3500 4000


The same equipment as used to test a crude for its asphaltene deposition tendency,
can also be used for wax prediction. In this case, however, the temperature is the
variable and the pressure kept constant.

69
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Wax Detection
Wax
Appearance
Test Direction
Temperature - C
D
i
f
f
e
r
e
n
t
i
a
l

P
r
e
s
s
u
r
e
0
2
4
6
8
10
12
14
16
15 20 25 30 35 40


Prevention
The best option to prevent deposition of asphaltenes, is to operate outside the
precipitation window as shown below. In practice, however, this is often not possible.
The other options to prevent deposition of asphaltene particles, are mainly based on
either preventing the crystals to grow by high erosion velocities of crystal
agglomeration inhibition, or by merely avoiding the particles to adhere to the metal
surface of the production tubing or facilities.

Both for changing the wettability and inhibiting crystal growth, mostly chemicals
(dispersants or surfactants) are being used.

Over the suitability/effectiveness of (electro) magnets in the production system, no
clear proof has been found of these products to be effective.

70
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Operate Outside of the Precipitation Window
Use High Flow Velocities to Erode Deposits.
Change Wetting Conditions to Minimise Adsorption.
Inhibit Crystal Agglomeration
Chemicals
Electromagnetism
Prevention
Dispersion Line
Pb Pc Pr
Asphaltene Content
Of Reservoir Crude
Asphaltene
Content
(%w)
Pressure
Precipitated
Dispersed Dispersed


Options for Control
When operating under asphaltene depositing conditions, control options have to be
available to prevent plugging of formation, tubing , valves or other production
systems.

Two (chemical) options are available; solvent washes and inhibitor injection.
Both methods are often not 100% effective and laboratory testing is required.
Even when not being 100% effective, in a number of cases they can be used
economically to manage asphaltene deposition problems.

Both types of chemicals have number of constraints as listed in the figure below.
A number of product types for both solvents and dispersants are listed in the last
figure on this topic.

71
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Options for Control
Options:
Solvent Washes to Remove Deposits
Continuous Inhibitor (Dispersant) Injection
Other (e.g. Magnetics)
Constraints:
Solvent Compatibility with Injection Lines
Chem. Inj. via Waswater must Remain in Solution
or Stable Dispersion.
Stability to High Temperatures
Compatible with Other Chemicals


Asphaltene Solvents/Dispersants
Solvents:
Most Contain Aromatics (= aquatic toxicity)
New Products under Investigation. e.g. Glycol Ether, Esters
Amino-ethanols, etc
Dispersants:
Mainly Surfactant Type Products
(Some products tested were found to be able to eliminate
formation of asphaltenic flocs.)



72
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

3. Drag Reducers

Introduction
Vast amounts of crude oil are transported in pipelines all over the world. Due to new
discoveries being evacuated along with existing production, and due to improved
production techniques for existing fields, several pipelines appear to have insufficient
capacity for current needs and have become limiting factors for production rates.
Increasing capacity is therefore a key factor for many operations.
Drag reducers are high molecular weight polymeric chemicals which are successfully
applied in several parts of the world to solve this problem. The best known example
of drag reduction is the trans-Alaska pipeline. The capacity of this 1300 km long 48
diameter pipe was increased from 188,000 m
3
/day to 220,000 m
3
/day (17%
increase) by the addition of 10 gram of polymer per m
3
of crude. Drag reducers are
also used in hydraulic fracturing where water soluble compounds are added to the
fracture fluid to reduce the horse power requirements.
Attention must be paid to the solubility of the products used, their compatibility with
other chemicals, in particular demulsifiers and their sensitivity to shear degradation.

Drag Reduction Drag Reduction
Improve Pipeline Capacity
Reduce Horse Power Requirements for Pumping
Shear Sensitive
Expensive
Compatibility with Demulsifiers
Pros and Cons:
Definition:
Long chain chemicals which improve the flow of hydrocarbons
in pipe/flow lines operating under turbulent flow conditions


Definition of Drag reduction
Drag reduction can be defined as the increase in pumpability caused by the addition
of a drag reducer to the crude stream. For a given flow rate, in a given pipe, this
definition is expressed by the following formula:

%dr = (dP - dP
1
) x 100/dP


where;
73
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
%dr = percent drag reduction
dP = pressure drop of untreated fluid
dP
1
= pressure drop of fluid with additive

This formula represents the actual performance of a drag reducer. In most practical
applications however, the improved pumpability of a fluid is used to increase the
capacity of a pipeline rather than to reduce the pumping costs. A formula which
represents the increased throughput potential is therefore more applicable. An
empirical formula has been proposed which defines the percentage throughput
increase (5Ti) as follows:

%Ti = [{0.01(100- %dr)}
-0.55
-1] x 100

From this formula it can be calculated that a 20% reduction in drag represents a
throughput increase of 13%.


Drag Reduction Drag Reduction
Formulas:
% Drag reduction (%dr) = (dP - dP
1
) x 100 / dP
dP = pressure drop untreated fluid
dP
1
= pressure drop treated fluid
% Throughput increase (%Ti) = [{0.01(100 - %dr)}^
-0.55
-1] x 100
Mechanism:
Not fully understood but believed to result from
aligning flow in the direction of the principle strain rate in
pipe lines under turbulent flow conditions


The exact mechanism of drag reduction is not yet fully understood. However, drag
reduction effects seem to depend on the stretching of individual molecules by high
strain rates in the flow. As the long drag reducer molecules are elongated they align
in the direction of the principle strain rate. It is suggested that threads occur in the
flow, inhibiting bursts and sweeps in the wall-layer flow, thereby reducing friction
under turbulent flow conditions. This explanation is consistent with the fact that the
effective application of drag reducers is restricted to turbulent flow conditions only.





Drag reducing Chemicals
74
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Drag reducers are long chain polymeric materials which should have the following
properties:
be readily soluble in oil
have a high molecular weight
be inert to chemical (compositional) changes within the crude
be compatible with other additives (e.g. demulsifiers)

The best drag reducers are essentially linear, high molecular weight compounds with
a maximum length. Several types of such chemical are commercially available and
include:
polymetacrylates
polydimethylsiloxanes
polybutadienes
polyisobutylenes
polyisoprene

Polyisoprene, a synthetic rubber with a molecular structure almost identical to natural
rubber, can be supplied as solids crumbs, suspended in a stable aqueous solution.
One advantage of this delivery method is the high concentration of active material in
the slurry as most drag reducers are supplied as a 1% solution.

A further advantage of the above product is that solid particles suffer less from shear
degradation. Shearing can induce break down of polymer chain, an effect which will
reduce the effectiveness of the drag reducer. For this reason drag reducers are
where possible injected downstream of booster pumps

Drag Reducer Chemicals Drag Reducer Chemicals
Properties:
be readily soluble in oil
have a high molecular weight
be inert to chemical changes within the crude
be compatible with other chemicals (e.g. demulsifiers)
Commercially available products
poly-metacrylates
poly-dimethylsiloxanes
poly-butadienes
poly-isobutylenes
poly-isoprene


Shell have developed a method whereby solid polymers are injected into the
pipeline. These polymers dissolve slowly, thus ensuring that the required amount of
75
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
drag reducer is available along the entire length of the pipeline. Additionally, solid
polymer is more likely to pass through pumps, etc. and so continue to dissolve and
provide drag reduction downstream.

Drag reducers are soluble in oil but not in water. For this reason the effectiveness of
these products is found to decrease with increasing water cut.
Due to their insolubility in water, sometimes slimy products are observed in
dehydration tanks. These slimes cause water in oil emulsions to become stabilised
resulting in a deterioration of the dehydration process. Testing of compatibility of
drag reducers with the demulsifier used in the system is therefore an important
requirement.

Drag Reducer Chemicals Drag Reducer Chemicals
Drag reducers are oil soluble only and their effectiveness
decreases with increased water cut
Types of Products:
solutions with concentrations from 0.5 - 10%
solids which must be dissolved onsite
solids which are injected directly (with some water)
Beware:
Many products break down under high shear conditions and
lose their effectiveness
Often slimey products enter the dehydration facilities and
disturb the oil water separation


















Economics of drag reducers
The economic viability of using drag reducers depend on either or both of the
following:
76
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
reduced energy consumption for pumping
increased pipeline capacity

The benefits to be derived from these two factors by the use of the drag reducer
must be greater than the cost of the drag reducer itself. These costs also have to be
compared with other capacity improvement options such as laying a further pipeline
for instance. Although laying a pipeline involves a larger up front investment,
especially if production restrains are severe, this option is likely to be more cost
effective in the long run.
Drag reducers therefore tend to be economically viable where such options are not
realistic, or where throughput restrictions are only temporary


Drag Reduction Drag Reduction
Economics depends on:
Reduced energy consumption for pumping
Increade pipeline capacity
Compare with laying (further) pipeline
Economically viable for temporary throughput restrictions


















Foaming
77
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Foaming is the phenomena where due to the low surface tension between liquids
and air, and the presence of sufficient mixing energy, the air and liquid become a
stabilised mixture called foam. Foam can also be called a gas liquid emulsion where,
in comparison with oil/water emulsions, both the gas external as the water external
emulsion can exist. The reduction of the surface tension is often caused by the
presence of natural surfactants in these liquids or the use of certain process
chemicals (e.g. detergents for cleaning, stimulation additives, etc.)
Foaming can cause a number of operational problems including the following:
The carry-over of liquids into the gas phase in separators resulting in a less
efficient gas liquid separation process. This is often the case with a liquid in gas
foam where gas is the continuous phase.
Disturbances in separation processes such as dehydration, deoiling, filtration and
other water treatment processes such as de-aeration using vacuum de-aerators,
etc.
Pump cavitation caused by the entrainment of gas in the liquid phase
Some tight gas in liquid foams can significantly increase the apparent viscosity of
the liquid phase requiring higher pumping energy.

As foaming can cause all the above negative effects, the use of defoamers is often
the only option to remediate foaming.
For aqueous foams often polyglycols can be used which work on weakening the
bubble film by also moving to the water gas interface thereby inactivating the
surfactant. Very often a very low concentration of defoamers is required to stop the
foaming to occur. The siloxanes is another group of defoamers which can be used to
stop foaming. As these products have a low water solubility, they are not
recommended to be used for the treatment of injection water as this may result in
well impairment. A third group of defoamers are the hydrophobic (=water hating)
surfactants which counteract the hydrophilic (=water loving) surfactant(compare with
demulsifiers which work on weakening the water droplet film).
Foaming
Occurs in Liquids with Low Surface Tension and Exposed
to Turbulence ( e.g. De-airator Towers, O/W, G/O Separators)
Results in:
Liquid Carry-Over and Lower Efficiency Operations
Separation/ Treatment Process Disturbances
Pump Cavitation (Gas Entrainment in Liquid Phase)
Defoamers:
Polyglycols (work on weakening bubble film)
Siloxanes (less suitable in water due to low solubility)
Hydrophobic Surfactants


78
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

4. Inorganic Scales


Hydrocarbon (Water) Processing Deposits
Hydrocarbon Based Deposits
Hydrates
Crystalline Water and Hydrocarbon Compounds.
Wax
Parafinic, Alkane, Component of Crude Oils.
Asphaltenes
Natural Compounds Dispersed in Crude Oils.
Aqueous Based Deposits
Scale
Inorganic Chemical Deposits.


Water is an excellent solvent for many chemical species including salts.
The concentration at which the salts are present in the water, varies significantly
from place to place. These salts are dissolved in the water in the form of ions. The
positive charged ions are called cations while the negatively charged ions are
called anions.
Some examples are:

Cations: Na
+
, Ca
2+
, Mg
2+
, Ba
2+
, Sr
2+
, Fe
3+
, etc.
Anions: Cl
-
, NO3
-
, HCO3
-
, SO4
2-
, CO3
2-
, PO4
3-


The combination of cations with anions results in the formation of salts.
Some salts such as Sodium Chloride (NaCl) have a high solubility which means that
large quantities can be dissolved in water before saturation is reached and NaCl
precipitation takes place.
Other salts such as Barium Sulphate (BaSO4) have a very low solubility of a few
milligram per litre only.
In an aquifer the salt content of the water is in equilibrium with the salts present in
the reservoir rock at reservoir pressure and temperature. In a carbonate reservoir,
the Calcium and the Carbonate concentration in the water phase are at their
saturation point.
By changing pressure, temperature, or another variable, the solubility of a certain
salt in the water can be exceeded resulting in precipitation (often in the form of salt
crystals) of a certain amount of that salt until saturation is reached for this new
situation.

79
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
4.1 Oil Field Water Scales


Scale
Oilfield Waters Contain a Variety of Dissolved Salts.
Seawater Contains SO4
2-
.
Formation Water Often Contain HCO3
-
, Divalent and Trivalent Cations.
Ion Concentration (mg/l)
Brent Nigeria Marmul Sirikit Champion Venezuela
Sodium 1640 8400
Calcium 59 100
Magnesium 10 70
Barium
Strontium
Chloride 2167 11000
Sulphate 10 50
Bicarbonate 841 4000
pH (@ 25C) 7.6 8.1
Salts May be Precipitated as Scale by:
Pressure and Temperature Changes.
Ionic Balance and pH Changes.
Mixing of Incompatible Waters.



Range of Water Quality Parameters Range of Water Quality Parameters
P a r a m e t e r s S e a w a t e r F o r m a t i o n W a t e r
D i s s o l v e d S o l i d s m g / l
T o t a l D i s s o l v e d S o l i d s 3 0 , 0 0 0 - 4 1 , 0 0 0 1 0 0 - 3 3 6 , 0 0 0
S o d i u m 1 1 , 0 0 0 - 1 6 , 0 0 0 4 0 - 1 3 5 , 0 0 0
P o t a s s i u m 3 0 0 - 5 0 0 0 - 1 , 0 0 0
C a l c i u m 3 0 0 - 5 0 0 0 - 5 0 , 0 0 0
M a g n e s i u m 1 , 1 0 0 - 1 , 5 0 0 0 - 5 , 0 0 0
B a r i u m 0 , 1 - 0 , 5 0 - 2 , 0 0 0
S t r o n t i u m 6 - 8 0 - 2 , 0 0 0
I r o n 0 0 - 1 0 0
C h l o r i d e 1 7 , 0 0 0 - 2 4 , 0 0 0 6 0 - 2 0 0 , 0 0 0
S u l p h a t e 2 , 4 0 0 - 3 , 2 0 0 0 - 5 0 , 0 0 0
C a r b o n a t e 0 0 - 1 , 0 0 0
B i c a r b o n a t e 1 2 0 - 1 5 0 1 0 0 - 3 , 0 0 0
A c e t a t e 0 0 - 1 , 5 0 0
P r o p i o n a t e 0 0 - 3 0 0
B u t y r a t e 0 0 - 5 0
S p e c i f i c G r a v i t y 1 , 0 2 0 - 1 , 0 3 2 1 , 0 0 0 - 1 , 2 5 0
D i s s o l v e d O x y g e n 6 - 1 1 0
C a r b o n D i o x i d e 0 0 - 2 , 0 0 0
H y d r o g e n S u l p h i d e 0 0 - 1 , 0 0 0
p H 8 , 0 - 8 , 4 4 - 1 0
T e m p e r a t u r e 0 - 3 0 2 0 - 1 5 0
T o t a l S u s p e n d e d S o l i d s 0 , 1 - 2 0 1 - 1 0 0




This precipitation of excess salt from a solution is called scaling.
The importance of this for the oil industry is that when scaling occurs in the
production system, it may restrict flow through injection and flow lines, impair the
80
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
formation around the well bore, etc. Galvanic Cell corrosion can result from scaling,
when for instance the tubing is covered with scale but at some places the scale
came off. The result is that the bare parts of the tubing are (via the conductive water)
in electric contact with other metal parts in the system whereby an electric current
will remove iron from the bare tubing parts resulting in pitting corrosion.

Apart from loss of production and damage to equipment, in some cases it can also
result in an HSE problem. This is the case if together with for instance Barium or
Strontium scale, also minute amounts of radio active material are co-precipitated.
As result the radio-active material builds up in the production facilities and cause an
environmental and/or safety hazard.

Impact of Scale Crystallisation
Reservoir
Reduces Near Wellbore Permeability; Resulting in High Skin and Lower Inflow.
Wells
Flow Restriction Resulting in Higher Pressure Losses or Lower Throughput.
Loss of Equipment Functionality (Esp. Pumps and SSSVs).
Galvanic Cell Corrosion.
Restricted Well Entry.
Flowlines and Surface Facilities
Flow Restriction Resulting in Higher Pressures or Lower Throughput.
Loss of Equipment Functionality (Esp. Pumps and Pressure Relief Valves).
Galvanic Cell Corrosion.
HSE
Sulphate Scales Often Contain NORM (Naturally Occurring Radioactive
Materials) - LSA (Low Specific Activity) Elements.
Usually Uranium and Thorium Decay Series Products.


The Viewgraph on the next page shows a number of scales which can be
encountered in oil field operations.
Rock salt (NaCl) can be expected to be formed when producing from an oil reservoir
with very high NaCl concentrations (over 300,000 mg/l). In contrary, it can also occur
when producing gas from a formation with a low NaCl content. When the gas is
produced, due to the pressure drop in the tubing part of the co-produced water will
evaporate in the gas thereby increasing the salt content in the water. When this
continues, the salt content can eventually reach saturation point and precipitate in
the tubing.
A number of the scales will be discussed in more detail below.
81
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Inorganic Oilfield Scales
Rocksalt NaCl
Carbonates CaCO
3
FeCO
3
BaCO
3
PbCO
3
2PbCO
3
.Pb(OH)
2
Sulphates CaSO
4
.
x
H
2
O
SrSO
4
BaSO
4
PbSO
4
Sulphides S
8
FeSx
ZnS
PbS
Oxides etc. Fe
2
O
3
, Fe(OH)
3
Others CaF
2
CaSiO
3
Pb metal, Pb(OH)Cl
Fe
3
(PO
4
)
2
Ca
5
[(OH)(PO
4
)] etc.


Carbonate scales are the most common scales encountered in oilfield operations.
Calcium is most often the Cation, but also Barium and Strontium Carbonates are
possible.
The figure below demonstrates the complexity of the equilibrium of the different ions
playing a role. From the figure, formation of a carbonate scale can only occur above
pH 4, as at this pH the first carbonate ions are formed. It is also clear that apart from
the pH, also the CO2 concentration plays an important role.
The CO2 content in the water is very pressure and temperature dependent.

Carbonate Scale
Carbonate Deposition is Complex and Dependent on the
Equilibrium between Bicarbonate, Carbonate, and CO2.
Total Carbonate = [CO2]

+ [H2CO3]

+ [HCO3
-
]

+ [CO3
2-
]
Carboxylic Acids May Affect HCO3
-
Determination.
Volatile Fatty Acids (VFA) May Be Reactants when Titrating for Bicarbonate .
Gives a False Value Indicating a Higher than Actual Scaling Potential.
Concentration Variation of Depressured Sample
Downhole Surface
CO2 mg/l 7660 100
HCO3
-
mg/l 202 2850
pH 4.7 6.9
Because of the Equilibrium Complexity and the
Loss of Gaseous CO2, it is Not Recommended
to Use Corrections of Surface Samples to
Downhole Concentrations Without Calibrating
Using an Actual Downhole Pressure Sample.


82
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
It is very important when taking samples for analysis, that the exact CO2 content at
reservoir conditions is known as well as the pH. To allow calibration for CO2, a
downhole sample has to be taken and analysed. These data are of importance in the
prediction of scaling.
Apart from the CO2 content (influenced by pressure and temperature), an increase
in pH will significantly affect the solubility of calcium carbonate by shifting the
equilibrium to the right hand side. Carbonate scale deposits are acid soluble and
hydrochloric acid (HCl) is often used for stimulating wells which are scaled up with
calcium carbonate.
Presence of large quantities of NaCl (or other dissolved solids), however, will
increase the solubility of Calcium Carbonate. This is called the No common ion
effect and is the result of increasing the ionic strength of the water solution.
The Stiff and Davis formula can be used for predicting the likelihood of carbonate
scale deposition. Scaling may occur when the Scaling Index is positive. The
accuracy of this formula is not very high and its use should be as a first indication
only.
Carbonate Scale Deposition
Carbonate Deposition is Affected by:
Pressure Decrease (decreases partial pressure of CO
2
).
Temperature Increase (decreases solubility of CO
2
).
pH Increase (Ca
2+
+ CO
2
+ 2OH
-
==> CaCO
3
+ H
2
O).
NaCl up to 20,000 ppm Increases Carbonate Solubility by ~2.5 times.
Can be Predicted with the Stiff and Davis Stability Index
Scaling Index (S.I) = pH - (K + pCa + pAlk).
pH = actual water pH.
K = a constant dependent upon temperature and ionic strength.
pCa = negative logarithm of calcium concentration.
pAlk = negative logarithm of total alkalinity.



Calcium Carbonate Scale












83
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

Calcium Sulphate deposition is mainly the result of mixing of incompatible fluids.
Typical is the injection of sea water with a Sulphate content of some 2000 - 3000
ppm into a Calcium containing reservoir. The calcium from the reservoir reacts with
the sulphate to form calcium sulphate.
There are different forms of calcium sulphate which include CaSO
4
.2H
2
0 (Gypsum),
the most common oilfield form at lower temperatures and CaSO
4
(Anhydrite).
The solubility of calcium sulphate increases to a temperature of 38
o
C, after which the
solubility decreases. Above this temperature the anhydrite form is becoming the
more dominant form and is less soluble compared to gypsum. Like all other scales,
also calcium sulphate solubility increases at increased pressure. Also the presence
of large quantities of dissolved salts other than calcium or sulphate, (i.e. sodium
chloride etc.), positively affect the solubility of calcium sulphate. In contrary to
carbonate scales, the solubility of sulphate scales is virtually pH independent. These
types of scale can therefore also not be dissolved with acid.
Sulphate Scale
Sulphate Scales are Generally a result of Chemical Interaction
between Formation and Injection Fluids.
Such as: Ca
++
+ SO4
--
=> CaSO4
Solubility Decreases with Decreasing Pressure.
But not as markedly as for the Carbonate system.
Solubility is Virtually pH Independent.
Solubility is Mildly Temperature Dependent
Gypsum Solubility Increases with Temperature to about 40C & then
Decreases.
Dissolved Na
+
, up to 160,000 ppm, Increases R-SO4 Solubility.
Can be Predicted with Skillmans Method
Solubility = 1000 [(X
2
+ 4K)
0.5
- X]
K = Solubility product constant (a function of ionic strength and temperature)
X = Excess common ion concentration (difference between Ca
2+.
and SO4
2-
)



Calcium Sulphate Scale


Apart from calcium, other sulphate scales include barium and strontium. These
scales have a very low solubility compared to calcium sulphate. Barium sulphate
solubility at ambient temperatures and pressure is only +/- 2 mg/l. In comparison the
solubility of calcium sulphate under similar conditions is +/- 2000 mg/l, while the
solubility of strontium sulphate is +/- 250 mg/l.
The solubility of these salts increase with increased temperatures (up to 100
o
C) and
pressure. Solubility is unaffected by changes in pH while increased salt content
again increases solubility.

84
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Over the last decade, naturally occurring radioactive materials (NORM), have been
found to co-precipitate together with mostly barium and strontium scales.

Barium/Strontium Sulphate Scale
Mostly Caused by Mixing of Incompatible Waters.
Compounds Have Very Low Solubility (Ba less than Sr).
Solubility Increases with Increased Temperature.
Even so BaSO4 solubility at 90C is still only 4 mg/l.
Solubility Increases with Increased Salt Content.
Solubility is Unaffected by Changes in pH.
Chemically Similar to Radium, may Co-precipitate with
Radioactive Scales.
Not Acid Soluble.


These radio-active materials with a low specific activity, can be present in the
producing formation, and leach out via the produced water. Together with normal
scale it can become deposited in the well bore, tubing or surface production facilities.
The importance is that as the scale layers building up in the system the radio-activity
level will increase and could pose health or environmental hazards.
At the end of this chapter, some more details on NORM will follow.
85
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Barium Sulphate Scale
Courtesy of Shell Expro


Iron based deposits or scales can be the result of Iron ions present in the water
naturally or the result of corrosion or Sulphate Reducing Bacteria (SRB).
Formation waters normally contain only a few mg/l of iron and values as high as 100
mg/l are rare. Precipitated iron compounds are a common cause of deposit formation
and injection well plugging, and can also be a sign of a serious corrosion problem.
Carbon dioxide (CO
2
), a corrosive gas, reacts with iron to form ferrous carbonate
(FeCO
3
).
Presence of hydrogen sulphide (H
2
S) in the produced water or gas together with
iron, will result in the formation of iron sulphides (FeS). The presence of H
2
S in the
production system can, apart from natural reasons, also be caused by SRB bacteria
in the presence of sulphate.
Oxygen combines with iron to various (corrosion) compounds. Ferric (Fe
2
O
3
) and
Ferrous Oxide (FeO) are common forms resulting from contact with air or oxygen
containing water. Other forms are the hydroxide forms of iron Fe(OH)
2
and Fe(OH)
3.
Iron deposits/scales can normally be removed with acids like HCl. Care has to be
taken by back production that depleted acid with iron can again deposit as iron
hydroxide. For this reason, often complex forming chemicals like citric acid or
ethylene diamine tetra acetic acid (EDTA) are used to avoid this re-precipitation of
iron. In case the iron deposit is the result of corrosion, a detailed investigation into
the cause(s) and possible remedial actions is required.
86
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Iron Compounds
Iron Based Deposits May Exist as:
Ferrous Carbonate FeCO3 Siderite.
Ferrous Sulphide FeS Pyrite.
Ferrous Oxide FeO Hematite
Ferric Oxide Fe2O3.Fe3O4 Magnetite.
Ferrous Hydroxide Fe(OH)2
Ferric Hydroxide Fe(OH)3
All Deposits are Insoluble in Water.
Hydroxides are difficult to treat with Acid.


Scale Prediction
Prediction of scaling is an important tool when developing new fields and/or water
injection projects.
The most simple form of prediction is by simple calculations such as the Stiff and
Davis (CaCO
3
) and the Skillman, McDonald and Stiff (CaSO
4
) indices.
The equation for the saturation index (SI) of calcium carbonate according to Stiff and
Davis is:
SI = pH - (K + pCa + pAlk)

pH = actual pH of the water
K = A constant which is a function of salinity, temperature and water
composition
pCa = The negative logarithm of the calcium concentration
Palk = The negative logarithm of the total alkalinity (CO3
2-
+ HCO3
-
)

The Skillman, McDonald and Stiff equation is:

S = 1000 [(X
2
+ 4K)
0.5
-X]

S = gypsum solubility (milliequivalent/liter)
X = excess common ion concentration/liter. This is the difference between the
calcium-
and the sulphate concentration.
K = solubility product constant ( a function of the ionic strength of the water and
temperature)

These calculations are a rather coarse method of predicting the likeliness of scale
formation and cannot be applied in more complex situations.
87
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Over the past decade, more sophisticated computer models have been developed,
amongst others, the KSEPL (RTS) developed Waters program. This software tool
was rather complex to run and did not have sufficient flexibility to predict a wide
range of scaling conditions.
A later development was Scalechem which, in the beginning also suffered from a
user unfriendly approach.
However, this program has been improved over the past years resulting in the
release of a user friendly Windows 95 version. This latest version is capable of
correlating high temperatures and pressures, accounts for flow rates and many other
features. The only scale it cannot accurately predict is metallic lead (Pb).
As for many other Process Chemistry areas, the accurate prediction of software tools
like Scalechem, is fully depending on the accuracy of the data used. In these
programs the composition of water at downhole condition is required from where the
software can calculate the composition when the sample is produced to surface.
Water samples, where possible, have to be analysed for pH, CO2 and HCO3-
content at actual downhole conditions (pressure and temperature). This is in
particular true where CO
2
takes part in the reaction equations. Analytical data of a
surface sample cannot be used without accurate calibration tables based on
downhole samples.
Prediction of Water Formed Scales
Calculations (Only Rough Indications)
Stiff and Davis Scaling Index (CaCO
3
).
Skillman, McDonald and Stiff (CaSO
4
).
Computer Programmes
Consider More than One Type of Scale.
Consider Multiple Factors which may Induce Scale.
Scalechem
Correlates for High Temperatures and Pressures.
Mixes Water and Gas Compositions.
Accounts for Flowrates, Temperatures and Pressures.
Predicts all Scales except for Pb
Currently Under Development for the New PT Computing Portfolio.
Available Q2-1997 as a User Friendly GUI version, under Windows 95.
Accurate Data Entry is Required for Meaningful Results.


Prediction of scaling conditions are an important tool in the development phase of a
production or water injection project. Knowledge of the situation to be expected can
be used to prevent scaling to occur or to take measures to manage scaling.
Different categories of approaches are available for the prevention or control of
scaling.
These include the following:

88
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Scale Prevention and Control
Category Summary of Method
Process Design Operate Under Less-Scaling
Conditions.
Ion Removal or Exchange Remove Ions to Prevent Them
Reacting.
Inhibition Leave Ions in Solution
Apply Chemical Treatment to
Disperse Precipitates.
Modify Crystal Growth Pattern.
Removal Allow Deposits to Accumulate
and Remove Periodically by
Chemical / Mechanical Means.

Process Design:
Taking measures in the design of the injection/production system to minimise or
prevent scaling.

Removal of the scaling ions:
In this case the injection water is pre-treated to remove one of the scaling ingredients
to prevent scaling after mixing with the water in the formation.

Inhibition
The use of chemicals to prevent the scaling ions to precipitate but stay either
dissolved or dispersed in the water phase.

Removal
In cases where scaling takes place at moderate rates, the most cost effective
approach sometimes could be to allow deposition, while periodically removing the
scale mechanically or chemically.

Process Design
As described above in the category of process design, options are mainly to take
measures in the production process to control scaling.
A number of options include the following:

pH control.
In particular for carbonate scales, the pH plays an important part in the
equilibrium.

CO
3
2-
+ H
+
HCO
3
-
+ H
+
H
2
O + CO
2

The equilibrium is moved from carbonate via bicarbonate to carbon dioxide by
adding acid (H
+
).
89
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
The control of the pH can be effected by dosing small concentrations of for instance
acetic acid which is low in corrosivity.
Otherwise where the water and gas phase contain carbon dioxide, maintaining the
pressure will keep the CO
2
content high, thereby preventing an increase of the pH
and consequently scaling.
As for carbonates, for iron scales, pH also plays an important role in the solubility of
these compounds.
pH control is not a measure which is widely applied as it may create increased
corrosion problems. Only where minimal adjustments in pH are required this option
could be investigated.

Temperature control
For water compositions where scaling is sensitive to temperature reduction,
sometimes the insulation of pipe- and flowlines may be sufficient to prevent or
minimise scaling.

Incompatible waters
In particular for water injection projects, the compatibility of the injection water with
that in the formation is very important.
For instance, if the injection water contains a large concentration of carbonate, and
the formation water calcium, together this could result in the formation of calcium
carbonate when these waters are mixed following injection.
A typical example is injection of sea water containing sulphate in a reservoir
containing either calcium, barium or strontium.
The use of software tools such as Scalechem can predict the likelihood of scaling to
occur either in the reservoir or in the producing wells.
Where possible, mixing of incompatible waters should be avoided. Where this is not
possible, two options are available to prevent impairment and scaling in the
production facilities.
These are: removal of incompatible chemicals from the injection water or the use of
scale inhibition chemicals.

90
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Operate Under Less Scaling Conditions
pH Control
Maintaining Low pH May Prevent Carbonate Scaling.
Temperature Control
Pipeline Insulation May Reduce Temperature Changes.
Avoid Mixing of Incompatible Waters
Carefully Select Injection Water.
Do Not Use Mixed Sources for Injection Water.
Process Design


Ion removal or exchange
In case a water source has to be used which is incompatible with the formation
water, one option is to remove or exchange the interfering ions with non-interfering
ones.
One method is to exchange the scaling ions such as calcium, magnesium, carbonate
or sulphate, by non scaling ones such as sodium (Na) and Chloride.
This can be done by using ion exchange units which use exchange resins.
The method, however, is very expensive and more applied to removing scaling
conditions for boiler feed water rather than for large scale water injection projects.

In the past scaling ions were removed by precipitating these chemicals and removal
of the deposits via filtration. Also this method is not widely applied as the
precipitation and filtration processes have to be complete to avoid solids to bypass
the filtration units and deposit later in the injector wells.

Ion removal, is a process, whereby the injection water is passed via a membrane
filtration system with pores allowing only the smaller ions to pass. Larger ions such
as sulphate and (bi)carbonate are too large to pass and are concentrated in a reject
stream. The additional advantage of this process in addition to removing a scaling
ion is that by the removal of the sulphate (the main feed stock for these bacteria) the
possibility of corrosion due to sulphate reducing bacteria is diminished.


91
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Ion Removal or Exchange
Remove One of the Offending Ions to Prevent Reaction.
Normally Only Applicable for Water Injection Where Early Break-Through and
Incompatibility is Expected.
SO4 can be Removed from Seawater.
Cross-flow Filter Membranes Reject Ions Based Upon Their Hydrated Size
and Charge.
Electro-Dialysis Reversal (EDR) or Ion Exchange Systems Replace the
Offending Cation with One That is Less Problematic.


The Viewgraph on the following page shows the result of a sulphate removal trial
from sea water conducted at the Orkney water test centre. It demonstrates that only
the larger ions are selectively removed while the smaller ones, are much less
affected. This technology, while sufficiently developed to be applied in the field, is in
most water injection projects still too expensive. The preferred way often is to use
scale inhibitors at the initial phase of the injection project in the injection water and
again in the producers during the period that a scaling mix of injection and formation
water is produced.

Sulphate Removal
Determinant
Seawater SRM Product
Sodium mg/l 11,120 10,050
Potassium mg/l 420 354
Calcium mg/l 420 274
Magnesium mg/l 1,340 620
Chloride mg/l 20,035 18.110
Sulphate mg/l 2,830 25
Bicarbonate mg/l 141 20
Orkney Water Test Center Trial

92
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS


Scale inhibitors
Scale inhibitors are most commonly applied to control the formation of scales. In
water injection projects these chemicals are used to prevent impairment in the near
well bore region, while for produced water, also the downhole- and production
equipment is given protection.
Scale inhibitors are chemicals which will delay, reduce or prevent scale formation
when added in small amounts to a normally scaling water.
One category of inhibitors are the chelating agents. These products work by reacting
with the scaling cations (Ca, Mg, Ba, Fe) by forming soluble complexes.
Examples of these products are the complexed organic acids such as Ethylene
Diamine Acetic Acid (EDTA), Mostly these chemicals are used in the form of a
sodium salt (e.g. EDTA-Na
2
) and are active over a specific pH range depending on
the Cation to react with.
When applying these chemicals, the dosage used should be sufficient to chemically
bind such a portion of the scaling cations that the concentration of free cations is
below the maximum solubility threshold for the scale in question.

Threshold type inhibitors are chemicals which achieve effectiveness at low
concentrations. At these low doses, these products may prevent precipitation of
scale by keeping the water supersaturated for a prolonged length of time. The time
for which these products keep this supersaturation is dependant on the chemical
water composition, the type of product and other factors including temperature,
turbulence in the system and the presence of nuclei (solid particles).
Their effectiveness at low dosing rates is caused by these chemicals to adsorb onto
the crystal growth sites thereby inhibiting their growth as well as settling on pipe
walls.
Several generic threshold inhibitors are available which all have their specific
application limits.
Polyphosphates were commonly used in the past but due, to their low temperature
tolerance (up to +/- 55
o
C), were later replaced by the more stable phosphonates.
These products are most effective for the inhibition of carbonate scales, while the
phosphates are also effective for barium- and calcium sulphate scale.
Another group of threshold inhibitors are the so-called polymers, polyacrylamides
and the polyacrylates. These products have a high temperature stability, and are
also effective for the inhibition of Barium Sulphate.
Very often blends of the above groups of chemicals are being used and tuned to the
typical scaling conditions encountered.


93
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Scale Inhibitors
React One of the Ions to Keep It In Solution or Dispersed.
Chelating Agents.
Use Active Sites to Chemically Bind (Chelate) with Ions which are
Susceptible to Scaling.
Complexed Organic Acids; EDTA, DTPA, NTA.
Organic Salts; Lignins, Tannins, Lignosulphonates.
Must be Applied Stoichiometrically for Effective Treatment.
Complexes may be pH sensitive.
Threshold Type Inhibitors.
Maintain Precipitates in Dispersed State by Adsorbing onto Crystal Growth
Sites and Inhibiting Crystal Growth.
Inhibit Agglomeration on Pipe Walls.
Effective in Low Concentrations.
Polyacrylamides, Polyacrylates, Polyphosphonates.
Laboratory Tests Are Essential for Cost Effective Treatment.


When inhibitors are being applied, they always need to be introduced before the
scale has been formed as most products do not or only slowly dissolve already
precipitated scale.

For water injection systems, where the water is self-scaling under system- or
reservoir conditions, the inhibitor must be applied continually from the start of the
injection at dose rates which are dependent on chemical type and scaling potential
but are typically in the range 1-50 mg/l. (see points listed on Viewgraph for
continuous injection).

If the scaling is the result of incompatibility between injection and formation water,
then the selected inhibitor may initially be injected at a higher dosage rate (in the
injection water) until a buffer zone of inhibited water is created in the injector
wellbore area. Dosage can thereafter be reduced or even be discontinued until the
injection water is close to breaking through in the producers whereby mixing with the
formation water will cause scaling in producers and/or facilities.
At that later stage squeeze injection of chemical is often applied rather than adding
the inhibitor to the injection water. (see points listed on Viewgraph for squeeze
injecting inhibitor). Inhibitor dosing in the injection water will not prevent scaling in the
production wells as the product will have long been adsorbed in the reservoir.
The frequency of squeeze injecting inhibitors in the scale prone producers can vary
dramatically and extremes between a few weeks and a few years have been
observed in practice. In most cases a high overdose of chemical will have to be
injected in the well where it ideally absorbs in the formation being slowly released
when producing the scaling water. In practice however, often around one third of the
product is produced back within a few days while another third will never be
produced back. This makes the application of squeeze inhibitors relatively
expensive.
94
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

Application of Scale Inhibitors
Inhibitors Must Be Introduced Before the Scale is Formed.
Continuous Injection.
Applicable for Scale in Wells and Surface Facilities.
Apply Upstream of Initial Scaling Point.
Ensure Good Mixing.
Injection Rates 1-50 mg/l.
Squeeze Treatment.
Applicable for Scale in the Formation (Near Wellbore).
Chemical Squeezed Into Formation.
Adsorbed onto Rock Surface or Precipitated in the Pore Space.
Gradually Released During Production thereby Providing Continual Inhibition.
Life of the Treatment can Cary from 1 Month to Several Years.
Can be Expensive as Generally 1/3 of Treatment is Immediately Back Produced
and 1/3 of Treatment is Often Lost in the Formation.


Non-chemical Crystal Growth Inhibition
Over the past decades many claims have been made that magnetism could prevent
or delay the onset of deposition of scales such as calcium carbonate. In the potable
water industry the use of magnets has been reported to minimise carbonate scale in
drinking water lines.
Also reportedly, in China and Russia many wells have been provided with magnets
for the same reason. Apart from preventing scale, also claims have been made that
these magnets prevent wax deposition.
During the seventies, some experiments have been conducted by KSEPL (now RTS)
in Rijswijk, but never any solid proof was obtained.
The view graph below describes some of the claims which are being made about the
way these magnets inhibit scale formation.

So far, no clear evidence has been found that magnets can reduce scaling, but as
the technology would be very cheap to be applied and in addition is environmentally
inert, a more detailed study of this phenomena could be worth wile. Research in this
subject is still underway, and funded by a number of oil companies.

95
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Non-Chemical Crystal Growth Inhibition
Physiosorption
Electro-Magnetic Crystal Growth Modification.
Applying a Strong Magnetic Field at the Time of Crystal
Formation May Modify the Crystal Shape and Inhibit Multi-
Crystalisation.
In Some Circumstances May Modify Post Formation Crystal
Shape Giving Some Deposit Degradation.
Applicable to All Crystalline Materials.
Have Been Successes and Failures
Evidence is Lacking and Theory is Still Under Discussion.
ARC Have Yet to Simulate Field Reported Success in Their Test Loop.
Environmentally Inert.
Relatively Inexpensive.


Even where scale inhibitors are applied, complete prevention of deposition is rarely
achieved. Failure of chemical dosing will occur periodically and removal of resultant
scale accumulation may be required.

Scale can be removed either chemically or mechanically.
Calcium carbonate scale can normally easily be removed with Hydrochloric Acid
(HCl) unless the scale is covered with oil. In this case a surfactant or solvent has to
be added to the acid.
When using corrosive acids such as HCl, corrosion protection via inhibitors is often
required, in particular with normal carbon steel tubing completions.

In contrary to carbonate scales, sulphate scale cannot be dissolved with regular
acids. Apart from physical removal, successes have been claimed by using mixes of
strong Ethylene Di-Amine Tetra Acetic Acid (EDTA) and other gelating agents which
are available via chemical suppliers.
Another possible, but more complex method is to pre-treat the sulphate scale with
ammonium carbonate in which the calcium sulphate with a relatively high solubility is
transformed into the less soluble calcium carbonate. The soluble ammonium
sulphate can then be flushed away prior to treating the generated calcium carbonate
with HCl.

Sulphide deposits like FeS are soluble in strong acids like HCl. Extreme care has to
be taken with these treatments as with this chemical reaction the very toxic H2S gas
is formed and safety precautions have to be taken.

In cases where the scale cannot chemically be removed, mechanical removal is the
only remaining option. Physical removal is difficult and may require the use of jack
96
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
hammers, reamers of high pressure water jets. Coiled tubing can be used for internal
removal, but more common is to pull the tubing from the well for cleaning.
Chemical Scale Removal
Calcium Carbonate are Best Removed by Acid.
CaCO
3
+ 2HCl > CaCl
2
+ CO
2
+ H
2
O
Corrosion Inhibitor is Required to Protect the Steel.
Use Less Aggressive Acids for More Frequent Applications.
Calcium Sulphate Scale can be pretreated with ammonium
carbonate prior to removal by hydrochloric acid
CaSO
4
+ (NH
4
)
2
CO
3
> (NH
4
)
2
SO
4
+ CaCO
3
This May Not Always be Effective - Mechanical Removal May be Needed.
Sulphate Scales May be Removed with EDTA.
Sulphide Deposits can be Removed with Hydrochloric Acid.
2FeS + 6HCl > H
2
+ 2FeCl
3
+ 2H
2
S
Care Must be Taken Due to Hydrogen Sulphide Production.


Radioactive scale
Trace quantities of the radioactive elements uranium (
238
U) and thorium (
232
Th) have
been present in the earths crust since its formation. Consequently, these elements
are also common in oil/gas bearing geological formations. Both
238
U and
232
Th are
the parent of a complex series of successive decays in which their radioactive
daughters are formed. They are called Naturally Occurring Radioactive Materials or
NORM. The most common radioactive materials or NORM encountered in E&P
operations are
226
Ra,
222
Rn (Gas),
210
Pb,
210
Po,
228
Ra and
228
Th.
Some of these daughters may be co-produced with oil/gas well fluids. Normally the
natural concentration of these radioactive isotopes is very low and will not cause an
HSE problem. However, these materials may concentrate and co-deposit together
with Barium and Strontium scales. The deposition of these concentrated radioactive
material is called Technologically Enhanced Natural Radioactive (TENR). Its
deposition on tubulars, flow lines and in production facilities can cause a serious
Health and Environmental hazard and requires the specialist contractors for the
removal of the scale and its disposal at safe locations such as nuclear waste
repositories.

Three different types of radiation can be distinguished:
The first type is called Alpha radiation consists of the emission of Helium Nuclei
from the radioactive element. As these helium particles are relatively large (atomic
weight = 4), their penetration depth is very small and are easily stopped in the
surface cells of the skin.
The second type is Beta radiation which consists of emission of electrons. As
electrons are relatively much smaller compared to helium nuclei, their penetration
depth is higher.
97
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
The third type of emission is Gamma radiation which is the emission of photons
which again are much smaller than electrons. Resultingly, the penetration depth of
photons is higher which makes this type of radiation more dangerous.

Another name for the most common oil field radio active scales is LSA or Low
Specific Activity scale. This is because the radioactive materials in the scale only
make up a very small portion of the scale deposit. Eventhough by building up a layer
of scale the total concentration of this material may build up beyond safe levels and
special care has to be taken in handling and disposing it.



NORM & LSA
Naturally Occurring Radioactive Materials.
Normally Daughters of Uranium and Thorium Decay Series.
Ra
226
and Ra
228
are the Most Commonly Occurring Derivatives.
Co-precipitate with the main Scaling Cations.
Radiation Types
Alpha Radiation (Helium Nuclei): Easily Stopped, Only Affecting Surface Cells.
Beta Radiation (Electrons): Penetrates Only a Few Millimetres.
Gamma Radiation (Photons): Much More Penetrating.
Low Specific Activity
Specific Activity is the Radioactivity per Gram of Material.
Radium and Thorium Form Only a Very Small Fraction of the Scale Volume.
Therefore Such Scales are Classed as Low w.r.t. their Specific Activity.
There is a Low Level of External Hazard.
There is Still a High Internal Hazard if Inhaled or Ingested.
All Exposure Should Be As Low As Reasonably Possible.


The final view graph on water borne scales shows the decay series for radium via
Alpha and Beta emissions.

98
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Radium Decay Series
Pa-234
1.2 m
2.3 MeV
U-234
2.5 x 10
5
y
4.8 MeV
U-238
4.5 x 10
9
y
4.2 MeV
Th-234
24 d
0.2 MeV
Th-230
8.0 x 10
4
y
4.7 MeV
Ra-226
1620 y
4.8 MeV
Rn-222
3.8 d
5.5 MeV
Po-218
3.05 m
6.0 MeV
Po-214
160 us
7.7 MeV
Po-210
138 d
5.3 MeV
Bi-214
20 m
43.3 MeV
Bi-210
5.0 d
1.2 MeV
Pb-214
27 m
1.0 MeV
Pb-210
22 y
0.06 MeV
Pb-206
Stable
0

U-234
2.5 x 10
5
y
4.8MeV
Radionuclide
Half-life
Radiation Energy
Mode of Decay

Uranium Protactinum Thorium Radium Radon Polonium Bismuth Lead


North Sea
LSA Scale
10 ppb
100-1000 Bq/g




99
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS



5. Bacteria and Biocides

Micro-organisms are currently divided into three major domains: the bacteria, the
Archea and the eucarya. Each group has unique characteristics which can have an
impact on various oilfield operations. As the group of bacteria covers most of the
aspects encountered in E&P operations, only the domain of bacteria is discussed
below.

The domain of bacteria can be subdivided into four main types: the aerobic-,
anaerobic-, the mesophilic- and the thermophilic bacteria. These types indicate the
conditions under which different categories of bacteria live and can multiply
themselves. A combination of these types is often used to describe the living
environment of bacteria (e.g. aerobic, mesophilic).

Aerobic Bacteria
Aerobic bacteria live only in the presence of oxygen, predominantly in well aerated
low salinity water. For this reason aerobic bacteria are mostly encountered in
injection water systems where use is made of surface water. Removal of all Oxygen
sources will result in these bacteria to die, the reason for the use of oxygen
scavengers which remove the oxygen from the water.
Examples of aerobic bacteria are iron bacteria, slime formers, sulphur oxidising- and
hydrogen oxidising bacteria.

Anaerobic Bacteria
The word anaerobic means without air. Indeed these bacteria can only live in
environments without oxygen, which is common for production streams and facilities.
An example of anaerobic bacteria are Sulphate Reducing Bacteria (SRB) which are
further discussed below.

Mesophilic Bacteria
Mesophilic Bacteria means that type of bacteria that only live and multiply in
moderate temperature environments (20 - 40
o
C). At lower temperatures these
bacteria can remain dormant which means that they can stay alive but not multiply,
but at temperatures well above 40
o
C, they will die.

Thermophilic Bacteria
In contrary to the mesophilic type, thermophilic bacteria can live at (much) higher
temperatures. Some SRB, the so-called t-SRB have been found to survive
temperatures of at least 120
o
C and pressures of 500 bar.

100
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Types of Bacteria
Aerobic Bacteria
Live in the presence of oxygen
Anaerobic Bacteria
Capable of living in the absence of oxygen
Mesophilic Bacteria
Thriving at moderate temperatures, usually between 20-40
o
C
Thermophilic Bacteria
Thriving at relatively high temperatures, above 45
o
C
Dormant
Active
Death
20 50 T
o
C
Pressure
Bars
700


Iron Oxidising Bacteria
Iron oxidising bacteria are aerobic bacteria forming iron oxide containing slime
colonies in water containing large quantities of ferrous oxide. They are commonly
observed in water injection systems where these slimes block filtration systems. As
these colonies grows denser, their base may become deprived of oxygen under
which SRB (with resulting corrosion) can develop. Most of these bacteria either use
organic matter or sometimes CO2 as a carbon source.
Iron Oxidising Bacteria
Deposit Iron Oxide and Hydroxide.
Their Activity Results in the Plugging of Filters with Iron
Oxide or Hydroxide Slime.
Corrosion Occurs Under the Deposits.
Detection is Very Difficult.

Sulphate Reducing Bacteria (SRB)
101
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
SRB consist of diverse types of strictly anaerobic bacteria, which can only grow in
the absence of oxygen, but can often survive aerobic conditions. They have in
common the ability to reduce sulphate, sulphite or thiosulphate to hydrogen sulphide
to support their metabolism. The sulphate is not a nutrient, rather is it similar to other
organisms using oxygen for their metabolic processes, and producing CO2.
SRB can tolerate temperatures from -5 to at least 90
o
C and are found in fluids with
pH ranges from 5 to 9.5 as well as pressures up to 500 bar. Reservoir souring (and
subsequent corrosion of well completions and production systems) following the
injection of sulphate and dormant SRB containing sea water is one of the main
challenges related to these bacteria.
H2S formed during the sulphate reduction process can cause metal failure in two
ways. Firstly the H2S can react with steel to form FeS thereby corroding the metal
parts. Secondly the hydrogen resulting from the reaction with iron can penetrate the
metal thereby making the material more brittle and susceptible to stress cracking.
SRB sometimes are enclosed by slimes or debris (=sessile bacteria) under which
they can concentrate and cause the so-called pitting corrosion.
The use of biocides in water injection systems is generally ineffective as a 100% kill
is required to prevent live SRB to enter the reservoir.
In the reservoir the few remaining live bacteria have sufficient time to multiply until
they reach the producing wells.
In production systems a 100% kill is not always necessary and reducing their
numbers to control their growth is often sufficient. However, if SRB are buried under
protective layers as mentioned above, penetration by the chemical is not always
achieved.
SRB, like many other bacteria, use as food supply the fatty acids normally present in
oil/gas reservoirs. Removing this food supply from the bacteria is the preferred
method but is in practice not easily achieved. Only where other bacteria provide this
feed stock a control may be practicable by killing these food suppliers.

Sulphate Reducing Bacteria (SRBs)
SRBs are Strictly Anaerobic - the Presence of Oxygen
Usually Prevents their Growth.
The Main Characteristic of SRBs is that they Reduce
Sulphate to H2S and CO2.
H2S Can Cause Metal Failure (Stress Cracking).
H2S May Lead to Formation Plugging by Iron Sulphide.
H
2
S + Fe => FeS + H
2
Biocides are Generally Ineffective as they Have to Kill 100%
of the Population.
Oxygen Will Often Kill SRB But May Cause Other Corrosion
Removing the Food Supply is the Preffered Method.
SO
4
2-
+ 2H
2
O + Organic Material + SRB => H
2
S + 2CO
2
+ 2OH

-


Sulphide Oxidising Bacteria (SOB)
102
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
In contrary to SRB, SOB only can thrive in oxygen rich environments.
They grow in well aerated systems utilising reduced sulphur compounds such as
sulphur, sulphite and sulphide, which are converted to sulphuric acid. These
bacteria can generate a pH in the range of 1 - 2 which is highly acidic and result in
severe localised corrosion of steel and concrete structures. SOB classically grow in
close association with SRB, where cycling sulphur compounds and variations in
oxygen levels, can lead to sustained corrosion problems.

SOBs are Strictly Aerobic - The Lack of Oxygen Will Inhibit
Their Growth.
The Sulphuric Acid Causes Pitting Corrosion.
Biocide are Generally Ineffective as they Have to Kill 100% of
the Population.
Removing the Oxygen Supply is the Preffered Method.
Sulphide Oxidising Bacteria (SOBs)
O
2
+ S
2-
+ 2H
2
O
Organic
Material + SOB = CO
2
+ H
2
SO
4


Bacterial Survival and Growth Conditions
As we have seen above, bacteria are able to live under extreme conditions and are
found in environments such as hot geysers, sulphur springs, and ice. Whether they
could also originate in oil reservoirs is still unproved as it would require survival, in
dormant conditions, over periods of millions of years at high pressures and
temperatures.
Limits on conditions for bacterial survival are ill defined. Under certain environmental
conditions however, they may be expected to proliferate. These are:

1. Presence of water
2. Carbon source
3. Nitrogen source
4. Inorganic salts - phosphate, iron
5. Electron acceptor (O
2
or SO
4
2-
)
6. Temperature range
7. Maximum pressure
8. pH range
9. Reduction - oxidation potential (Eh) range
10. Salinity range
11. Upper limit on toxic agents (e.g. high H
2
S inhibits SRB)
During growth, bacteria may substantially modify the nearby environment by
creating:
103
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

1. Inorganic by-products (e.g. H
2
S, CO
2
, H
2
SO
4
)
2. Soluble organic by-products (e.g. fatty acids)
3. Insoluble organic by-products (e.g. slimes, polysaccharides)
4. Oxygen depletion, pH and Eh change.

Growth of bacteria can be restricted by a lack of any one of their nutritional
requirements or unfavourable conditions with restrict their growth. Their growth may
be limited by a single factor, small changes in this limiting factor may significantly
affect bacterial growth whilst changes on other parameters have no effect.
By using these conditions, the growth of bacteria can be controlled.

Biocides
Where no control options are available to the continued growth of bacteria,
bactericides or biocides can be applied.
As most of these products have a potential negative impact on the environment or
could cause health or safety problems, extra care should be taken by their selection
and application in the field. Before applying any of these chemicals, all relevant HSE
data have to be requested from the chemical supplier and approval from
environmental legislative bodies is often required.
Different products are available for the different types of bacteria.

Inorganic bactericides
Chlorine is widely used to control the growth of aerobic bacteria in surface water
injection systems and no evidence of bacteria becoming immune have been
reported. It is a cheap product and generally effective at low dosage rates (e.g. 0.2 -
1 mg/l). Chlorine, however, is a corrosive chemical and attacks carbon steel. In
addition, when applied in produced water, it could react with the dissolved oil and
create persistent toxic chlorinated products. Oxygen free water often contain soluble
iron and the use of Chlorine would result in the iron to become oxidised by it and
become insoluble.
Mostly the Chlorine (or better Hypochlorite) is generated via the electrolysis of
Sodium Chloride (from sea water) as follows:

NaCl + H2O => NaOCl + H2

Sodium Chloride Sodium Hydrogen
Hypochlorite

The NaOCl is ionised into Na
+
+ OCl
-
the latter being the most active disinfecting
compound.
The Hydrogen generated if combined with oxygen is very explosive requiring a safe
disposal at the process unit by blowing with air below a concentration of 1%.

Hypochlorite solutions are very corrosive to carbon- and stainless steel and for
chemical injection pumps special alloys such as Hastelloy C or plastics are required.

Other effective biocides for the control of aerobic bacteria are chlorinated phenols,
but as these products are slow biodegradable, their use in the oil industry is very
limited, if at all allowed.
104
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

Organic bactericides
Anaerobic bacteria are less sensitive to chlorine as often these bacteria are located
underneath deposits or slimes and the chlorine cannot penetrate. In addition, as
chlorine is a strong oxidiser, the presence of soluble iron would result in iron
deposition.

A wide range of organic bactericides have been developed to prevent the
accumulation of anaerobic bacteria. Many of these products have practical
limitations or are only effective against one specific type of bacteria.
A number of these products are discussed below:

Aldehydes
Among the aldehydes, formaldehyde is a well-known broad spectrum Biocide which
is affecting the DNA in the microbial cells. Mutation in the DNA can lead to the
development of resistant strains resulting in the Biocide becoming ineffective.
Besides formaldehyde, also glutaraldehyde is a commonly used product. The
effectiveness of glutaraldehyde against bacteria increases with increasing pH.
Both products are effective general anti-microbial agents, but penetration into
biofilms is poor. For this reason the aldehydes are often blended with quaternary
ammonium compounds to assist in penetration. Another consideration when using
these products is their toxicity and suspected carcinogenity, which limits their
application in the field.

Quaternary Ammonium Compounds (QAC)
The quaternary ammonium compounds are considered low toxic and are used in the
food industry. This in contrary to aldehydes which are now considered toxic and
possibly carcinogenic.
At low concentrations these products show high rates of biodegradation and are of
low environmental risk if accidentally discharged.
A disadvantage of the low toxicity of the products is that their killing rate is low
compared to the aldehydes.
QAC are very surface active and may remove biofilms without killing all microbes.
This can lead to plugging and downstream contamination effects after Biocide
treatment.

Acrolein
Acrolein is a highly reactive acrylic aldehyde with a pungent odour and difficult to
work with. It is a very effective Biocide at low concentrations and short contact times.
In addition to being a Biocide, it is also an active sulphide scavenger.
Acrolein can since recently be safely generated on-site from non-hazardous
precursors and, if this novel technology can be developed into a fully functional
system, acrolein Biocide will become more widespread.



Application of biocides
Biocides can be either dosed continuously at low dosage rates or injected batch
wise. For water injection systems where the reservoir requires protection against
bacteria, continuous Biocide injection is applied, while in production water systems
105
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
batch injection is more commonly used. The frequency on the batch treatments can
vary from daily to monthly and depends mainly on the rate of recovery of the
remaining bacteria or recontamination.
100% kill of all bacteria is the ideal in Biocide treatments but in practice not often
achieved. Very often a few microbes escape alive and are able to multiply again after
some time. Some bacteria including SRB, are known quickly to become immune for
a particular Biocide. To prevent this to happen the applied chemical has to be varied
with another type of product on a regular (say monthly) basis.

Bactericides
Aerobic Bacteria
Chlorine
Chlorinated Phenols
Anaerobic
Less Sensitive to Chlorine
Amines, Aldehydes
Quaternary Ammonium Compounds
SRBs Quickly Become Immune, Biocides Must be Varied.
Biocides Must Kill 100% of the Population to be Effective.
Biocides Are Toxic and May Cause Environmental Impact.
Removing the Food and Oxygen Source is Preferred.



106
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

6. Corrosion

Corrosion is an electro-chemical process. This means that an electrical current flows
during the corrosion process. For the current to flow there must be a driving force or
a voltage source, and a complete electrical circuit.
The driving force or voltage source in the corrosion process is the energy stored
during the refining process of the metal from its original oxide- or salt form. The
circuit is mostly consisting of one half of the metal surface to act as the anode
(where the corrosion or oxidation takes place) while the other half is the cathode
(where the reduction reaction takes place). Both are connected via a conductive
water phase.
The following steps can be identified in the corrosion process:
1. The driving force results in electrons to escape from the metal at the anode.
2. The electrons flow from the anode to the cathode.
3. At the cathode a reduction reaction takes place.

The rate of corrosion is dependent on many factors including the following:
1. the type of metal (compare gold with iron or magnesium). The most difficult to
refine is the easiest to corrode.
2. the composition of the electrolyte (water with conducive salts)
3. the electron conduction between cathode and anode (compare with thickness of
electric cable and type material)
4. The pH of the water
5. The presence of dissolved gases like CO2, etc.
6. The oxygen content of the water.

Corrosion
Corrosion May be Considered as an Electrochemical
Reaction Involving Three Main Steps:
There is a Loss of Electrons from the Anode.
Fe
0
>

Fe
2+
+ 2e
-
Electrons Flow Through the Steel from Anode to Cathode.
A Reduction Takes Place at the Cathode to Complete the
Electrochemical Cell.
For example: Oxygen may be Reduced: 1/2 O
2
+ H
2
O + 2e
-
> 2OH
-
Types of Corrosion
Oxygen Corrosion: 4Fe + 6H
2
O + 3 O
2

>
4Fe(OH)
3
Carbon Dioxide Corrosion: Fe + CO
2
+ H
2
O
>
FeCO
3
+ H
2
Hydrogen Sulphide Corrosion: Fe + H
2
S
>
FeS

+ H
2
Bacterial Corrosion: Produces One of the Above Types.

`
107
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Common types of Iron corrosion encountered in the E&P Industry include the
following:
Oxygen corrosion
Carbon dioxide or sweet corrosion
Hydrogen Sulphide or sour corrosion
Bacterial corrosion.

The above types of corrosion are all the result of a (bio)chemical attack on the iron.

Another type of corrosion is galvanic corrosion.
Galvanic corrosion takes place when two different metals are placed in contact in an
electrolyte. The corrosion rate of the more reactive metal will increase while the
corrosion rate of the less reactive metal will decrease.
This principle is often utilised in a beneficial way in cathodic protection. Steel from a
facility or pipeline is connected to a more reactive metal such as magnesium and is
thereby protected against corrosion.

Under deposit corrosion occurs when two pieces of metal which are in different
environments, e.g. different concentrations of corrosive agent. This results in an
electrical current which increases corrosion under the deposit due to differential
concentration. This happens often under deposits of sand tar, debris, etc. in
combination with the presence of dissolved oxygen.
Another form of under deposit corrosion can result from the presence of SRB
underneath the deposit. In this case the release of H2S causes pitting corrosion.

Corrosion (Contd)
Galvanic Cells
Current Increases Corrosion Rate of Least Noble Metal
Used in Cathodic Protection
Under Deposit Corrosion
Differential Concentration Cell in presence of Dissolved Oxygen


Corrosion Inhibitors
Apart form using more corrosion resistant alloys, sometimes chemicals can be
applied to reduce corrosion rates in production facilities. Most of the products
reduce the corrosion rate by forming a protective water repellent layer on the metal
parts in contact with the corrosive medium. For this reason corrosion inhibition
injection has to be conducted in a continuous mode to ensure the protective film
stays intact. Because of their hydrophobic nature most corrosion inhibitors are
oil/condensate soluble. The few water soluble products available are found to be less
effective.
108
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Another group of chemicals is claimed to work on the induction of passivity of the
metal towards corrosion rather than by forming a water repellent film.


Corrosion Inhibitors
Most Common are Hydrophibic Adsorbing Materials that
Repel Water. A thin film of the product is reducing contact
between fluids and to be protected metal.
Most Water Soluble Inhibitors are found to be Less Effective
Presence of Water is the Main cause for Corrosion.
Compatibility with Demulsifiers, Drag Reducers, Hydrate
Inhibitors, etc, but also with Materials used.
Avoid Foaming and Emulsion problems


Because of their water repellent nature, corrosion inhibitors are often found to be
incompatible with many demulsifiers and can result in stable emulsions to be formed.
Also incompatibilities with other process chemicals such as drag reducers and
hydrate inhibitors have been observed.

For this reason, a detailed screening of potential corrosion inhibitor products is
required to make sure that, in addition to its effectiveness to reduce corrosion, no
incompatibilities with other system fluids or materials are the result. Further,
environmental aspects will have to be taken into consideration.

Selection of suitable products becomes more and more important now high
temperature, high pressure (HTHP) reservoirs are being produced and with the
production of hydrocarbons via sub sea installations.

Where chemicals are being applied to reduce corrosion rates, a proper monitoring
programme has to be in place to ensure actual corrosion is in agreement with the
design values.

A typical inhibitor screening program could be as follows:

Preliminary:
Test products recommended by supplier (maximum 2 per supplier)
exposure (weight loss) in a rotating cage @ 5 m/s for 1 to 7 days
electrochemical tests @ 1 m/s for 2 days
autoclave tests under actual anticipated pressures and temperatures
109
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
test metal in a solution of 10% NaCl, 10% CaCl2
test welded pipeline specimens

Advanced testing:
In flow loop tests, submit to intermittent slug-, annular dispersed-, and stratified
flow conditions
test the effects of other chemicals like scale- and wax inhibitors in the flow loop

Final testing:
Subject the inhibitor to test its corrosion protection efficiency by subjecting a metal
piece to impingement jet and high shear stress flow conditions under ambient and
actual field conditions, the presence of salt and oil, etc.

The ultimate test remains to test the performance of the inhibitor under actual field
conditions. And by monitoring using smart pigging, coupon monitoring and analysing
the iron content in the water.

INHIBITOR TESTING
LABORATORY TESTS:
Use suppliers recommended products
Tests in low pressure environment
Autoclave tests with weightloss coupons (res. P+T)
Flowloop testing
Field trials
FIELD MONITORING:
Smart pigging
Coupon monitoring
Iron counts
HTHP Environments and Subsea Installations make
selection of most suitable products more important







Oxygen Corrosion is mainly of importance in water injection systems whereby
oxygen is present in the surface water and is not totally removed.

110
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Oxygen attack is proportional to the rte at which oxygen is transferred to the steel
surface (as influenced by oxygen concentration and fluid velocity) and the surface
temperature (see Viewgraph).
It generally initiates as uniform corrosion upon exposed steel surfaces. Scale
deposition on these surfaces reduce these initial corrosion rates, but can locally
result in under deposit corrosion causing increased rates or pitting corrosion.
In surface waters at ambient temperatures oxygen content ranges between 7 and
8.5 ppm. This will cause a long term corrosion rate for steel between 0.5 and 3
mm/yr.
Oxygen can diffuse in significant quantities into pressurised systems (e.g. across
pump seals and vessel gaskets), while systems operating below atmospheric
pressure are exceptionally prone to oxygen leakage.

Oxygen Corrosion
Mainly of Importance in Water Injection Systems
Oxygen attack on steel is proportional to:
Oxygen Concentration
Fluid Velocity
Temperature
Generally results in uniform corrosion on steel surfaces
Pitting corrosion can occur under scales/deposits
At O
2
concentration < 5 ppb corrosion is negligible



111
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Oxygen Corrosion
Solubility of O
2
, effect of O
2
concentration and temperature
on corrosion of Mild Carbon Steel in Pure Water
C
o
r
r
o
s
i
o
n
,

m
m
/
y
Oxygen, ppm
Ox yge n Co rro si o n of M i l d Ca rb on S te e l
0
1
2
3
4
5
6
7
8
1 2 3 4 5 6 7 8 9 10
49oC
32oC
9oC


Oxygen attack is usually prevented by oxygen removal or exclusion. However,
upstream oxygen removal systems, corrosion should be avoided either by the use of
corrosion resistant alloys, such as selected stainless steels or non-metallic materials
(e.g. Glass Reinforced Epoxy, plastic piping), or in vessels, by the use of cathodic
protection. The use of corrosion resistant materials and CP throughout the injection
system will eliminate the need for oxygen control equipment or chemicals, but this
can only be considered if oxygen contamination of the reservoir is acceptable (i.e. no
dissolved iron present).

Oxygen can be removed/excluded from the water either mechanically via deaeration,
vacuum-, or (gas)stripping towers.
The mechanical methods are often applied to remove the main part of the oxygen
from the water stream while the remainder is removed chemically using oxygen
scavengers. The advantage of this approach is that less chemical is required
(cheaper) and that only small amounts of sulphite (a feed stock for SRB) will enter
the water via the oxygen scavenger.

112
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
O
2
Corrosion Prevention
O
2
Removal or Exclusion
Deairators/Vacuum/Stripping Towers
Oxygen Scavenging
Use of Corrosion Resistant Materials
Stainless Steel alloys
GRE piping/Coating
Cathodic Protection
Eliminates need for O
2
Control
Only to be considered if Reservoir can accept O
2


Oxygen scavengers
Oxygen scavengers are all chemicals which react with the oxygen in the aqueous
phase. The most commonly used product is Ammonium bisulphide (for reaction
equation see Viewgraph below).

The advantages of this product include the following:
reacts fast with oxygen in water and removes one ppm of oxygen per 6 ppm
NH
4
HSO
3
.
It does not react with air, so can be stored easily
It does not require a catalyst to activate
Is normally supplied in concentrated liquid form and easy to inject into the system
to be deoxygenated.

Besides above advantages the product also has some disadvantages which are:
The product is corrosive in concentrated form (requires plastic drums)
Due to the oxidation from SO
3
into SO
4
, it provides a food supply to SRB

Other oxygen scavengers are sometimes applied in water injection systems but have
other negative aspects.
Sodium sulphite is a powder and unstable is solution. The reaction rate with oxygen
in water is slow compared to the above ammonium bisulphide and requires a catalyst
(normally tracers of Cobalt ions) to become activated.

113
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Oxygen Scavengers
Ammonium Bisulphide:
2NH
4
HSO
3
+ O
2
===> (NH
4
)
2
SO
4
+ H
2
SO
4

6 ppm NH
4
HSO
3
reacts with 1 ppm O
2


Does NOT react with Air
Does not require a Catalyst
Corrosive in Concentrated Form
SO
4
supply to SRB
Other Oxygen Scavengers:
Sodium Sulfite : Na
2
SO
3
Sodium Metabisulfite : Na
2
S
2
O
5
Sulfur Dioxyde : SO
2


Another product is sodium metabisulfite which when contacted with water hydrates
into sodium bisulphite as follows:

Na
2
S
2
O
5
+ H
2
O 2NaHSO
3


The main disadvantage of sodium bisulphite over the ammonium product is that it
can be supplied in much lower concentrations and therefore much larger volumes
need to be injected.

Sulphur dioxide is also a potential oxygen scavenger but is a very corrosive gas and
potentially dangerous gas. In water with oxygen the gas forms sulphuric acid which is
very corrosive. For these reasons its applications have been very limited in the field.

2SO2 + 2H2O + O2 2H2SO4 (sulphuric acid)

The reason for the stability of concentrated bisulphite solutions can be found in the
Viewgraph below. Oxygen does not react with the bisulphite (HSO3) ion but only with
the sulphite (SO3) ion. The sulphite distribution is like the one for carbonate
(discussed under scaling) depending on the pH. High concentrations of ammonium
and sodium bisulphite are slightly acidic (below pH 4.5) and as can be seen from the
114
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Viewgraph, no sulphite is present in the product below that pH. Normal water
sources have a pH value above 4.5 and as result when the product is diluted with
water the pH shifts upward resulting in the formation of some sulphite. If oxygen is
present in this water, it will react rapidly with the sulphite resulting in the equilibrium
trying to restore the situation by forming more sulphite. The chemical equilibrium for
sulphite looks as follows:

SO2 + H2O HSO3
-
+ H
+
SO3
=
+ 2H+

Factors Affecting Sulfite Reaction Rate
Distribution of Sulfite Species as a Function of pH
0
10
20
30
40
50
60
70
80
90
100
0 1 2 3 4 5 6 7 8 9
pH
%

S
u
l
f
i
t
e

S
p
e
c
i
e
s
SO2
HSO3-
SO3=
As Only SO
3
=
reacts with O
2
No reaction with O
2
below pH=4,5


H2S corrosion
H2S corrosion is often encountered where gas with a high H2S content is produced.
H2S is a gas but very soluble in water where it behaves as a weak acid. It reacts
with iron to form a very insoluble iron sulphide corrosion product and usually adheres
to the steel surface as scale. It is an excellent electron conductor and is cathodic to
the underlying steel resulting in accelerated corrosion at defects in the scale layer.
The FeS can also lead to well plugging when precipitating in the near wellbore area.
Apart from its presence in the produced gas, H2S can also be generated as result of
sulphate reducing bacterial activity.
H2S itself is a very toxic gas and can be fatal when inhaled at levels of 5 ppm only.

H
2
S can be removed from water streams by means of air, nitrogen, or flue gas
stripping. In case air is used oxygen corrosion has to be taken care of.
H
2
S can be chemically removed or inactivated in water streams via oxidation with
chlorine (Cl
2
) or hydrogen peroxide (H
2
O
2
).
The reaction with chlorine is as follows:

4Cl
2
+ 4H
2
O + H
2
S H
2
SO
4
+ 8HCl
115
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

The reaction with hydrogen peroxide looks like this:

H
2
O
2
+ H
2
S S
0
(free sulphur) + 2 H
2
O

Aldehydes, generally used as biocides, also react with H
2
S as sulphide scavengers.
Apart from acrolein, relative large dosage rates are required to remove the hydrogen
sulphide.

In gas streams H
2
S can be chemically removed by for instance the Sulferox system
whereby the H
2
S is converted to inert Sulphur. Amine and Claus units can also be
used to remove the H
2
S.


H
2
S Corrosion
Aspects:
Highly Toxic and Hazardous to Personnel
General and Sulphide Cracking Corrosion
FeS Precipitation (Well plugging)
Can be Result of SRB in System
Chemical Removal:
Chlorine (only for small amounts of H2S)
Hydrogen Peroxyde
Aldehydes (also work as biocide)
Physical Removal:
Air or Fluegas Stripping



116
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS

7. HSE Aspects


Properties
In many of the production processes, chemicals are used to improve or optimise
these processes. Also, the produced gases, liquids and solids themselves, are all
mixtures of chemicals.

All these chemicals have their own particular Health, Safety and Environmental
specifics or properties which include for instance:
Toxicity to mammals, fish, etc.
carcinogenity (materials increasing the risk to develop cancer)
Corrosivity (property of the material to oxidise or corrode materials)
Flammability (ease of the material to burn or explode when in contact with fire)
Radioactivity (emission of alpha, beta, or gamma particles)
(Bio)degradation. Rate with which a (toxic) material decomposes to harmless
products.

The HSE properties of all chemicals used in E&P operations need to be known
before their use is allowed. These properties are important to be known for all
products used and produced during oil field operations as this will allow to apply
measures to safeguard against the negative aspects of these products and to avoid
any health safety and environmental accidents.
The measures to protect against harm caused by these products can include the use
of protective clothing such as masks, goggles, breathing equipment, chemically
resistant gloves etc.
In addition of the above properties, all chemicals which can cause damage to
humans or nature, require information on how to handle in case of a chemical spill.

Environmental Legislation
In many countries the disposal of E&P waste is subjected to environmental
Legislation. This legislation sets rules for the safe disposal of particular E&P waste
streams prohibiting or minimising any negative environmental impact.
The legislation differs from country to country for the different waste streams,
however, the tendency world-wide is that more and more stringent rules are being
applied. For instance, in many European countries, produced water is only allowed to
be re-injected into the reservoir of its origin and even in this case, should comply with
certain restrictions on chemical composition, etc.
Even, in the absence of legislation (or a very limited legislation) in a particular
country, Shell Companies world wide have to obey the Group policies and rules with
regard to the Environment in all their operations.

One area of increasing concern is the presence of radioactive materials in many of
the E&P produced waters. In their normal concentration in the produced water,
activity levels are normally far below acceptable levels. However, by co-precipation
with other scales in the production facilities and tubing, the radioactive components
may become enriched (the so-called Technologically ENhanced Radioactive
materials, or TENR), to activity levels well above allowed levels. Removal of these
scales is only allowed to be conducted by approved radiological workers.
117
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
The best approach to avoid these operational problems is to prevent the build-up of
these scales by the use of scale inhibitors.

Operational wastes include, apart from the radioactive scales above, also sand and
silt produced from the reservoir, wax, asphaltenes, residual emulsion, spent and
unused chemicals, containers, filter backwash sludge, etc.

Depending on their properties, wastes can be categorised as hazardous, or non-
hazardous wastes. In particular legislation on hazardous wastes is very strict and
their safe disposal requires many control systems.
HSE Aspects
HSE Aspects of Process Chemicals and Produced materials
Toxicity (people, fauna)
Carcinogeneity (people, fauna)
Corrosivity (people)
Flammability (people, nature)
Radio-activity
Environmental Legislation of Waste Streams
Produced Water
Waste Injection Water
Radioactive Scales
Operational Wastes
Drill Cuttings


Since 1990, all Shell Operating Units (OUs) are required to monitor and report the
quantities of all E&P waste streams as well as indicate their disposal route. These
data are used as a tool to improve the Environmental performance of these OUs
and to set benchmarks.
The next Viewgraph shows the discharge of chemicals against their total use in Shell
Expro UK for the year 1994. The figure shows that a relative large fraction of these
chemicals is discharged.

118
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
HSE: Chemical Discharge - Expro HSE: Chemical Discharge - Expro
Total Chemicals Used - 7,625 Tonnes.
Total Chemical Discharged to the Sea - 2,970 Tonnes (~40%)
Total Oil in Water Discharged to the Sea - 1,154 Tonnes. 1994 Data
F
u
l
m
a
r

A
K
i
t
t
i
h
a
w
k
e

A
G
a
n
e
t

A
A
u
k
B
r
e
n
t

A
B
r
e
n
t

B
B
r
e
n
t

C
B
r
e
n
t

D
C
o
r
m
o
r
r
a
n
t

A
C
o
r
m
o
r
r
a
n
t

N
D
u
n
l
i
n
O
s
p
r
e
y
T
e
r
n

A
l
p
h
a
E
i
d
e
r

A
0
200
400
600
800
1000
1200
1400
M
e
t
r
i
c

T
o
n
n
e
s

p
e
r

Y
e
a
r
Chem Used
Chem Di scharged


A study in 1994 in BSP Brunei, indicated that of all chemicals ordered, between 20
and 40% is wasted and is disposed.
The wastage of chemicals are mainly the result of:
improper handling or storage or the use of wrong handling equipment
leakage of liquid chemical from poorly maintained chemical injection systems
inaccuracy of dosing rates or lack of attention of the operator
products having reached the expiry date either as result inadequate stock
management
accidental- or sabotage spills

This disposal is sometimes controlled, for instance to hazardous waste disposal sites
or by incineration but, like for spills and leakages, can also be uncontrolled often
resulting in a negative environmental impact.
For many of the accidental spills measures can be taken to prevent the product to
cause damage, for instance by installing drip pans underneath chemical injection
pumps or providing rain cover for chemicals stored in metal drums.
By systematically looking at the potential chemical waste streams and taking simple
measures to avoid spillage, a significant reduction in the waste volumes is possible.
This reduction has next to the environmental benefit also a financial reward as less
chemicals have to be ordered.

119
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
Minimise Chemical Waste Minimise Chemical Waste
Estimated 20-40% of All Chemicals is Wasted as Result of:
Improper Handling/Storage
Leakage from Injection Pumps and Containers
Overdosage
Products Expiry Date has Passed
Remains in Empty Container
Spills


It is common wisdom that most process chemicals have a negative impact on the
environment. For instance demulsifiers because of their interfacial activity, often
have some toxicity to marine life. Other chemicals are not directly toxic but have an
impact on the environment because they consume oxygen from the water during
their degradation process.
For some products, the period that they negatively affect the environment can be
short lived, while for other products this period can be very long.
To minimise the impact of process chemicals, one option could be to prevent these
chemicals to contaminate the environment (e.g. water, soil or air). In practice this is
not possible as, apart of spillages, eventually a portion of these products has to be
disposed of.
Therefor, the best option to avoid impact is by not using chemicals. In practice, it is
sometimes possible to engineer-out certain process problems. For instance, for
some crude streams with emulsion problems, instead of chemicals heat can be
applied to fully break these emulsions. In another case it is sometimes possible to
prevent stable emulsion by avoiding excessive pressure drops in the production
facilities.
Up till now it has not been possible to engineer out all problems, and process
chemicals are still quite often necessary in order to allow undisturbed production of
hydrocarbon streams. Where chemicals are required, it is important that
environmental aspects are also taken into consideration in the screening/selection
process. Apart from the (cost)effectiveness and performance of the product, the
most environmentally suitable product should be chosen.


120
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
If Used with Unsufficient Care:
Most Process Chemicals Have a Negative Impact on
(Human) Health or the Environment
This Impact Can be Short-lived (e.g. Biodegradable Products)
Or Persist for a Very Long Time (e.g. Certain Radio Isotopes,
pesticides, etc.)
The Impact Can be Minimised by:
Using Most Environmentally Suitable Product
Applying Safe Handling Practices
Avoiding Spills
Minimise Chemical Waste
HSE Aspects of Process Chemistry HSE Aspects of Process Chemistry


For the environmental impact of a chemical to be established, many details about the
product are required.
Firstly, the chemical supplier has to provide all relevant toxicity and environmental
data including biodegradation rate and how to handle in case of spills, contamination
and accidents.
Another important aspect when using chemicals is to know which part of the product
is soluble in water and disposed with the production water and which part is oil (or
gas) soluble.
Eco-toxicity testing with a Micro-Tox unit can be used to measure the toxicity of
produced water containing chemicals. This analytical method, being a qualitative
testing, can be used to quickly measure the compounded effect of toxic chemicals in
produced water.

Another very important aspect in the selection of chemical relates to the local
environmental legislation on waste streams. Legislation can be very complex and
can differ from country to country.
For countries where no specific or only limited legislation exist, Shell Companies are
to consider the Group policies and advise.

To assist Operating units in the management of their waste streams EP-HE, the EP
Health, Safety and Environmental department, has issued the EP 95000 guidance
documents. A significant part of these documents cover environmental subjects and
include the following:
EP 95-0375 Environmental Quality Standards - Air
EP 95-0376 Monitoring Air Quality
EP 95-0377 Quantifying Atmospheric Emissions
EP 95-0380 Environmental Quality Standards - Water
EP 95-0381 Monitoring Water Quality
121
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
EP 95-0385 Environmental Quality Standards - Soil and Groundwater
EP 95-0386 Monitoring Soil and Groundwater
EP 95-0387 Contaminated Soil & Groundwater
EP 95-0390 Waste Management Guidelines
EP 95-0391 Classifying Waste
EP 95-0397 Oil Spill Dispersants

These guidelines, in addition to local legislation, can be used to select the most
acceptable (long-term) disposal route for the individual waste streams of an
Operating Unit.

Environmental Aspects Environmental Aspects
Supplier to Provide Toxicity/Environmental Data
Which Part of Chemical is Disposed with Water Phase
What is Eco-Toxicity of Product (Micro-Tox)
What is Local Legislation wrt Use/Disposal of Products
Identify (Longterm) Acceptable Disposal Options for:
Chemical Waste
Water Phase
Sludge
Deposits/Scale


Minimise Impact
This Viewgraph illustrates options which can be used to minimise the environmental
impact of waste streams by applying a management approach.

For produced water options are listed in order of environmental preference and
should be followed where technically feasible and economically acceptable.
The first and environmentally most attractive option is to avoid or significantly
minimise the production of water. Technically this is possible by selecting the
completion interval such that water breakthrough does not occur or very late in the
production lifetime of the wells. This can sometimes be in contradiction with the
production technically optimum completion interval. A second possibility could be to
apply downhole dehydration whereby the downhole separated water is directly
pumped into the water leg of the formation rather than being produced to surface.

Where the minimise production option has been optimised, the next step is to
dispose this water in the most acceptable manner. Virtually all countries accept re-
122
PRODUCTION CHEMISTRY - DEPOSITS AND EMULSIONS
injection of this water into the original reservoir as the best solution, sometimes
under the condition that this water is not contaminated with toxic chemicals.
Another, almost as good solution is to inject the water into a dry or non-potable
aquifer. The definition potable or non-potable can differ from place to place but in
most situations the salinity of the sea water is used as the limit value.
The next option is disposal of the water into the sea. All countries have set quality
criteria for this water before it is allowed to be disposed. One of these criteria related
to the allowed oil in water content which is in most countries 40 mg per litre in
offshore waters. Apart from the oil content, many countries since recently also have
set limits to the toxicity and oxygen demand.
Disposal to near shore or surface waters is one of the least attractive options and
water quality requirements maintained by most legislators, therefor are more tight
when compared to offshore disposal.

For solid wastes sludges and deposits, are similar philosophy is applied where again
avoiding is the best option. Downhole injection of sludges, including drilling muds, is
becoming more popular. Incineration is also applied often as an acceptable manner
to de-toxify certain chemical wastes.
Stabilisation can be used where waste materials are encapsulated with insoluble
materials such as lime cement, etc.
Controlled land farming is also applied where the leachates from the area can be
tested to avoid leakage of hazardous material from the land farm area.


Minimise Environmental Impact Minimise Environmental Impact
Water Management:
Minimise Production (Downhole Dehydration/Completion)
Re-Injection into Original Reservoir or Non-Potable Aquifer
Disposal Into Sea after Treatment to Required Quality
Standards
Disposal Into Near-Shore or Surface Waters after Treatment
Sludges/Deposits
Avoid Generation/Production
Downhole Injection
Incineration
Stabilisation (e.g. with Lime)
Controlled Landfarming



123