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BP Exploration

Appendix 7 – Production Chemistry Reference Documents

APPENDIX 7

PRODUCTION CHEMISTRY REFERENCE
DOCUMENTS
 Oilfield Wax
 Asphaltenes
 Water Chemistry & Scale

BP Exploration
Appendix 7 – Production Chemistry Reference Documents

BP Exploration
Appendix 7 – Production Chemistry Reference Documents

APPENDIX 7 PRODUCTION CHEMISTRY REFERENCE DOCUMENTS
OILFIELD WAXES
INDEX
Page No.
1.

INTRODUCTION TO WAX

1

2.

PIPELINE FLOW CHARACTERISTICS FOR CRUDE OILS

1

3.

2.1
2.2

Introduction
The Questions to be Answered

2.3

Experimental Parameters
2.3.1
Pour Point
2.3.2
Viscosity
2.3.3
Yield Stress (Pipeline Start-Up)

2.4

Destroying Sample Past History

2.5

Modelling Pipeline Systems
2.5.1
General Purpose Model
2.5.2
Modelling Static Cooling of a Buried Pipeline

2.6

Overcoming Pumping Problems
2.6.1
Insulating or Heating Flowlines
2.6.2
Dilution
2.6.3
Thermal Pre-Treatment
2.6.4
Oil-in-Water Emulsion
2.6.5
Core Flow
2.6.6
Local Crude Oil Processing
2.6.7
Chemical Additives

WAX DEPOSITION IN CRUDE OIL PIPELINES
3.1

Introduction

3.2

Mechanisms of Wax Deposition
3.2.1
Molecular Diffusion
3.2.2
Shear Dispersion
3.2.3
Gravity Settling

3.3

Appropriate Laboratory Measurements
3.3.1
Wax Content
3.3.2
Wax Appearance Temperature
3.3.3
Wax Deposition Tendency

3.4

Prediction Deposition Rates in Pipeline Systems

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7

BP Exploration
Appendix 7 – Production Chemistry Reference Documents

3.5

Controlling Wax Deposition
3.5.1
Pigging
3.5.2
Chemicals
3.5.3
Hot Oil Flushing

FIGURES 1-20

Page 2

BP Exploration
Appendix 7 – Production Chemistry Reference Documents

1.

INTRODUCTION TO WAX

Waxes are a natural constituent of crude oils and condensates consisting of mainly heavier (>C17)
paraffinic hydrocarbons. These may be straight or branched chain or cyclic, and they affect
production in two ways. Firstly they can have an adverse affect on the viscosity of the oil. This has
important implication to pipelines, either in-field or export. They can impart non-Newtonian
behaviour, ie that the viscosity of the oil depends upon the shear rates applied to it. A good common
example of this is household non-drip paint. Here, under low shear the paint does not flow (ie nondrip), but at high shear when applied by paintbrush, the paint flows naturally to cover the surface.
Such behaviour in production operations normally manifests itself during shut-downs. Following a
shut-in, when flow restarts, the initial shear rates may be very low. At low shear rates the apparent
viscosity may be high, in some cases so high that the available pressure from the pumps is insufficient
to start flow. This is particularly a problem in subsea lines where the fluid temperature falls,
compounding the high viscosity.
Secondly, wax crystals can be deposited from bulk. In a pipeline system, this may reduce the internal
dimensions, but the real effect upon flow through the line is an increase in the surface roughness of
the pipewall. This causes an increase in the energy needed to pump the fluids through the line. Thus,
for a given pumping pressure, the volume throughput would be less in lines where wax deposition
has taken place. Wax deposition has also been noted in risers, manifolds, at wellheads and in
separators in addition to pipeline systems.
Each of these phenomena are discussed below.
2.

PIPELINE FLOW CHARACTERISTICS FOR CRUDE OILS

2.1

Introduction

Most crudes are relatively fluid and easy to pump. However, this may not be the case for waxy or
heavy crude oils. Typical ranges in the characteristics of crudes affecting pumpability are shown in
Figure 1. If a crude has a pour point of 50°C, but the flowing fluid temperature in the line is only
40°C, there is potentially a pumping problem. Therefore, it is important to understand not only the
characteristics of the oil, but also the operating conditions of flow, temperature and pressure, and
whether gas is present (ie two-phase (gas/liquid) flow). Neither is it sufficient to consider only
normal flowing conditions. Unfortunately, periodic shut-ins are inevitable, whether planned or
unexpected. If the fluids stop flowing in the line, heat transfer to the pipewalls and into the
environment could cool the pipeline fluids significantly. For instance, over a period of days shut in,
the temperature of the contents of a subsea pipeline could fall to that of the surrounding sea water.
This could be as low as -2°C in regions subject to Arctic currents. The characteristics of the crude at
these low temperatures may differ considerably. Generally low temperatures increase viscosity, but
in the extreme, some crudes can form a gel structure which requires considerable pumping pressure
to move and restart flow.
2.2

The Questions to be Answered

In a real system, fluids, their flow rates and the environment surrounding the pipeline may all affect
pumpability problems. We therefore need to address the following:
(a)

What are the flowing (equilibrium) pressure, temperature and flow characteristics?

Page 3

Figure 3 describes the pressure drop across a pipe at different flow rates for three different types of crude. Even if this minimum pressure is available. The following equations describe shear rate for two different flow regimes:  DL   8 x(MeanSpeed) Diameter  DT  DL x 0. Figure 4 shows the fluid temperature with respect to the surrounding soil for a buried line for 50 and 300 hours following a shut-down as a function of distance along the line. Thus. simple test but provides only a rough guide and is of no use in quantitative predictions. viscosity depends upon "speed" or rate of shear as well as temperature. Rate of shear is the velocity gradient normal to the direction of flow. there are several measurements that can be made in the laboratory. Figure 2 shows typical temperature profiles for different flow rates and how the local environment affects the profile. can it be restarted? The viscosity of the crude oils can increase to a point that they exhibit a yield stress. the pressure across the pipeline is much greater for the viscous than the fluid crudes. or during shutdowns. (c) How long does it take a pipeline to cool? In a subsea pipeline exposed to the seawater. become non-Newtonian at lower temperature. Shut-down problems can therefore be avoided if flow can be restarted with the available pumping pressure within a specified period of time. (b) If a pipeline is shut-down and allowed to cool. The applied shear stresses are lower. Thus.BP Exploration Appendix 7 – Production Chemistry Reference Documents Crude oil flowing temperatures fall along the length of the line. cooling of the fluids in the line would be much more rapid than in a buried land line. 2. in the latter stages of field life. particularly the more viscous ones. The flow rates determine the type of flow which also has a large effect on the viscosity. During normal operation.0048x(Reynolds No) Page 4 Laminar Flow Turbulent Flow . That is until a certain minimum pressure is applied there will be no flow at all. the flowrates may drop. the flow rate for a line filled with cold viscous oil may not be high enough to allow hot incoming oil to warm the line up and achieve the normal operating flow again. the "viscous" crude behaves in a similar manner to the "fluid" crude. It is a very widely used. its viscosity increases away from the pipeline inlet.3. 2. Turbulent flow imposes high shear stresses under which many crudes show Newtonian like behaviour. most flowlines are in turbulent flow . That is. for high pipeline throughputs. At high flow rates. and this enables temperature to dominate the viscosity of the crudes.1 Pour Point This defines the temperature below which flow may not occur.2 Viscosity Crude oils. Thus. Thus.3 Experimental Parameters In order to characterise the crude oils. the flow regime determines the apparent viscosity of the oils. In a pipe this is zero at the centre and maximum at the pipe wall.3. However. 2. the thermal capacity of the surrounding environment must be considered.

the key parameters are cooling rate.3. or the mechanical shear it is subjected to may affect these wax structures. >2200. a pour point depressant added. 2.4 Pa. Brookfield UL or Haaka Rotovisco. it is still a very useful quantitative guide. However. Here the sample is heated to 80°C for 1 hour. It is conducted in a model pipeline (see Figure 6). This model pipeline restart pressure can be scaled up to full size pipelines via the pipe wall shear stress: Sw  ShearingForce (Pressure Pa )x(Diameterm )  Pa PipeWall Area 4x(Lengthm) For 1000psi across 10km of 10 inch line SW = 4. In any process. A small pressure is applied. cooled at three different rates (simulating pipeline flow) before loading into the viscometer to measure viscosity. 2. This is done by heating the sample to a temperature sufficient to melt the wax crystals and return the wax to solution. and if no flow is detected from movement in the oil level a higher pressure is applied. Then.BP Exploration Appendix 7 – Production Chemistry Reference Documents NB: for turbulent flow Reynolds No. comparative viscosity and yield stress measurements can be made. Figure 5 shows a family of typical results obtained for a 'non-Newtonian' crude. Thus. Additionally. again under appropriate shear. The process is known as beneficiation. This is because this may have generated wax crystals of different shapes and sizes dispersed throughout the sample.0 is normally applied. and the samples returned to their 'reservoir state' before they had been subjected to such history.5 Modelling Pipeline Systems Page 5 . Figure 7 indicates how previous history and how the sample is subsequently handled alters the measured viscosity. then under appropriate shear rates cooled at a rate of 15°C per hour to 45°C (simulating flow to platform). Therefore to make meaningful and comparable measurements. Viscosity should be measured in concentric cylinder viscometers such as the Ferranti Portable. the rate at which the sample is heated or cooled. temperature cycles and mechanical shear.4 Destroying Sample Past History The pour point. This is equivalent to 6psi across the model pipeline in Figure 6. in which the oil is cooled to the tests temperature in a similar manner to that which would occur in a pipeline on shut-down. 2. A safety factor of about times 2. A range of different flow rates and temperature should be covered in order to simulate pipeline flow. Figure 8 shows a typical laboratory simulation. then. Typical pipeline rates of shear are between 1 and 1000s-1. these structures must be destroyed. The restart pressure at which flow is first detected (a movement of 20mm during 15 minutes) is then gives the yield stress. This simple scale-up is complicated in reality by the presence of void spaces and many other factors. warmed to 65°C at a rate of 15°C per hour (simulating platform processing).3 Yield Stress (Pipeline Start-up) This is measurement of the force needed to start flow again following a shut-down. the behaviour towards the end of the pipeline can be effectively determined. by cooling in a controlled manner. viscosity and yield stress as measured today depend very much on the previous thermal and mechanical history of the oil.

6 Overcoming Pumping Problems There are a number of ways to alleviate pumping problems. The associated theory is a combination of fluid dynamics and heat transfer. since cooling still occurs albeit more slowly. For instance.1 General Purpose Model This programme (S007) can account for pressure. which have been validated in practical applications.6. but does not take account of complete separation of the gas and liquid phases ("slugging". both in the pipe and in the surroundings as a function of time following shut-down. 2. It assumes that the mixture can be treated as a single fluid but of variable density. this may not overcome problems following a shut-down. typical studies may include: (a) Temperature profile along the length of a pipeline using heat transfer correlations for: Oil to pipe Pipe and insulation or concrete coating conductivity Pipe to air or water (and part buried) Conductivity through ground or sea-bed (fully buried) Transfer from ground to air or sea-bed to water. If relying solely on insulation. Page 6 . Inputs required are basic physical conductivity data. etc. particularly by heat tracing flowlines. (b) Pressure drop calculations for: Laminar flow Smooth turbulent flow (Blasius correlation) Rough turbulent flow (Colebrook-White correlation) (c) Non-Newtonian behaviour accounted for by using viscosity measurements under shear rates matching those at pipe wall in Newtonian equations. (d) Some assessment is also made of the increase in flow rate as cold oil is displaced by warmer oil during start-up. thermal conductivities and other physical parameters. This programme can handle two-phase flow if it assumes that this flow is homogeneous. Over many years Sunbury have developed a number of programs.5. temperature and flow calculations.1 Insulating or Heating Flowlines Increasing the fluid temperature may be prohibitively expensive. It is based upon on the finite difference and Schmidt approximation technique.5.BP Exploration Appendix 7 – Production Chemistry Reference Documents Computer programs link laboratory measurements to full scale predictions. 2. 2. pipe dimensions.2 Modelling Static Cooling of a Buried Pipeline This programme SQ13/19 predicts the temperature at different distances from the pipe centre.) Input data are laboratory measured viscosity (over appropriate temperature and shear rate range). For example: 2.

5 Core Flow If a layer of water can be maintained at the pipe wall very viscous oil can flow as a plug or solid core. but may be impractical.6. if produced fluids are transported for some distance before processing. Pour Point Depressants These are chemical additives that influence the shape of wax crystals and therefore the viscosity and yield stress of a crude oil as it is cooled.6. Figure 12 shows a typical effect upon the characteristics of a crude oil. viscosity or yield stress can be significantly improved. 2.6 Local Crude Oil Processing In some instances. and there is no guarantee that a suitable pour point depressant can be found for every waxy crude. In essence a lower viscosity state can be achieved if the waxy crude is cooled statically under controlled process conditions as opposed to dynamically under flowing pipeline conditions. Some Page 7 .6. With a suitable surfactant. has been used in Indonesia. they must be injected while the oil is still hot. Their performance depends very much on crude type and the additive itself.6. pumping pressures may simply rise as a function of water cut. 2. This is the basis of a BP developed process.4 Oil-in-Water Emulsion The viscosity of an oil-in-water emulsion is very much closer to that of water than it is oil (see Figure 10). particularly if the diluent must be transported to the right place. However. before wax crystals are first formed. which has been used for many years in the Indian Nahorkatiya field. All of the shear occurs in the water. Figure 9 shows typical performance data for pour point depressants. reducing pumping pressures accordingly. However.BP Exploration Appendix 7 – Production Chemistry Reference Documents 2. 2. (see Figure 11) Conversely. heavy crude can be processed in the field before transport.7 Chemical Additives There are two main chemical types that are used to affect flow properties. 2.3 Thermal Pre-Treatment The sensitivity of waxy crude oils to thermal and mechanical history (see Figure 7) can be turned to advantage by applying beneficial pre-treatments in the field. An extension to this is to use surfactants in the water to keep the pipe wall water wetted and keep the water and oil apart. a water-in-oil emulsion can have a viscosity greater than the oil.6. 1.6. The annular ring of water is first created by a special injection system. shear stresses and water cut. pour point depressants and drag reducers. 2. Thus. which acts as a lubricating layer. This technique. They can significantly reduce both normal pumping pressures and yield stress after an extended shut-down.2 Dilution Diluting the viscous or heavy crude with a either a lighter crude or refined light fraction will aid pumpability. The economic consequences need careful consideration even if the separated fractions have a subsequent use such as local energy production. developed by Shell. for example by separating the heavier fractions. Work is now underway to examine how viscosity of these emulsions varies with temperature. It should be noted that additive doped waxy crude is even more sensitive to mechanical shear. such an emulsion can be deliberately formed. Clearly this will not be an option in many cases. They operate by two totally different mechanisms.

must not be broken down by mechanical shear such as in centrifugal pumps and have no downstream effects on refinery equipment or on refinery products. Eddy currents are generated at the pipe wall and grow in size as they move into the mainstream flow resulting in energy dissipation in the fluid and hence frictional pressure losses in pipelines.g. For crude oil pipelines they should be oil soluble. These chemicals work by reducing the frequency of turbulent eddy bursts from the pipe wall and hence stabilising the wall layer.4-1. Drag reducing additives are high molecular weight polymers. Turbulent Drag Reducing Additives Turbulent flow is characterised by fluid moving in irregular random motions transverse to the direction of flow. 2. In the Trans Alaska Pipeline.BP Exploration Appendix 7 – Production Chemistry Reference Documents additives perform excellently in the absence of shear and not at all with shear. and chemical costs alone can run into thousands of dollars a day. applying a drag reducer may be cheaper than upgrading pumps. The effectiveness of a drag reducer is expressed in terms of the percent drag reduction. If pipelines are operating at their maximum line pressure. toluene).65 million b/d for the same pumping pressures and pipeline conditions. Alternatively. Typically. Therefore this is not a cheap option. They are usually supplied as highly viscous fluids containing around 10%wt of active polymer dissolved in a kerosene carrier. if flow rates are limited by available pumping pressures. Evaluation of additives is therefore a complex process. Drag reduction is the proportional reduction in the pipeline pressure drop when a drag reducer is injected into the pipeline. Injection rates of as high as 100-1000ppm are commonly required. Flow in crude oil and oil product pipelines is usually turbulent with Reynolds Numbers normally at the upper end of the range 103 . The rate of energy dissipation within the turbulent eddy flow is reduced and the frictional drag and hence pressure drop in the pipeline is reduced. They work by reducing turbulent flow losses and hence frictional pressure drop within the flowing oil and do not coat the pipe wall nor change the bulk oil properties as viscosity improvers or pour point depressants do. At a given flow rate the percent drag reduction is defined as: %DR  DP  DPDR x100 DP Page 8 (1) .106. They are oil soluble and form 'snake like' long chain structures in the flowing oil which interact to reduce the frequency of turbulent eddy bursts at the pipe wall. However pour point depressants have been used economically in the Indian Bombay High and North Sea Beatrice fields. usually with molecular weights of at least 5 x 105. Figure 14 shows data on the increased flowrate achieved by drag reducer addition. drag reducers may provide an attractive alternative to uprating the line. Figure 13 shows data of how the flowrate can be increased for the same pumping pressure. drag reducers have increased throughput from 1. Another possibility is using drag reducers to increase pumping efficiency and allow booster pumping stations to be shut down. Recent applications include in water injection wells where the benefit of increased water injection has more than offset the cost of the chemical. A common type of drag reducers are the non-crystalline polyalpha-olefins. pour point depressants are polymers at concentrations of 20-50 percent in a hydrocarbon solvents (e.

Alternatively a drag reducer can be thought of increasing the flow for the same pipeline pressure drop. The relationship between percent drag reduction and percent flow increase can be estimated from the percent drag reduction using the equation: Page 9 .BP Exploration Appendix 7 – Production Chemistry Reference Documents where P is the pressure drop of the untreated oil and PDR is the pressure drop of the oil containing drag reducer. The percent flow increase can be defined as: %FI Q 2  Q1 x100 Q1 (2) where Q2 is the increased flow rate with drag reducer and Q1 is the original pipeline flow rate.

BP Exploration Appendix 7 – Production Chemistry Reference Documents Page 10 .

Wax can accumulate on the pipewall and if left untreated built-up into a wax layer. If susceptible to mechanical shear. Note that drag reducers have no effect on frictional pressure losses in laminar flow. wax deposits frequently include entrapped oil. Such information is required to assess how regularly remedial treatments are required. sharp bends. The wax layers can also reduce the effective cross sectional area of the pipe causing a loss in throughput in systems which are pressure limited. WAX DEPOSITION IN CRUDE OIL PIPELINES 3.BP Exploration Appendix 7 – Production Chemistry Reference Documents (3) Equation 3 assumes the pressure drop for both the treated and untreated oil is proportional to flow rate raised to the 1. Smaller diameter pipelines will generally have greater turbulence and therefore improve drag reducer performance. ie the temperature at which wax crystals first start to form. They may be relatively soft and easily removed or dense. providing additional benefit) 2. and the rate at which it can deposit wax onto a cooled surface. For example wax deposition in the first Forties pipeline caused a steady pressure drop increase of about 4% per day unless remedial measures were taken. In reality.8 power. Drag reducer performance can be affected by either the properties of the oil in the pipeline or the pipeline construction as follows: 1. sand. corrosion products or inorganic scale. Performance is impaired by high water contents or high levels of dispersed wax crystals. the temperature at which wax is first observed. Main pipeline pumps are likely to completely degrade drag reducing polymers. This impacts upon the location of the injection points. and hence estimate likely operating costs. 3.1 Introduction In addition to affecting the flow properties of a crude oil. To assess the risk of wax deposition. or orifice plates could reduce drag reducer performance. there is a laminar boundary layer adjacent to the pipe Page 11 . wax can also be deposited.2 Mechanisms of Wax Deposition In a pipeline operating under turbulent flow. This can occur if the internal surface of the pipeline falls below the wax appearance temperature of the crude. The laboratory generated data is subsequently used in pipeline models to simulate the real system. the crude oil is examined for its wax content. Figure 12 shows typical flow increases and drag reductions for both a light and a heavy crude oil. Hence higher temperatures therefore improve performance (Higher temperatures may also increase the solubility of the drag reducer. and other solids such as asphaltenes. The model can then predict the wax build up in a pipeline. 3. This increases the surface roughness at the pipe wall and leads to an increase in frictional pressure drop across the pipeline when the fluids are in turbulent flow (as is the case under normal operating conditions). 4. valves. 3. and the consequential pressure drops that could occur. They work best with lower viscosity oils. hard deposits. firstly.

as the temperature of the oil at the pipe wall falls below the wax appearance point there is a small concentration gradient and deposition will take start. the oil is under-saturated with dissolved wax and the concentration gradient of the dissolved wax is zero. Since the pipe surface is inherently rough. If the temperature of the pipewall is less than this. 3. dT dr = radial temperature gradient close to the pipewall (∞C/m). The rate of transport of dissolved wax to the pipe wall is given by Ficks diffusion equation: n  D dC dC dT D  dr dT dr where n = mass flux of dissolved wax molecules to the pipe wall (kg/cm2).1 Molecular Diffusion As a crude oil is cooled the solubility of the crude for its wax falls. molecular diffusion can take place. At a particular temperature (characteristic of each crude) the wax reaches its saturation point and begins to precipitate out. Molecular diffusion transports wax which is in solution and precipitates it directly on the pipewall. Page 12 . usually cooling towards the pipewall. Across the laminar boundary layer there is a temperature gradient. namely molecular diffusion and shear dispersion. r = density of solid wax (kg/m3). This is the cloud point or wax appearance temperature. If the crude and the pipewall are above the wax appearance temperature. The diffusion coefficient for a crude oil is inversely proportional to the crude's dynamic viscosity: D = B/ where B = constant for a particular crude (N). wax will precipitate out directly on the cold pipewall. Over the laminar sub-layer there is a high rate of shear. and a high temperature gradient. which results in a wax concentration gradient between the dissolved wax in the turbulent core and the wax remaining in solution at the pipe wall.  = dynamic viscosity of crude oil (Ns/m2). Shear dispersion transports solid particles of wax already precipitated in the turbulent core to the pipewall. velocity and wax concentration are almost independent of radial position. However. The rate of wax deposition is determined by what happens in this laminar region.2. Each is discussed below. dC dr = concentration gradient of dissolved wax with respect to distance from pipewall (∞C/m) dC dT = concentration gradient of dissolved wax with respect to temperature (∞C-1). There are two principal mechanisms by which wax deposition is thought to take place. This causes dissolved wax to diffuse towards the pipe wall where it is subsequently precipitated. it provides suitable nucleation sites and the precipitated wax becomes incorporated into an immobile layer.BP Exploration Appendix 7 – Production Chemistry Reference Documents wall and a turbulent core in which temperature.

and wax buildup cannot occur by this mechanism. there is no molecular diffusion. cause some lateral movement.2 Shear Dispersion Small wax crystals suspended in a flowing crude. are carried at the same speed and in the same direction as the fluid. 3. however. its flow rate. depending upon the temperatures of the fluids and the pipewall. and fall as the crude cools towards the temperature of the environment. the material of the pipeline and the environment surrounding the line. there is no tendency for nucleation to occur at the pipe surface. Thus. if the fluids are at the same temperature as the pipewall. The higher shear rates at the pipewall. that is when the bulk oil temperature has fallen well below the wax appearance point.2. Thus wax particles already precipitated out in the fluids can form a deposit on their own or combine with wax already deposited by molecular diffusion. Shear dispersion becomes important only when the precipitated wax content in the turbulent core is high. Therefore wax deposition rates are at a maximum when the bulk oil temperature is high. There is thus a wax deposition profile along the length of a pipeline. known as shear dispersion. This tends to cause less tenacious deposits than those formed by molecular diffusion. Since shear dispersion transports solid wax particles. These two parameters are themselves determined by the nature of the fluid.BP Exploration Appendix 7 – Production Chemistry Reference Documents The wax diffusion coefficient and the radial temperature gradient both fall as the oil temperature falls in a pipeline. Page 13 .

The average heat transfer H is calculated by: H=TxQxC where T is the difference between the inlet and outlet temperatures of the coolant. although rather less important mechanism by which wax can be deposited from a crude in a pipeline.3 Wax Deposition Tendency The basis of laboratory measurements lies in building up actual wax deposits on cooled surfaces in test cells under controlled conditions.3 Gravity Settling There is a third. This may be determined visually through optical microscopy through crossed polars or by differential scanning calorimetry which measures heat changes on precipitation of wax. Wax crystals tend to be more dense than the bulk fluids. The inlet and outlet temperatures of the coolant are monitored together with its flow rate throughout the test.3 Appropriate Laboratory Measurements In determining the risk of Wax deposition. BP defines the wax content from the weight of material precipitated when a sample of asphalt-free crude is dissolved in dichloromethane and cooled to -32 C. wax separated from a crude oil at 0 C is likely to have a different composition to that separated at 20 C. we can predict the likely deposition rates in the field. if flow stops the wax can settle out. The simplest deposition cell is a static cell (Figure 15) which comprises a water-cooled flat box which is immersed in a reservoir of oil maintained at approximately 8°C warmer than the depositing plate surface. The amount of wax that can deposit in a pipeline is low and usually will redisperse once flow is re-started and the fluids heat up once more. gravity settling tends to be a problem only in storage tanks. Whilst an increase in shear rate should encourage more wax particles to disperse towards the pipe wall. and the average heat transfer through the plate.3. the amount of wax out of solution and the shape and size of the wax particles. 3. the same wall shear stress may increase the rate at which these loosely held deposits are stripped away. based upon laboratory generated data. H. the deposition tendency M/H of the crude can be measured for particular plate temperatures. Each test is normally run for a period of six hours after which time the cell is dismantled and the deposit is inspected.3. For instance. 3.2. For Page 14 . This provides measured an estimate of the daily rate of wax build-up per unit of heat transfer and is characteristic of each crude. Although turbulent flow is more than able to overcome gravity and keep the wax crystals suspended. M. Q is the flow rate of coolant C is the specific heat of the coolant. deposition tests are performed under shear. M can be determined.3. By measuring the daily wax build-up on the plate. several laboratory measurements are used.2 Wax Appearance Temperature The wax appearance temperature is that below which wax crystals are precipitated. The oil and plate temperatures are also monitored. 3. Thus. By knowing the heat transfer rate through a pipe wall. To simulate full scale conditions more accurately.BP Exploration Appendix 7 – Production Chemistry Reference Documents The parameters that affect the shear dispersion mechanism are: the wall shear rate. 3.1 Wax Content Wax contents may only be assigned with reference to the conditions under which the wax is separated. removed and weighed and the daily mass of wax deposited. 3.

Results also indicate that deposition is reduced under conditions of shear. This arrangement closely simulates full scale pipeline deposition in that the cooled surface is subjected to the highest rate of shear. but the equipment is rated to higher pressures to simulate more closely the situation in field pipelines. To predict wax deposition throughout a pipeline system.BP Exploration Appendix 7 – Production Chemistry Reference Documents these measurements a coaxial shearing cell (Figure 16) is used which comprises a water cooled stationary inner cylinder around which an outer cylinder rotates to impart the appropriate rate of shear to the oil in the 6mm gap between the cylinders. These slugs will alter the shear stresses at the pipewall. Hence the model will also produce pressure drop profiles of a pipeline.000 bbl/day. Wax deposition will also be affected by the flow type. Until this point the fluid temperature maintains the pipewall at above the wax appearance temperature. 3. This balance between an increased rate of deposition and the possibility of stripping off deposits is why these laboratory measurements are required and that field conditions should be matched as closely as possible. the increase in friction factor and hence pressure drop can be estimated from the predicted increase in pipe wall roughness. the location inn the line where deposition first occurs and the overall rate at which wax deposits. By using a Colebrook-White correlation which takes into account the inherent roughness of the pipe wall. This phenomena could be due to an increase in shear dispersion. Figure 19 shows typical wax profiles in mm/day wax build-up down the line in the first Forties export line for flow rates of 450. although this is poorly understood at present. or even stripping off wax already deposited. Generally stabilised crude samples are used to determine deposition rates. even though molecular diffusion may be higher. At 450. At 600. A crude with its dissolved gas will be less viscous. a series of deposition rate laboratory tests are needed covering the temperatures likely to be encountered. increasing the surface roughness by an amount equal to the thickness of the wax layer. The wax is assumed to be distributed evenly over the depositing region.4 Prediction Deposition Rates in Pipeline Systems BP has developed a model to predict deposition rates in pipeline systems (based upon Fick's diffusion equation and molecular diffusion theory) using the laboratory wax deposition tendency data. Clearly. Deposition in multiphase lines is the next big where research is needed to understand the effects.000 bbl/day and 600. The total daily deposition rate in the line was predicted to be 19 tonnes/day. affecting the rate of wax deposition. Figure 17 shows typical deposition curves as measured under static and shear conditions for stabilised crude and also under shear conditions with "live" crude spiked with gas at 350psi. Page 15 . in a multiphase line. and hence should increase the rate of deposition from molecular diffusion. The design is similar to a coaxial cell. The test procedure is similar to that described for the static cell. Figure 18 shows how the deposition tendency decreases with increasing shear as measured in a coaxial cell. but is probably due to wax deposits already formed being stripped off at higher wall shear rates. but the effect of dissolved gas can be established from tests in a pressurised shearing cell. Deposition rates rise quickly from this point but then fall off again further down the pipeline where the fluid temperature falls closer to that of the pipewall. For instance. gas slugs may travel the length of the pipeline. the increased flowrate alters the temperature profile.000bbl/day deposition is not predicted until some 40km down the line.000 bbl/day. the gas has a greater effect upon other factors. It is interesting that dissolved gas tends to reduce the deposition tendency.

There are three main types of chemicals: (i) Wax Crystal Modifiers or Wax Inhibitors Wax crystal modifiers inhibit deposition by co-crystallising with the wax crystals and preventing structured lattices from forming at the pipe wall.2 Chemicals Pigging may be operationally inconvenient or even impossible and an alternative method of the wax removal is required. Whilst this may increase the rate at which wax is brought to the surface by shear dispersion. Therefore. This is because these crystal modifiers do not influence the higher molecular weight waxes. carried along by the flow of crude. the heat transfer will be limited by the concrete and not by thin layers of wax which form on the pipe wall. the initial deposition rate drops off until the wax layer is thick enough to insulate sufficiently to create no temperature difference between the fluids and the depositing surface. This means that the equilibrium thickness is likely to be unacceptably high from an operational point of view. However. In pipelines which are submarine and concrete coated. Generally. 3. Chemical additives can provide an effective means of controlling wax deposition. 3. the shear stresses at the depositing surface increase. The pig is sent down the line. As the thickness of the wax layer increases.5 Controlling Wax Deposition The three most common methods of controlling wax deposition are: 3. there is no universal wax inhibitor and to identify the most effective additive the chemicals must be tested under the specific operating conditions for which they will be used. Thus it is usually still necessary to pig the line occasionally. One of these additives actually increased deposition at certain temperatures. Work is currently examining these longer term effects. Figure 20 shows how simply temperature can affect the performance of several inhibitors. Some inhibitors may reduce the amount of wax deposited but can make it harder to remove the wax that does deposit.5.BP Exploration Appendix 7 – Production Chemistry Reference Documents As the wax layer is allowed to accumulate.5. the shear may be sufficient to strip off further wax. the equilibrium thickness may not be that predicted from molecular diffusion alone.1 Pigging This is the most commonly used method for removing wax deposits accumulated on the pipe wall. and mechanically scrapes off the wax and redisperses it in the bulk oil in front of the pig. Page 16 . This will subsequently reduce further deposition by increasing the temperature at the depositing surface and reducing the temperature gradient in the boundary layer. Thus. it will act as an insulating layer thus reducing heat transfer. there are other effects which impact upon the equilibrium thickness. complete inhibition of wax deposition is economically not feasible and it is more efficient to slow down the deposition process and periodically remove the built-up wax deposits using an alternative method such as pigging. However. Most will only slow down the process of wax deposition and will not completely inhibit the formation of wax deposits. The pig is unlikely to completely remove the wax deposits but leaves behind a smooth layer which reduces pipe wall friction and hence pressure drop.

They chemically coat small wax particles and decrease their tendency to stick together at the pipe wall. (iii) Surfactants/Detergents If the crude oil contains produced or added water then paraffin surfactants can be very effective in removing or inhibiting wax deposition. A good dispersant can penetrate an accumulated mass of wax.3 Hot Oil Flushing An increase in flowing temperature and flow rate will encourage wax removal even in the absence of any wax dispersant. laboratory test results show that wax layers can be completely and quickly removed. 3. wax/oil ratio and resilience of the wax deposits. Page 17 .BP Exploration Appendix 7 – Production Chemistry Reference Documents (ii) Dispersants These chemicals are usually added to remove existing deposits. If flowing temperatures are increased significantly (~10°C) with no increase in shear. The effectiveness of hot oiling in a pipeline system as a removal mechanism will depend on the hardness. but can also inhibit wax deposition.5. coat individual particles and allow them to move freely into the surrounding oil. These additive cause the wax crystals to become "hydrophilic" so they preferentially adhere to the water molecules and not to each other or the pipe wall. by "softening" the wax on the wall and making it unstable and easy to remove.

4 6.3 5.6 3.5 2.1 5.5.2 2.5 3.5.4 3.2 5.2 Asphaltene Flocculometer Modelling ASPHALTENES IN OILFIELD OPERATIONS 3.1 Flow Through Visual Cell 2.6 3.1 3.7 3. INTRODUCTION 1.3 3.1 1. DETERMINING THE RISK OF ASPHALTENE DEPOSITION 2. Pipeline Studies Ula Asphaltene Deposition Study The Effect on Asphaltene Precipitation of Miscible Gas TREATING ASPHALTENE PROBLEMS 5. What are Asphaltenes? Asphaltene Precipitation Chemical Treatment 5.8 4.3 2.3 5.2 4.1 Dissolving Precipitated Asphaltenes 5.5.4 2.2 2.1 4.2 3.5. 1.1 2.BP Exploration Appendix 7 – Production Chemistry Reference Documents ASPHALTENES INDEX Page No. Effect of Temperature Effect of Pressure Effect of Gas Lift Effect of Acid Stimulations Effect of Miscible Gas Effect of Oxidation Effect of Electric Fields Effect of Mixing Different Streams TYPICAL ASPHALTENE STUDIES 4.2 Asphaltene Inhibitors Plastic Coatings Engineering Solutions Operational Changes REFERENCES FIGURES 1-12 Page 18 . Sampling Asphaltene Content Resin Content Molecular Weight of Asphaltenes and Resins Onset of Asphaltene Flocculation 2.

One theory suggests that asphaltenes are present in a micellar state in which there is a central core consisting of very high molecular weight asphaltenes with many condensed aromatic rings. Boussingault. Figure 2 illustrates this. Lower molecular weight solvents such as propane will precipitate larger amounts of material since the precipitate also contains some resin material. but insoluble in normal alkanes such as n-heptane. Therefore asphaltenes are classified according to the precipitant and no single molecular structure is appropriate. the standard IP test for the asphaltene content of a crude oil determines the n-heptane insolubles. but are absorbed by surface active materials such as Fuller's earth. As the distance from the central core increases. Others suggest that asphaltenes do not exist as cumbersome aggregates. but soluble in turpentine. depending upon the solvent. This is surrounded by a region of sheets of lower molecular weight asphaltenes and resins strongly bound by electrostatic forces. they form part of the high molecular weight fraction of a crude oil that. but as single asphaltene molecules stabilised in solution by resins through hydrogen bonding. They contain a broad distribution of polarities and molecular weights and the material precipitated will vary with the solvent used. 3% nitrogen and 5% oxygen. For instance. There is a close relation between asphaltenes and the higher molecular weight resins and polycyclic aromatic hydrocarbons that exist in crudes. The result is an onion-like structure with layers of resins surrounding further layers of resin-like asphaltenes surrounding a central asphaltene core. heavy polycyclic aromatics oxidise to form neutral resins. Now. Asphaltenes probably arise from further oxidation of resins. and up to 10% sulphur.1 What are Asphaltenes? The term "asphaltenes" describes a group of compounds naturally present in crude oils whose chemical structures are complex and difficult to analyse. In crude oils the asphaltenes are not normally present in true solution. the number of condensed aromatic rings falls and there is a gradual transition to less polarity and less aromaticity. in 1837. plus traces of heavy metals such as vanadium and nickel. INTRODUCTION 1. They have a very strong tendency to associate with themselves and resins and form aggregates. Resins are described as the material that is soluble in the nalkanes that precipitate asphaltenes. Figure 1 is an attempt at illustrating a typical asphaltene molecular structure. Page 19 . Generally. The nature of precipitated asphaltenes also varies between different crudes.BP Exploration Appendix 7 – Production Chemistry Reference Documents 1. the asphaltene fraction of a crude oil is usually defined as the heavy polar aromatic fraction that is soluble in hot aromatic solvents such as toluene. 7-10% hydrogen. since its appearance was similar to that of the original asphalt. The resultant molecular weight of the precipitated material therefore can vary enormously from thousands to millions. Analysis of n-pentane precipitated asphaltenes might typically show 8085% by weight carbon of which 50-60% is aromatic. They are not fully understood and various theories exist to describe their chemistry and behaviour. first used the word "asphaltene" to describe that part of a crude oil distillation residue that was insoluble in alcohol. along with maltenes constitute "asphalt". During geological timescales.

The resultant deposit may be a very viscous sticky fluid that can contain entrained oil. The physical state of the asphaltene molecules or micelles in crude oil is determined by the stabilising nature of the resins. highly condensed core species.BP Exploration Appendix 7 – Production Chemistry Reference Documents 1. Crudes that are aromatic in nature and have a high resin content will be less liable to asphaltene deposition. These figures do not illustrate the amount of alkane required to form a precipitate. Any operations that causes the stabilising layers to be removed can result in the unpeptized asphaltene molecules or micelle flocculating and forming a deposit. The stabilising effect of resins can be illustrated by the nature of the asphaltene precipitate formed when n-alkanes are added to a crude oil. asphaltenes are only a problem when they are precipitated. Figure 4 illustrates how much of an asphaltenic crude can be precipitated by alkane solvents from propane to n-heptane. They have also been seen in production equipment. Tubing deposits can cause severe problems to wireline operations. Page 20 . If asphaltenes are precipitated by lighter n-alkanes. Asphaltene deposits have been observed in production tubing. These pack closely together leading to a very hard deposit. To identify whether asphaltene precipitation is likely and where it may occur. The nature of the deposits is determined by the crude oil and the conditions under which precipitation occurred. fewer of the peptising resins may be removed. resulting in a precipitate with a lower molecular weight. they will be composed of the high molecular weight. nor the weight of precipitate for a given volume of alkane. Asphaltene deposition in the reservoir has been reported causing permeability reductions or changes to wettability. resulting in lower recoveries. or more sticky and tar-like. Higher alkanes produce a precipitate containing a lower percentage of resins and consequently less precipitate. In the stable well dispersed state. For instance. The risk of asphaltene deposition is therefore a result of not only the amount of asphaltene and resin material in the oil.2 Asphaltene Precipitation In the oil industry. such as separators. Lighter alkanes can only remove some of the lighter outer resins which more closely resemble alkanes in structure. where asphaltenes have collected after having been precipitated further upstream. the precipitation process itself must be understood. the asphaltenes are referred to as being peptized by resins and maltenes. if all stabilising resins are stripped away and asphaltenes precipitate. The nature of the crude oil itself also has an effect. Asphaltene deposits can appear hard and coal-like. the but also of the solvency power of the oil for its asphaltenes. Figure 3 shows the molecular weight of the asphaltene precipitated by a homologous series of n-alkanes. restricting flow and causing production declines. Longer alkane chain lengths are able to remove more of the peptizing resins. An aromatic oil will be a good solvent for the peptised asphaltenes while a paraffinic crude will be a poor solvent. Downhole safety valve problems have been attributed to asphaltenes in BP's Ula field and other asphaltene problems have been encountered Clyde and in the Middle East in Kuwait.

Frequently. When the fluids are below their bubble point in the reservoir. Even when the bubble point falls in the production tubing between the perforations and the wellhead it is not easy. 2. [1]. which is finally evaporated off leaving the solid weight of asphaltenes. to obtain a representative sample from which to determine the risk of asphaltenes the oil must not have lost any of its asphaltenes. The solvency of a crude for its asphaltenes can be determined via either a flow through cell apparatus or using a laboratory titration technique. Page 21 . This could be achieved by sampling into a high pressure vessel. A known amount of the oil from which the asphaltene has been removed is separated. Resins are then eluted by backflushing the column with chloroform/methanol. The resins are recovered by evaporation. Once sampled. Resins are isolated on an amino propyl normal phase HPLC column. the crude oil must be characterised for its asphaltene content and its solvency for its asphaltenes. Once the intermolecular force which stabilises the asphaltene resin micelle is broken.1 Sampling Studies have shown that asphaltene precipitation can be essentially irreversible. This method extracts asphaltenes and the waxy fractions from a crude oil using n-heptane. 2. asphaltene precipitation takes place. Wellhead samples may have lost some asphaltenes. and pressurising the sample to above its bubble point. The resin content of a crude can be measured by an HPLC technique. Before any characterisations are undertaken. the amounts lost are likely to be only a fraction of the total asphaltene content. 2.2 Asphaltene Content The asphaltene content of an oil can be determined by the IP laboratory test method IP 143. To achieve this. it is important that a representative sample of crude is taken. Using isocratic elution with the same solvent. When this resin encapsulation shield is removed by addition of n-alkanes. samples must be taken at pressures above the bubble point and maintained single phase. Asphaltenes are then extracted into toluene. further asphaltene deposition should be avoided. It is important to establish the balance of the asphaltene and resin fractions of the crude since this information is essential to identifying the instability of a stock tank crude sample. Typical assays include asphaltene and resin contents and their respective molecular weights. determined by weight and reported as a percentage of the original oil. DETERMINING THE RISK OF ASPHALTENE DEPOSITION In order to establish the risk of asphaltene precipitation during oilfield operations.3 Resin Content Resins provide a protective shield around the asphaltenes to prevent them from aggregating and precipitating.BP Exploration Appendix 7 – Production Chemistry Reference Documents 2. saturates and aromatics are eluted from the column for a specific time period. providing the well has been flowing for some time. this is clearly impossible. Each is discussed below. the precipitated asphaltene cannot be easily resolubilised. Therefore. and then the effect of the external conditions determined. only wellhead samples are available. The asphaltene content of a crude oil is insufficient alone to predict the likelihood of asphaltene precipitation. however. and as such is of limited value without further information.

4 Molecular Weight of Asphaltenes and Resins Gel Permeation Chromatography can be used to establish the molecular weight distributions of asphaltene and resin fractions precipitated under known conditions. 2. 200 µl sample solution injection with eluent flow of 1 ml/min. 103 Â. Page 22 . Waters 410 refractive index detector. 100 Â. On reduction of pressure. and asphaltene flocculation can take place. BP use the following conditions. the solvency of a crude for its asphaltenes is reduced. Equipment calibrated using polystyrene standards in THF. Waters µ styragel columns 104 Â.5. Mw etc are calculated using an 'Expertese software' package. The technique is not appropriate for all crudes. In other words. 500 Â. BP have used two methods to establish how close to asphaltene instability a crude will be.2 Asphaltene Flocculometer The solvency of a crude oil for its asphaltenes can be determined quantitatively by titrating the crude with an n-alkane flocculant and measuring the volume of alkane required before sufficient resins are removed to allow asphaltenes to precipitate. It has been found that crudes with a resin to asphaltene ratio approaching unity tend to be more susceptible to the influence of n-alkane additions. 2.BP Exploration Appendix 7 – Production Chemistry Reference Documents 2. GPC data collection using a Waters 860 data system.2 w/v% solutions in tetrahydrofuran (THF). The sample solutions are then characterised by GPC. 2. The pressure required for this to commence is then noted. crudes with a ratio tending to unity are more likely to suffer from asphaltene precipitation than those with a ratio less than unity. since the solvency of many for their asphaltenes is sufficient that a pressure drop alone will not result in asphaltene flocculation. Resin and asphaltene samples are individually made up as 0. The asphaltene flocculometer was designed by the Institute Francais du Petrole and built by Geomechanique of Paris.1 Flow Through Visual Cell This apparatus allows a crude oil to be pumped through a windowed cell at pressures and temperatures similar to those experienced under field conditions.5 Onset of Asphaltene Flocculation The asphaltene and resin contents do not define whether asphaltenes will be precipitated from any given crude under operational conditions. Light scattering is used to detect the onset of asphaltene flocculation. whilst an oil sample is titrated at the required temperature and pressure. Asphaltene and resin molecular weight parameters Mn.5. A narrow path length and a powerful light source are used to examine the transmittance through the oil as the pressure and/or temperature are altered. This can be observed by the formation of flocculated black deposits which adhere to the window.

These data provide an immediate comparison between different crudes. A new reservoir crude can be ranked with crudes where asphaltene risks are well known. A second fibre optic carries the reflected light to a silicon photo-diode which converts the returned light into a voltage signal. a known volume of the test oil sample is transferred to the pressure vessel. The volume of flocculant added is recorded against the voltage signal from the photo diode. A diagram of the flocculometer is shown in Figure 5 and the fibre optics shown in Figure 6. the oil reaches the threshold of flocculation. To measure the onset of flocculation.6 Modelling Wellhead samples are often the best that are available. Page 23 . The conditions that the crude oil will encounter are then examined. then asphaltene flocculation can occur. Since it is possible that asphaltenes have been lost from these. One fibre optic is connected to the light source and carries light into the sample. The model defines the stability of asphaltenes in terms of a critical chemical potential for the associated resins based upon the physical characteristics of the crude oil. As the flocculant is added. The information needed to run the model includes standard PVT data. and the resin potential calculated for the expected temperatures and pressures. The probe consists of two fibre optic cables and a mirror assembly. before being reflected by a mirror. If the resultant resin potential is exceeded. The titration takes place in a 500cm3 pressure vessel which is equipped with a magnetic stirrer and temperature controlled heating jacket. and the vessel heated to operating temperature. The voltage response is plotted by a chart recorder. BP has constructed a computer model to predict when and where asphaltene problems are likely. the oil sample is titrated with the flocculant. studies to determine the onset conditions necessary before asphaltene precipitation can occur may underestimate the risks. Predictions made using the model have been confirmed by field measurements (see section 4). The steel tube containing the fibre optic probe and mirror assembly is immersed in the oil. Partly to overcome these problems. a wellhead or a stock tank sample. a recombined high pressure sample. For stock tank samples an over pressure of nitrogen is applied. downhole samples are preferable but must be injected at pressure via a suitable piston vessel. The model has been used to predict the onset conditions for asphaltene precipitation in several BP fields in the North Sea and in Alaska. When sufficient flocculant is added. and to predict the potential for asphaltene problems in fields under development when only small samples are available. At the end of this fibre optic. The flocculant is added by a positive displacement Gilson pump. condensates or hydrocarbon mixtures. Nitrogen has been shown not to influence the test results. 2. which can be immersed in the oil sample. This may be a downhole pressurised sample. across a 1-10mm adjustable gap. and there is a marked decrease in the returned signal. asphaltene and resin molecular weights and the production temperature and pressure profiles. the light travels through the sample. depending upon sample availability or the pressure rating of the flocculometer.BP Exploration Appendix 7 – Production Chemistry Reference Documents The detection system is a 900nm monochromatic light source attached to an optical probe contained inside a steel tube. Clearly. Once at temperature. Figure 7 shows a typical output trace from the flocculometer with the onset of flocculation marked. the crude becomes lighter and there is an increase in the returned signal. as asphaltene particles scatter the reflected light.

combined with streaming potential effects in the production tubing will affect the stability of the crude [4]. and both are due to species becoming insoluble in the parent crude oil.3]. Peptisation occurs when the surface tension is over 26dynes per cm. 3. ASPHALTENES IN OILFIELD OPERATIONS As stated in the introduction. Whilst they may be observed in the same deposit. asphaltenes deposits can cause production rate declines by blocking tubing or reducing the permeability to oil in the reservoir surrounding a producing well. For asphaltenes the picture is more complicated. The model can predict the impact on asphaltene precipitation of introducing lift gas into a production stream for any given conditions. it is not surprising that asphaltene and paraffin wax deposits are often confused.1 Effect of Temperature Whilst the effect of temperature is critical in the mechanism for paraffin wax precipitation. pressure and the chemical composition of the crude. the mechanisms by which they form are different. Higher temperatures result in a reduction in surface tension and hence a greater push towards asphaltene precipitation. The effects which contribute to the insolubility of asphaltenes and their subsequent precipitation are discussed below. In production systems changes in temperature. then the more oil-like the deposit may appear. any actions of a chemical or electrical nature which depeptise these particles will lead to flocculation and precipitation [2. 3. The effect is thought to be due to the influence of temperature on the surface tension of the solvent. then an increase in temperature increases the amount of precipitate for a given amount of solvent. The peptizing or precipitating properties of different solvents with respect to asphaltenes have been shown to be related to their surface tension. With asphaltene molecules stabilised as colloidal particles peptised by resins. artificial lift would be expected to increase the risk of asphaltene precipitation since the lift gas consists essentially of light straight chain hydrocarbons that remove resins. it is much less obvious how temperature affects the precipitation of asphaltenes. Such information has been used in optimising the design of artificial lift apparatus to minimise the risk of asphaltenes. The more resins are precipitated with the asphaltenes. Page 24 . For instance.BP Exploration Appendix 7 – Production Chemistry Reference Documents One major advantage of this model is that changes to the operating conditions can be examined for their impact upon the risk of asphaltene precipitation. Little work has been reported. The model has also been used to establish the impact on asphaltene precipitation of a miscible gas flooding programme. but it appears that when asphaltenes are precipitated by non polar solvents such as alkanes. Thus. Temperature is the dominant effect for wax deposition. More importantly from an operational standpoint is the fact that asphaltenes precipitate more rapidly at higher temperatures. Flocculation can occur when the solvent has a surface tension below 25dynes per cm.

This has the effect of increasing the molar volume of the lighter ends in the crude. Firstly. 3. Acid stimulation treatments have been shown to adversely affect the asphaltene stability of certain crudes causing sludging and rigid film emulsions [8].6]. Page 25 . At the bubble point. and no further precipitation would be expected once pressures fall below the bubble point.BP Exploration Appendix 7 – Production Chemistry Reference Documents 3. This is enhanced during acid treatments. ie lower down in the tubing. There may be a secondary effect of two phase flow where the greater shear forces at the tubing wall strip away any further depositing asphaltenes. and hence increasing the likelihood of asphaltene precipitation. destabilising them and leading to precipitation. These are the very species which remove the stabilising resins from asphaltene molecules or micelles. gas breakout occurs. The magnitude of the risk depends upon how close to flocculation the oil was before mixing with lift gas and the nature of the lift gas. Asphaltenes may precipitate at pressures above the bubble point. Different species in the oil expand at different rates depending upon their compressibilities. No deposition is found further up the tubing at pressures below the bubble point. The lighter ends such as methane expand to a greater degree than the heavier components. As the fluids rise in the tubing the pressure gradually drops and the oil expands.2 Effect of Pressure Pressure has a large effect on the flocculation of asphaltenes.e. increasing their influence on the stabilising resins. formation damage has occurred which subsequently was considered to be due to asphaltene deposits plugging the formation. This effect is shown in Figure 9. dissolution of CO2 into the crude depeptises the resins in much the same manner as light hydrocarbons. further increasing the risk of asphaltene precipitation. i. ethane and propane are lost from the oil. Studies of asphaltene deposition in production well tubing have found that deposition occurs below the depth at which the bubble point for the crude occurs. In wells where gas lift has been installed. where lighter gases such as methane. There are examples in the literature of methods to limit these effects [9]. occurs at a depth just below where the fluids are at their bubble point. there can therefore be an increased risk of asphaltene precipitation. CO2 tends to strip out the lighter hydrocarbons. The greatest chance of precipitation however.5 Effect of Miscible Gas In some CO2 miscible flood programmes. The loss of these alkanes therefore increases the solvency of the crude for its asphaltenes.4 Effect of Acid Stimulations Production wells subjected to acid stimulation can result in asphaltene deposits when during normal production none were observed. 3. Asphaltene sludges and emulsions stabilised by asphaltenes have been observed. Solubility theory and thermodynamic equations of state can be used to confirm this reduction in asphaltene solubility as an oil approaches its saturation pressure [7]. 3. when the oil is still single phase [5. An illustration of typical asphaltene deposition in production tubing is shown in Figure 8.3 Effect of Gas Lift Lift gas usually consists mainly of light alkanes which are able to strip away the peptizing resins. Little is reported on the nature of the deposits but it appears that CO2 can destabilise asphaltene micelles by two mechanisms. The polar nature and consequent surface activity of asphaltenes attracts them to oil/water interfaces. Secondly.

In this field. additions of other hydrocarbons could reduce the solvency number and make asphaltene instability more likely. In a major export line. 4. and any crude which is susceptible to asphaltene precipitation is likely to have lost asphaltenes before this point in the production system. 4. This could occur. This is discussed in more detail in Section 4 below where a study on a North Sea export line is reported.6 Effect of Oxidation Exposure to air can cause resins to oxidise. For instance. Mixing different crude streams can have a significant impact on the risk of asphaltene precipitation. Oils can thus be classified on a common scale and the compatibility of entrants to the pipeline determined. This method is an adaptation of a method reported by Reichart [11] for measuring the solvency of various mixtures of bitumen solutions.BP Exploration Appendix 7 – Production Chemistry Reference Documents 3. 3. This work has been subsequently published (6). the effect is likely to be small. asphaltenes were considered responsible for several operational difficulties experienced in the production facilities. describes the stability of the crude for its asphaltenes and is used to define a solvency number.7 Effect of Electric Fields The polar nature of asphaltenes can cause an attraction to positive or negative electrodes. However. Therefore the fluids should be tested to ensure compatibility. The volume of alkane titrated to induce asphaltene flocculation. there may be several streams from different reservoirs all using the same line.1. Page 26 . for instance. This can be done using the asphaltene flocculometer apparatus for both single crudes and blends. the resultant measured asphaltene content was shown to rise. TYPICAL ASPHALTENE STUDIES 4. a BP field in the Norwegian sector of the North Sea. Where this has occurred.2 Ula Asphaltene Deposition Study A programme of laboratory and field studies was carried out to determine the onset point of asphaltene precipitation and to predict future trends as operational conditions changed in Ula. Pipeline Studies The addition of oils or condensates in common pipelines can alter the overall solvency of the blend. This effect would not normally be considered important during normal operations. in electrostatic separators. and electrodeposition has been reported (10) in some heavy crudes. When a given crude blend has been assigned a solvency number.8 Effect of Mixing Different Streams Each hydrocarbon has a given asphaltene content and a particular solvency for its asphaltenes. a light condensate with little asphaltenes can destabilise a crude with a high asphaltene content which on its own has good asphaltene solvency. at set conditions of temperature and pressure. 3.

Chemical Treatment 5.1 was used to establish that asphaltene flocculation started at 30 bar above the saturation pressure and ceased once the saturation pressure was reached.1. Long chain carboxylic acids have been identified as effective for deasphalting. Page 27 . This is also the proposed mechanism for a recently developed polymeric asphaltene dispersant chemical produced by Nalco. Further. with the relatively high asphaltene and resin content. 4.1 Dissolving Precipitated Asphaltenes Despite the worldwide occurrence of asphaltenes in oil fields and the many examples in the literature detailing the serious effects on production resulting from deposition. It was predicted that miscible gas would only result in asphaltene precipitation at very high levels against Prudhoe crude. there is a lack of data on successful inhibition.1. The actual potential was then calculated when miscible gas was added at various mixing ratios to the crude and compared to the critical. Subsequently. A similar survey for a Clyde well is illustrated in Figure 10. preventing flocculation. A Kinley Caliper survey indicated that the restriction in the diameter of the tubing thought to be caused by asphaltene deposition coincided precisely with the pressures at which asphaltene flocculation would occur as identified in laboratory studies. Further.BP Exploration Appendix 7 – Production Chemistry Reference Documents The flow through apparatus described in Section 2. BPX developed an asphaltene precipitation model which calculates a critical chemical potential for the stabilising resins. the asphaltene stability in terms of the resin critical potential was determined. Figure 11 illustrates the results of the modelling study for Ula. This is illustrated in Figure 12. 5. Long chain anionic surfactant have also been reported as effective although this chemical type would not be suitable in production systems since they would encourage formation of emulsions. For the fluids examined.3 The Effect on Asphaltene Precipitation of Miscible Gas A study was undertaken into the effect of miscible injectant gas (MI) on asphaltene stability at Prudhoe Bay. This study characterised the Prudhoe Bay crude oil. Typically hot aromatic solvents such as xylene prove effective. probably by reacting with precipitated asphaltenes via hydrogen bonding. If the actual potential calculated for given pressure and temperature conditions exceeds the critical. TREATING ASPHALTENE PROBLEMS 5. since changes to wettability can alter the relative permeability to oil. although production wells must be shut in for several hours for such a treatment. aromatic solvents can pose environmental hazzard and tend to dissolve elastomer seals. asphaltene precipitation is possible if the pressure is between about 100 and 200 Bara. then asphaltene precipitation can occur. 5. There is an additional risk if the solvent reaches the formation. and through modelling. the amount of asphaltene that could be precipitated would be high and any deposit would be tar-like. and cause a dramatic reduction in oil production rates.1.2 Asphaltene Inhibitors Several treatments have been reported using long chain molecules that mimic the stabilising effect of a resin layer.5. Many operators however rely upon periodic solvent washes to remove asphaltenes that have formed.

Page 28 . no commercial equipment is available. Mechanical scraping devices can been used to remove blockages in production tubing. since liquid hydrocarbons and condensates are at a premium. although at the time of writing. Coiled tubing has also been used to inject asphaltene solvents/inhibitors (12). Plastic Coatings Epoxy resin coatings have been applied to tubulars (12) in an attempt to stop asphaltenes from sticking and building up into a deposit. lowered and powered from coiled tubing. considerable work is underway to develop improved asphaltene inhibitors. These were designed as a preventative treatment. 5.3 Engineering Solutions Dual completions have been used in the Prinos field in Greece to allow the injection of Xylene [13] directly into the production stream. 5. In one field a downhole hydraulic motor has been used.4 Operational Changes The greatest risk of asphaltene deposition occurs at pressures just above the bubble point. 5. This may not of course be an option. If the reservoir pressure can be reduced by rapid depletion such the bubble point occurs away from the production tubing in the reservoir itself. then asphaltene precipitation will not impact production.BP Exploration Appendix 7 – Production Chemistry Reference Documents C-10 through to C-20 aliphatic alcohol partial esters of phosphoric acids are claimed to improve the stability of asphaltenes in bituminous oils at dose rates of as low as 50ppm. deployed by "squeezing" it into the petroleum bearing formation in a similar manner to many scale inhibitor treatments. although in this reported case results were disappointing. and has been found to be the most economical method of controlling asphaltenes (12). A recent report (10) has indicated ultrasonic treatments can clean up asphaltenes deposited in near wellbore regions. Details are limited of how effective this method was and the high cost of such completions probably eliminates this is a possible solution in most cases. At the time of writing. possibly as a result of the relatively poor performance of the chemicals used. No improvement was reported here although the technique may still have some merit.2.

1994 "Ultrasonic Treatmentfor Removal of Asphaltene Deposits During Petreoleum Production. Jan-June 1983 [9] Newberry M.H. 1994 [11 ] Reichert C. Nicoll and Dick G.E. and Mansoori G. J. 1982 Investigation of Physical and Chemical Criteria as Related to the Prevention of Asphalt Deposition in Oil Well Tubings. Sept-Oct 1986 [12 Akbar S. 1985 "Formation Damage Prevention through the Control of Paraffin and Asphaltene Deposition.J. and Saleh 1989 A Comprehensive Approach to Solve Asphaltene Electrical and Other Effects Related to the formation and prevention of Asphaltenes Deposition. Jan. Park and S.M. Feb 4-6 [3] Lichaa P. Petroleum Tech. and Barker K. & Mansoori G. Dallas. 16-17. San Antonio. 1965 A Solution to the Problem of Asphaltene Deposits . 1988 Asphaltene deposition in Production Facilities." JCPT Montreal.A. Pet. 1985 [10 ] Gollapudi U k.Hassi Mesoud Field. SPE Paper 5308 Oilfield & Geothermal Chemistry Symposium. MSc thesis. [5] Adalialis S." SPE 27377 Louisiana . SPE Paper 18473. February 7-10. Bang S S. 387-391. and Herra L. 1987 Asphaltene Flocculation Duriong Oil Production and Processing: A Thermodynamic Colloidal Model.M.BP Exploration Appendix 7 – Production Chemistry Reference Documents 6. and Islam M R. Texas. Fuhr B J. March 10-12." SPE Paper 13796.A. [6] Thaver R. Tech. [4] Haskett C. J. (April 1965). REFERENCES [1] Institute of Petroleum. London Standard Methods for Analysis & Testing of Petroleum and Related Products IP143/84 [2] Leontatritis K. SPE Paper 16258. 1983 High-Pour-Point and Asphaltic Crude Oils and Condensates. and Tantera M. Imperial College University of London. The Role of Asphaltene Deposition in EOR Gas Flooding: A Predictive Technique. SPE/DOE Paper 17376 Page 29 . and Klein LL 1986 "Measurement of Asphaltene Flocculation in Bitumen solutions. [7] Kawanaka S. Algeria. 35. [8] Tuttle R. Petroleum Engineering Department. Oklahoma City.E. Symposium on Oilfield Chemistry.J.N.

11-14 March. [13 ] Adailas. Page 30 . Manama. 1982 Investigation of Physical and Chemical Criteria as Related to the Prevention of Asphaltene Deposition in Oil Well Tubings. Deposition Problems in Some Deep Wells. Bahrain. Middle East Oil Technical Conference and Exhibition. SPE Paper 17965. MSc Thesis. S.A.BP Exploration Appendix 7 – Production Chemistry Reference Documents ] A.

1.2 Scale Inhibitor Mechanisms 4.BP Exploration Appendix 7 – Production Chemistry Reference Documents WATER CHEMISTRY AND SCALE INDEX Page No.1.1 Thermodynamic Background 3. 1.3 Organic Polymers 4. Drilling and Completing Wells Water Injection Reservoir Damage Water Production Production Operations The Cost of Failure SCALE PREDICTION 3 3.1 Effect of Bulk Ionic Strength on Solubility 3.1.1.2 Treatment of Non-aqueous Phases SCALE INHIBITORS 7 4.3 8 Static Scale Precipitation Test Dynamic Scale Precipitation Test (Tube-Blocking Test) Dynamic (Porous Media) Tests 6.5 Effect of Pressure on Mineral Solubility 3.2.4 Phase Behaviour 3.4 2.1.1 Nucleation and Growth 4.5 2.2.2 2. 5.1 Concept of the Ion Pair 3.2. 4.1 5.2 Inhibition 4.1 2. SCALE DISSOLVERS 10 Page 31 .1.2 Effect of Temperature on Mineral Solubility 3.3 Effect of Specific Ions on Mineral Solubility 3. THE OCCURRENCE OF SCALE 1 2.1. PROBLEMS CAUSED BY SCALE 1 2.1 Inorganic Phosphates 4. APPLICATION OF SCALE INHIBITORS 9 7.2.3 2.2 Organophosphorous Compounds 4.1 Scale Inhibitor Types 4.2 Geochemical Aqueous Modelling 3.2 5.2.3 Blending Scale Inhibitors LABORATORY EVALUATION OF SCALE INHIBITORS 5.1.6 3.

BP Exploration Appendix 7 – Production Chemistry Reference Documents TABLE 1 FIGURES 1-5 APPENDIX 1 SCALE PREDICTION STUDY FOR FORTIES TABLE 1 FIGURES 1-5 APPENDIX 2 SCALE PREDICTION STUDY FOR PRUDHOE BAY TABLE 1 FIGURES 1-2 Page 32 .

two incompatible waters mixing (e. which can lead to problems under some circumstances. Typical analyses of Magnus. Ula and Prudhoe Bay formation waters and North Sea water are given in Table 1. However. some formation brines naturally contain significant levels of dissolved iron in the reduced ferrous state. The deposition of mineral scales is dependent on a number of variables including: (i) (ii) (iii) (iv) (v) (vi) (vii) degree of supersaturation of scaling ions in the water rate of temperature change degree of agitation during formation of scale crystals size and number of seed crystals presence of impurities change in pH of solution changes in pressure Common oilfield scales form in one of two ways. adherent deposit of inorganic mineral which constitute 'scale'.1 Drilling and Completing Wells Scale can cause problems if the drilling mud and/or completion brine is intrinsically incompatible with the formation water. However some areas are more difficult and costly to treat than others. Iron scales (sulphides when production is sour. It is not only the oil industry that suffers from scale. hydrous oxides when production is sweet) often reflect corrosion in the system. THE OCCURRENCE OF SCALE Water is the most common and in many respects the most important fluid known to man. PROBLEMS CAUSED BY SCALES Scale does not restrict itself to any particular location in the oilfield. Water is always in the process of dissolving or depositing solids and it is the precipitation of these dissolved solids as a hard. a change in conditions such as temperature or pressure can promote carbonate scale from a formation water. with iron originating from the pipework or vessels in the system itself. Secondly.g. hydrous oxides and carbonates may also form solid deposits that give similar problems. scale can build up in domestic kettles and steam irons. 2. it would be simpler to produce oil and gas. complex salts of iron such as the sulphides. For example. as would allowing a high-calcium brine to encounter a formation water rich in bicarbonate. Firstly. strontium and barium. 2. Forties. Miller. Were it not for water however. Oilfield scale is generally thought of as the carbonates or sulphates of the Alkaline Earth metals calcium. Nineteen centuries ago the Romans experienced calcium carbonate scale in their aqueducts and canals. Wytch Farm. allowing a sea-water based mud to contact a formation water rich in barium and strontium ions would be undesirable. These formation waters reflect the typical variations in formation water chemistry encountered in BP's reservoirs. However. a formation water with sea water ) can promote sulphate scale. Page 33 . In areas of hard water.BP Exploration Appendix 7 – Production Chemistry Reference Documents 1.

Initially. When injection water breakthrough occurs in production wells additional (and potentially much more serious) scale problems may arise. There is thus an increased risk of invasion and formation damage due to scale subsequently resulting in very high skin factors. Obtaining representative water samples as soon as possible are important to assess the consequences of drilling mud filtrate invasion in future wells in the field. 2. Experience suggests that problems are first observed in the production tubing rather than in the near well region. 2.3 Reservoir Damage This is an aspect of scale precipitation which is only now being seriously addressed by reservoir engineers. scale blocks in the oil producing zones could kill a well. sea water injection into an aquifer rich in strontium or barium ions could cause problems. Thankfully. and the movement and mixing of waters within the reservoir are needed before any predictions are possible. protection against scale may be desireable. Any mixing of incompatible brines can cause severe scaling wherever it occurs (whether in the production wells or in the reservoir). 2. There is no way of knowing accurately the chemistry of the formation water that will be encountered and often a more dense mud than is actually required will be used to reduce the chance of kick backs. a risk of carbonate scale formation occurs. The effect on oil production from scale precipitation in the bulk reservoir will be small.4 Water Production As soon as a production well begins to cut water.2 Water Injection Problems may arise at the commissioning stage of new injectors if the injection water is intrinsically incompatible with the formation water. this is often only a temporary effect until the injection water has flushed away the formation brine from around the near wellbore region. Timely remedial treatments to reduce downhole scale formation can then also protect the near formation. productive zones could be entirely blocked off. Such damage may be ignored if fracturing past the damaged zones is practical. However. In the extreme. Page 34 . Scale formation in the near wellbore region of a producer could have a beneficial effect if it is restricted to the water producing zones. For example. the consequences of scaling in the near wellbore region could be significant. However. for instance by deploying a scale inhibitor for the first few days.BP Exploration Appendix 7 – Production Chemistry Reference Documents Drilling the fist well in a new prospect can be particularly hazardous. A better understanding of the reservoir/fluid interactions such as ion exchange and mineral dissolution/precipitation. thereby reducing water cuts. The severity of the problem obviously depends on the water chemistry but is aggravated by high drawdowns when large pressure drops increase the risk of carbonate scale in the formation or across perforations.

3. the costs involved could be very large.BP Exploration Appendix 7 – Production Chemistry Reference Documents 2. valves. some of it will dissolve. filters and all associated pipework are at risk.5 Production Operations Once water is first produced. If excess barium sulphate is suspended in water.(aq) Page 35 (1) . desalting. a typical workover for a North Sea well may cost several hundred thousand pounds for a platform well and up to two million pounds for a satellite well. The latter possibility may arise from a process operation (sand-washing. pumps. 2. even if a well which has suffered sea water breakthrough does not suffer damage. the water which that well produces is unlikely to be compatible with 'pure' formation water and mixing such waters in the production system is sooner or later bound to cause problems. Factors such as fluid dynamics (which influence the transport of ions to and from a surface) and crystal size and shape (which influence transport in porous media) are undoubtedly important. Platform production shutdowns are enormously expensive. To predict the formation of scale in systems of this kind requires a sophisticated computer model together with accurate kinetic and thermodynamic data. For example. cleaning or replacing damaged equipment and from lost production. a platform processing 125000 barrels of oil per day generates £2. If scale precipitation in the body of the reservoir is proved to impair ultimate oil recovery. 3. Solubility limits of mineral salts may be exceeded by changing the temperature and pressure.6 The Costs of Failure These include the cost of stimulating damaged wells.1 Thermodynamic Background Consider barium sulphate. involving not only reduced cash-flow but also reduced gross revenue.000 of gross revenue daily. or by mixing incompatible waters. This last point is particularly important. the gross cost of 1 day's lost production is £200. detailed information is unknown and accurate prediction is therefore often a compromise. The following equilibrium then applies: Ba SO4 (s)  Ba2+ (aq) + SO42. It is thus vital to ensure that scale is predicted well in advance. a sparingly soluble salt.500. until the solution is saturated. Frequently. SCALE PREDICTION Scale formation from oilfield brines takes place in a multicomponent. and that effective remedial treatments can be put in place. process equipment such as heat exchangers. If a well produces 10000 barrels of oil per day.000 (@ £20/bbl).) or because waters from different wells are mixed in the production system. etc. The technical target for such a predictive model is to assess: - how much scale will form as a result of a given operation where it will form how damaging it will be Satisfying the last criterion is rather difficult. multiphase environment.

By definition. Both are functions of temperature and pressure. ASO42- (2a) This equation can be rewritten in the more familiar terms of concentrations as follows: K = [mBa2+ . pressure and the concentration of specific divalent ions in the solution. ÿSO42-] (3) where m is the molality and ÿ the activity coefficient of the ions in aqueous solution. such that: K = ABa2+ . Therefore. the concentration of carbon dioxide gas in solution is an additional factor to consider. For carbonate scales. Activity coefficients usually have a value in the range 0-1. mSO42-] . and the presence of other ions in solution also has a marked effect upon the value of the activity coefficients. temperature. K. [ÿBa2+ . Production from oilfields is however a dynamic process which may only approach thermodynamic equilibrium in the reservoir. For a two-phase system the concentration of CO2 in solution is related to the partial pressure of CO2 in the gas phase (Henry's Law). µ. Care should therefore be taken in relying on thermodynamic based predictions without some understanding of the processes involved. Most scale prediction models are therrmodynamic in nature and take account of all of the above effects.0 and represent deviations from ideal solution behaviour. The importance of these parameters are discussed below. thermodynamic scale prediction models overestimate the risk of scale. the activity of a pure solid is unity. thus the equilibrium constant can be written: K = ABa2+ .BP Exploration Appendix 7 – Production Chemistry Reference Documents This extent of this reaction can be described by the equilibrium constant. The total concentration of ions is given by the ionic strength. the solubility of barium sulphate scale depends on solution ionic strength. Page 36 . i In summary. where: µ = ci zi2 (4) where C is the concentration of the ith ion and Zi its valency. to determine the solubility of barium sulphate (or any other mineral) in a given water requires not only the equilibrium constant K but also the activity coefficients to be calculated. Generally. ASO42-------------------A BaSO4 (2) where A is the activity of each species.

calcium and strontium may not be high enough to cause precipitation of their respective sulphates. For example. they are nevertheless able to 'tie-up' significant levels of sulphate in the form of ion-pairs. barium sulphate (and all other scales) becomes more soluble. A solubility plateau is then reached. The effect of temperature on solubility is more pronounced for strontium sulphate than for barium sulphate.1. the dissolution of strontium sulphate is an exothermic process (over the same temperature range). This can be understood in terms of ionic activities: the presence of foreign ions shields the barium and sulphate ions from each other.1. 3. The effect of magnesium. calcium and strontium ions (ie other divalent cations) on the solubility of barium sulphate. Even though the respective concentrations of magnesium. reducing their activities and allowing more of them to co-exist in solution.SO4 (aq)  Mg.SO4 (aq)  Ba2+ (aq) + SO42. These other ions affect the solubility of the scale and may change the predominant phase of the scale. At these ionic strengths the ions are 'unhappy' because they are not well solvated. the following equilibria operate: BaSO4(s) MgSO4(s) CaSO4(s) SrSO4(s)     Ba.1 Effect of Bulk Ionic Strength on Solubility A plot of barium sulphate solubility as a function of ionic strength is given in Figure 1. (For comparative purposes. is small). Page 37 .(aq) Ca2+ (aq) + SO42.3 Effect of Specific Ions on Mineral Solubility The solubility of any given scale is affected by the concentration of other ions in the brine.(aq) Sr2+ (aq) + SO42. and their activities begin to increase again with ionic strength. This effectively reduces the overall activity of sulphate ions in solution. and then further increases in ionic strength reduce the solubility. is conventionally understood by the formation of ion pairs.SO4 (aq)  Sr.(aq) (6) (7) (8) (9) where the species M.2 Effect of Temperature on Mineral Solubility The dissolution of barium sulphate in water is an endothermic process (over the temperature range 35-110°C). Increasing the temperature therefore reduces the solubility of strontium sulphate.(aq) Mg2+ (aq) + SO42. thereby increasing the solubility of barium sulphate in that solution. In contrast. in a mixed electrolyte.1. the ionic strengths of various formation waters and North Sea water are included in Table 1). Therefore. The former property is considered here.SO4 (aq)  Ca.SO4(aq) are the ion pairs. 3. Appendix 1 contains an example of a scale prediction study illustrating the effect of temperature on both sulphate and carbonate scale formation. in absolute terms.BP Exploration Appendix 7 – Production Chemistry Reference Documents 3. increasing the temperature causes more to dissolve (although the effect. As ionic strength increases from zero.

CO2 (g)  CO2 (aq) (10) H2O + CO2 (aq)  H2CO3 (11) H2CO3  H+ + HCO3 -  CO32. hemihydrate. the overall effect may be summarised as follows. relevant thermodynamic data. aragonite. Figure 2 shows the solubility of calcium sulphate as gypsum or anhydrite as a function of temperature. A reservoir brine. The operational consequences are as follows. since the equilibrium constants for the equation above vary over several orders of magnitude. For example. can deposit scale when the brine is produced as the pressure falls.1. To take account of pressure effects. In a system as complex as that shown above.5 Effect of Pressure on Mineral Solubility The effect of pressure on ionic equilibria in aqueous systems is neglected in many scale prediction models due to the scarcity of reliable. the effect of a pressure drop may not be immediately apparent. the pH also increases. As a consequence of the reduction in H+ concentration. initially at equilibrium with calcite and containing a high concentration of CO2 . Calcium carbonate may exist as calcite. and anhydrite (the anhydrous form). A reduction in calcite solubility results. However.1.BP Exploration Appendix 7 – Production Chemistry Reference Documents 3.+ H+ H2 O  H+ + OH Calcite (S)  Ca2+ + CO32- (15)  CaHCO3+ (16)  CaCO3° (17) HCO3 Ca2+ + HCO3 Ca2+ + CO32- - - - (12) (13) (14) Le Chatelier's principle indicates that a drop in pressure will tend to move an equilibrium in the direction where the total volume of the system is increased. calcium sulphate may exist as gypsum (the dihydrate). H2CO3 and H+ concentrations decrease. 3. or the metastable vaterite. The imposed temperature and pressure largely determine which morphological form will be most stable. Appendix 2 contains an example of a scale prediction study showing the effect of pressure and CO2 on calcite scale formation. K values for each of the following reactions must be known as a function of pressure when considering the formation of calcite scale. the variation of the equilibrium constant with pressure must be known for every pertinent equation in the model. Page 38 . For instance. whilst CO2 (aq) and CO32.increase.4 Phase Behaviour Some scales are capable of existing in more than one crystal form.

commonly relying upon chemical inhibitors to achieve it. the second method is more common. CO2. Geochemical models (ie that take account of ion pairs) represent the aqueous phase as a set of equilibrium equations. Scale inhibitors are chemicals that stop or interfere with scale nucleation. This has proved useful for instance in modelling sulphate reduction/oxidation of carbon containing species. The preferred BP model. The usual strategy is to adopt a 'prevention is better than cure' approach. These methods may be inappropriate if production losses are incurred and can be extremely costly. ie by treating the water chemically or mechanically in order to prevent or control scale formation from the outset. H2S. Firstly. an association constant for the coalescence of the anions and cations can be measured experimentally. Equilibrium constants for all mineral dissolution and ion pair formation reactions (for example equations 1. SPAM. With this information.2. for instance by mechanical removal or chemical dissollution.2. ie the three elements leading to scale problems. CH4. includes up to seven gases. Although these ion pairs do not form true complexes.BP Exploration Appendix 7 – Production Chemistry Reference Documents 3.1 Concept of the Ion Pair The natural attraction between ions of opposing charge can temporarily overcome the thermal energy that tends to separate the hydrated ions in solution. 4.2 Geochemical Aqueous Modelling The first truely successful treatment of brines was by Debye and Huckel. 6-17) are contained in a database which the model uses to correctly define the aqueous phase. SCALE INHIBITORS Scale in the oil industry is generally controlled in two ways (Figure 3). These 'contact' ion pairs which form may be very short lived and are better described as 'sticky collisions'. 3. Thus. together with the activity coefficient calculation outlined in the previous section. predictions of scale formation and other phenomena can be made with greater accuracy. it may be periodically removed after it has formed. Current aqueous models use various extensions of their theory to calculate the activity coefficients of the ions in solution. 3. Partitioning data has now also been included and other organic matter such as CH2O can also be included as a reactant. Page 39 .2 Treatment of Non Aqueous Phases In addition to solid and aqueous phases already discussed. N2. The ion pairs that form in solution may retain some or all of their water of hydration. NH3 and H2 although others can be readily added if thermodynamic data are available. This deviation from Debye-Huckel theory must be taken into account if a scale prediction model is to describe a brine satisfactorily. gases are also included in ion pair models. On average a significant number of the ions may be present as ion pairs and the resultant solution properties deviate significantly from simple Debye-Huckel theory. These extensions increase the range of the original model to encompass high ionic strength brines as are often found in oilfield operations. precipitation and adherence to equipment.

Typical substrates in the oilfield include sand grains. Once the crystal is sufficiently large. strontium and barium scales. They are readily soluble in water.1. Scale inhibitors used in the oil inductry generally fall into four main types: 4.1. The most common classes of inhibitors include polyacrylates. However. Organophosphonates These are often based on amines and are compounds containing the hydrolytically more stable -N-C-P moiety. These form either in bulk solution or on a substrate.1 Inorganic Phosphates These compounds are both cheap and easily prepared. polyphosphinocarboxylates. These compounds have excellent thermal and hydrolytic stabilities. Once formed.2 Organophosphorous Compounds This family of scale inhibitors can be further sub-divided into two classes.BP Exploration Appendix 7 – Production Chemistry Reference Documents 4. 1. Organophosphonates are now commonly deployed as scale inhibitors for calcium. Effective polymers tend to have a low molecular weight (typically 1000-5000) and have regularly spaced ionisable groups. Organic Phosphate Esters These chemicals are derived from inorganic phosphates and alsol suffer from hydrolytic instability. either in solution (homogeneous nucleation) or on a substrate (heterogeneous nucleation). 4. the cluster can grow along well defined crystal planes as more ions or more ion clusters become attatched to the growing crystal surfaces. 4. metallic surfaces and scale crystals themselves (the latter called secondary nucleation). even at fairly modest temperatures.1 Nucleation and Growth The first stage of the scale-forming process is nucleation. non-toxic and effective at low treatment concentrations (typically 0. The size of the cluster can vary but is generaly of the order of about 10 ions.5-20 ppm).1 Scale Inhibitor Types It is estimated that there are now more than 2000 chemical scale inhibitors commercially available. 2. polyvinylsulphonates and polyacrylamides. Nucleation is the creation of a sub particle or ion cluster consisting of several individual scaling ions. clay (and other) minerals. they hydrolyse in water to form orthophosphates that have little scale inhibitor activity.2 Scale Inhibitor Mechanisms 4. their use in oilfield applicationsis limited since. 4. particularly in controlling calcium carbonate scale. it can not be held in suspension and will fall out of the fluid due to gravity. Page 40 .1. Smaller ion clusters are thermodynamically unstable and break apart.2. polymalates.3 Organic Polymers Polycarboxylic acids are now more commonly used in oilfield applications. Examples of the chemical structure of all four inhibitor types are given in Figure 4.

Perhaps the single most important conclusion is that a chemical which shows excellent activity in one water chemistry may not necessarily perform well in another. All scale inhibitors operate in a 'threshold' manner. The strategy used in BP is to test several chemicals in simple tests under a wide range of conditions that are likely to be encountered. ie. Evidence suggests that some inhibitors operate by promoting the formation of multitudes of ion clusters but preventing their growth beyond a few nanometers in size. effectively removing the propensity to form other clusters or for growth of those clusters already formed. if not in detail. Typical inhibitor concentrations recommended for deployment in the field would be 5-50 ppm. That is. Page 41 . there is no universal scale inhibitor system. However. These are discussed below. 4. The reasons for this synergism could be that different chemical types act via different mechanisms. but large enough to avoid being engulfed in the growing crystal (although this can be beneficial. blocking active growth sites and preventing further crystal growth. but should readily diffuse over the crystal surface to other active sites as they form. but are sufficiently large to disrupt it. Test methodologies and interpretation of results can vary widely from company to company. Generally they interfere with either nucleation and/or with crystal growth. 4. The best of these can then be selected for further examination in more complex tests that match more closely the field conditions. at concentrations below the level required to react directly with scaling ions. Other inhibitors may operate by adsorbing onto the crystal surface and preventing the crystal from adhering to pipe walls or other substrates. One possible explanation is that the anionic polymer chain interferes with the nucleation process whilst the smaller phosphonate molecule adsorbs onto crystal nuclei. easily-removed scale). Good crystal growth inhibitors have a strong affinity for the active growth sites. to evaluate scale inhibitor performance in the laboratory prior to deployment in the field. Nucleation will only occur once the concentration of the scaling ions exceeds the solubility limit of the mineral scale in question within the physical conditions imposed.BP Exploration Appendix 7 – Production Chemistry Reference Documents Many crystals dropping out lead to scale deposits.3 Blending Scale Inhibitors Some synergistic behaviour between different scale inhibitors (particularly the polyacrylates and phosphonates) has been observed. gradually removing scaling ions from solutions.2. LABORATORY EVALUATION OF SCALE INHIBITORS There are many techniques used to study scale deposition and inhibition but few testing standards have been laid down within the oil industry. there are some common tests which are similar in approach. These inhibitors must be sufficiently small to be able to do this.2 Inhibition There are many proposed mechanisms by which scale inhibitors operate. Scale growth can continue. 5.2. until the concentration of the scaling ions falls below saturation. Those inhibitors that disrupt nucleation are small enough to diffuse readily in the bulk brine in order to get to the ion cluster. if it leads to the formation of soft. The result is that the saturation of the scaling species in the bulk fluid is reduced.

Here. Any build up of scale in the coil is detected by a differential pressure transmitter which monitors the pressure drop across the coil. The time taken for the coil to block in the presence and absence of scale inhibitors is noted and in this way a suitable ranking of scale inhibitors can be achieved. but provide vital data for optimising scale inhibitor deployment. can provide information on the nature of the deposit and the effect of the inhibitor on crystal growth. At a differential pressure of 100 psi the coil is judged to be blocked and the apparatus automatically shut down. the brines are stored at an appropriate temperature for a defined time (usually 16 hours). Additionally. 5. After this time the supernatant is filtered and analysed for scaling ions remaining in solution. Two incompatible brines are pumped separately at temperature and pressure into an oven where they mix and flow through a coiled capillary tube.2 Dynamic Scale Precipitation Test (Tube-Blocking Test) Unlike the static scale precipitation test. Page 42 . scale is induced to form not in tubes but in porous media . 5. A schematic diagram of the apparatus is given in Figure 5. Tests of this nature are particularly useful in designing scale inhibitor 'squeeze' treatments where the elution characteristics of scale inhibitors flowing through porous media determine the timing between successive squeeze treatments. If relatively small amounts of scale are deposited from these. The mixing ratios are chosen to represent the 'worst case' in terms of scale formation for the situation under investigation. but have the benefit in approaching field conditions of temperature. this test takes into account the adherence of scale to pipework.BP Exploration Appendix 7 – Production Chemistry Reference Documents 5. These tests are more complex and thus more expensive. when used in conjunction with microscopy and spectrometry techniques. This test is quick and cheap and. The effectiveness of a chemical is then determined by its ability to retain scaling ions in solution compared to the supernatants from uninhibited bottles. The test can however be less accurate for water chemistries with very high concentrations of scaling cations. Apparatus available ranges from simple core flooding at ambient conditions to full reservoir condition rigs that can operate up to150°C and 10000psi and in the presence of live crudes. the behaviour of chemical inhibitors in reservoir substrate can be determined. and optimum inhibitor dosage concentrations identified.3 Dynamic (Porous Media) Tests In these tests. pressure and can be conducted in the presence of dissolved gases such as CO2. Synthetic brines are prepared in the laboratory and mixed in defined ratios and pH values in the presence and absence of scale inhibitors. gravimetric analysis of the scale deposits themselves can be valuable. then the difference in concentration of supernatant scaling ions could be very small compared to the magnitude of the concentration. Once mixed. identified from computer scale predictions. Such tests are usually labour intensive.1 Static Scale Precipitation Tests This procedure is an adaption of the NACE Standard Testing Method for screening scale inhibitors.

Successful treatments have as long a half-life as possible. the concentration of scale inhibitor in produced fluids falls off exponentially. In this technique production is stopped and a concentrated solution of scale inhibitor is pumped into the well and out into the formation. giving protection against scale formation until the scale inhibitor is exhausted. In some cases it may be necessary to install continuous injection facilities downhole to ensure proper deployment of scale inhibitor. completion brines. and process water used for sandwashing or desalting. Following a squeeze.BP Exploration Appendix 7 – Production Chemistry Reference Documents 6. Experience within the industry is increasing. However. For example. There are many factors controlling the rate of inhibitor returns and effectiveness of squeeze treatments such as: - Adsorption/desorption behaviour of scale inhibitor on reservoir rocks and minerals. - Precipitation of scale inhibitor in the reservoir. Work from Heriot-Watt university suggests a very steep rise in the adsorption isotherm at low inhibitor concentrations is a prerequisite for good squeeze lives.e. scale formation could occur in the near wellbore region. nor be affected itself by them. Compatibility in this sense is understood to include direct chemical interaction and mechanistic antipathy. After a well has suffers sea water breakthrough. production is resumed. and batch (squeeze) treatment of production wells is now a routine operation. A good scale inhibitor must be: - efficient: i.) In order to optimise the field performance. when the well is re-squeezed. the precipitation process must be carefully controlled in order to avoid blocking pore throats and suffering irreversible loss of chemical. A precipitation/resolution mechanism can increase the squeeze lifetime over adsorption/desorption treatments. squeeze treatments may be needed to ensure protection of perforations and near wellbore. inhibitors are often incorporated into drilling muds. APPLICATION OF SCALE INHIBITORS Scale inhibitors should be used wherever a risk of scale damage is predicted (or known to exist from past experience). and as new chemicals are developed. Scale inhibitors have been used in injection water that is incompatible with the formation brine present in the zones into which the water is being injected. injection of a scale inhibitor into a production header is wasted if it does not contact incompatible waters before they mix in the production system. it must be able to inhibit the scale in question. After a shut-in period of usually 6 -~24 hours. For example. a chemical must be deployed correctly. and the scale inhibitor leaches back into produced fluids. - stable: it must be sufficiently stable under the conditions imposed. an improvement in Page 43 . - Entrapment of scale inhibitors in the formation for other reasons. - Modification of inhibitor properties by the porous media. - compatible: it must not interfere with the action of other oilfield chemicals. such as changes in relative permeabilities of fluid mobilities as a result of actually applying the treatment. Continuous injection of scale inhibitors into production systems is commonly practised. across perforations or in the tubing. irrespective of the mechanisms operating. Whilst downhole injection of an inhibitor may protect the tubing. (This is more fully discussed elsewhere in this Course.

In water/brine the solubility of barium sulphate is in the range 5 -~50 mg/l. Chelation or sequestration is the formation of soluble metal ion complexes in the presence of substances which would normally give a precipitate. Carbonate scales may be most readily dissolved with mineral acids. The process of chelation is illustrated below: Consider a system in which barium sulphate scale is present. more barium sulphate dissolves to maintain the equilibrium of reaction (1). and as the reactions continues further the barium sulphate gradually dissolves. EDTA (EthyleneDiamineTetraAcetic acid) forms the basis of many commercial chelants for sulphate scale. Page 44 . CaCO3 + 2HCl  Ca Cl2 + CO2 + H2O The sulphates (especially barium sulphate) are particularly hard to remove once formed.BP Exploration Appendix 7 – Production Chemistry Reference Documents squeeze treatments can be expected. They are largely insoluble in acid and require chelants and/or mechanical removal (such as high pressure water jetting). Often. Successful use of chelants requires a clean scale surface on which to operate. therefore. There are. SCALE DISSOLVERS The dissolution of scale in a liquid is the reverse of the crystallisation process by which scale was laid down. some barium ions in solution:BaSO4  Ba2+ + SO42- Ba2+ + L  BaL L = chelating agent (1) (2) As the barium is complexed in reaction (2). oilfield scale is coated in hydrocarbons which must be removed first (for example by using an appropriate surfactant) before the chelant can work. 7.

58 100 1655 79003 1. SEA WATER (Sherwood) + Na + K Mg2+ Ca2+ Sr2+ Ba2+ Fe2+ ClSO42HCO3TDS  7805 29370 76950 28100 52225 8000 11010 200 372 960 1630 3507 83 460 25 70 20 70 <1 11500 0 504 2808 574 252 <1 52360 11 760 4550 140 <1 1.359 496 86747 1.28 2222 22107 - 124 36058 0.712 Page 45 .35 134 247214 5.5 129340 1130 113 615 65 770 <1 46050 4 2249 34675 1157 91 107 153025 44 84 180 24 4 115100 10 1368 428 8 <1 <1 19700 2960 1650 21350 0.BP Exploration Appendix 7 – Production Chemistry Reference Documents TABLE 1 WATER ANALYSES MAGNU S FORTIES WYTCH MILLE R ULA FARM PRUDHO E BAY N.

0 * All concentrations in mg/L Page 46 .9 8.BP Exploration Appendix 7 – Production Chemistry Reference Documents APPENDIX 1 SCALE PREDICTION STUDY FOR FORTIES TABLE 1 WATER ANALYSES* ION Sodium Potassium Magnesium Calcium Barium Strontium Sulphate Bicarbonate Chloride pH FORTIES CHARLIE SEA WATER 28200 365 490 2770 250 640 6 390 54800 10890 460 1368 428 0 8 2960 124 19700 6.

BP Exploration Appendix 7 – Production Chemistry Reference Documents APPENDIX 2 SCALE PREDICTION STUDY FOR PRUDHOE BAY PRODUCED WATER ONLY TABLE 1 PRUDHOE BAY PRODUCED WATER ION MASS (mg/L) Sodium Potassium Magnesium Calcium Strontium Barium Chloride Sulphate Bicarbonate 8000 83 84 180 24 4 11500 10 2222 pH 7.7 Page 47 .

BP Exploration Appendix 7 – Production Chemistry Reference Documents Page 48 .