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Water Formed Scales

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Water Formed Scales

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Water Chemistry

Mineral Scale in Oilfield Production

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Water Chemistry

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Measurable Properties of Aqueous Solutions Major Impurities in Oilfield Waters and Associated Problems Water Sampling and Analysis Scaling Tendency Calculations

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Measurable Properties of Aqueous Solutions

Density and Specific Gravity Total Dissolved Solids (TDS) pH Temperature Alkalinity

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Density and Specific Gravity

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Density - mass per unit volume (g/cm3) Density altered by addition of soluble matter

Solids increase density

(example : Salts)

Gases decrease density

(example : Carbon Dioxide)

Specific Gravity (S.G.)

=

Density of Water Sample Density of Pure Water

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Measurable Properties of Aqueous Solutions

Density and Specific Gravity Total Dissolved Solids (TDS) pH Temperature Alkalinity

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Total Dissolved Solids (TDS)

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Inorganic (i.e. metal cations and non-metal anions) Cations Na+, Ca2+, Anions HCO3-, Cl-, Organic anions (i.e. formates/acetates) HCOO- [ Na+] CH3COO- [ Na+]

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Total Dissolved Solids (TDS)

Density versus Total Dissolved Solids (T.D.S) (NaCl brine)
T.D.S (mg/litre) - Thousands 350

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300 250
200 150 100 50 0
1.00 1.02 1.04 1.06 1.08 1.10 1.12 1.14 1.16 1.18 1.20 1.22

Density(g/cm3)
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Total Dissolved Solids (TDS)

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Dissociation Mineral salts dissociate in the aqueous environment forming ionic species NaCl + H2O = Na+(aq) + Cl-(aq) Cation Anion Ionic species are capable of carrying a current through a solution when a voltage is applied

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Total Dissolved Solids (TDS)

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Dissociation Na+ (aq) Cl- (aq) Cathode (-ve) Anode (+ve)

The conductivity of a solution is dependant on the salt present, e.g. NaCl

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Measurable Properties of Aqueous Solutions

Density and Specific Gravity Total Dissolved Solids (TDS) pH Temperature Alkalinity

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Potential Hydrogen (pH)

Defined as

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The pH of a water is the logarithm of the reciprocal of the hydrogen ion concentration, expressed in moles per litre

1 + pH = log = -log [H ] + [H ]
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Potential Hydrogen (pH)

pH Scale

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The pH scale runs from 0 to 14

pH7 Neutral midpoint

0 2 ACIDIC

10

12

14

BASIC

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Hydrogen ions are responsible for lowering the pH Hydroxyl ions are responsible for raising the pH

Potential Hydrogen (pH)

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pH is a logarithmic function and hence solutions having a pH of 6 are 10 times more acidic than those with a pH of 7 pH is temperature dependant and wherever possible the pH of a solution should be measured at S.T.P. or using a pH meter within its range of temperature compensation

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Measurable Properties of Aqueous Solutions

Density and Specific Gravity Total Dissolved Solids (TDS) pH Temperature Alkalinity

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Temperature

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Measurable in Celsius or Fahrenheit Conversion of units is often necessary SG, TDS and pH are temperature dependent Accurate temperature measurements vital for scaling tendency calculations

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Measurable Properties of Aqueous Solutions

Density and Specific Gravity Total Dissolved Solids (TDS) pH Temperature Alkalinity

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Alkalinity

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Alkalinity : the ability of a water to accept hydrogen ions It is NOT a measure of pH Basic species responsible for alkalinity are:

Bicarbonate (HCO3-) Carbonate (CO32-) Hydroxyl ions (OH-)

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Alkalinity

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CO2 (aq) + H2O

H2CO3 (aq)
Carbonic acid

Carbon dioxide dissolves in oilfield waters to give carbonic acid

H2CO3 (aq)
Carbonic acid

H+ (aq) + HCO3- (aq)

Carbonic acid dissociates in water to give hydrogen ions,

bicarbonate ions and on rare occasions carbonate ions

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Alkalinity

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Ratio of species present

1.0 0.8

[H 2 CO 3]

3] [HCO -

[CO ]

23

[CO

23

-] OH +

Ratio of species present

0.6 0.4 0.2 0

10

11

12

pH
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Measurable Properties of Aqueous Solutions

Ratio of species present

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1.0

[H2CO3 ]

[HCO3- ]

0.8 0.6

0.4

The pH of oilfield waters seldom rises above pH 8.3 because the main contributor to oilfield alkalinity is bicarbonate ion [HCO3-] [CO32- ]

0.2

pH
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Water Chemistry

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Measurable Properties of Aqueous Solutions Major Impurities in Oilfield Waters and Associated Problems

Water Sampling and Analysis Scaling Tendency Calculations

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Major Impurities in Oilfield Waters

Dissolved Gases Dissolved Solids Suspended Solids

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Oil
Micro-organisms

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Dissolved Gases

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Dissolved gases are the primary contributors to most corrosion problems Can cause general or pitting corrosion General corrosion - slow - occurs randomly Pitting corrosion - localised corrosion - extremely high rates - devastating results

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Dissolved Gases

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Main Dissolved Gases are:

Carbon Dioxide Oxygen Hydrogen Sulphide

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Carbon Dioxide

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Dissolves to give H2CO3 (carbonic acid) Corrosive

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Oxygen

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Dissolved Oxygen

Causes severe corrosion even at low concentrations

Pitting corrosion can be very rapid Most severe type of corrosion

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Hydrogen Sulphide

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May occur naturally May indicate the presence of bacteria Corrosion rate accelerator Extremely toxic Highly flammable

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Major Impurities in Oilfield Waters

Dissolved Gases Dissolved Solids Suspended Solids

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Oil
Micro-organisms

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Dissolved Solids

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Salts - metal cations (Ca2+, Ba2+, Sr2+) Non metal anions (SO42-, CO32-, Cl-) Examples: Ca2+ + CO32CaCO3

Ca2+ + SO42Ba2+ + SO42Sr2+ + SO42-

CaSO4
BaSO4 SrSO4

Na+ + Cl -

NaCl

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Major Impurities in Oilfield Waters

Dissolved Gases Dissolved Solids Suspended Solids

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Oil
Micro-organisms

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Suspended Solids

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Examples:Salts/Scale/Sands/Clays/Corrosion Products

Problems:Erosion corrosion Under deposit corrosion Reduced residence time Difficult to resolve oil/water emulsions

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Major Impurities In Oilfield Waters

Dissolved Gases Dissolved Solids Suspended Solids

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Oil
Micro-organisms

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Oil

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Forms reverse emulsions Food for bacteria in separation systems Food for bacteria in re-injection systems Food for bacteria in pipelines O/W overboard levels

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Major Impurities In Oilfield Waters

Dissolved Gases Dissolved Solids Suspended Solids

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Oil
Micro-organisms

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Micro-organisms

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Bio-fouling Emission of hydrogen sulphide Corrosion - indirect

Corrosion - direct

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Water Chemistry

Baker Petrolite

Measurable Properties of Aqueous Solutions Major Impurities in Oilfield Waters and Associated Problems

Water Sampling and Analysis Scaling Tendency Calculations

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Water Sampling and Analysis

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Water Sampling Water Analysis

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Water Sampling

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Reasons for sampling:

Determine original water composition - analyse Assess scaling potential Determine oil in water levels Monitor residual chemical levels

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Water Sampling

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Where to sample?

At the bottom of the well At the well head After the production manifold At the end of the production train At any other relevant point in the process equipment

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Water Sampling

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How to sample:

Flush sample point thoroughly

Always use glass bottles, if available, with a polylined cap. Never use metal cans

Always label the bottle, not the cap, with indelible ink
Minimum volume required - 500mls Take two samples from each sample point

Ideally fix one sample (e.g. with acid or EDTA) leave other sample unfixed

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Water Sampling

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Sample procedure - oil in water:

Sample directly from sample point Do not overflow the bottle Always use glass bottles, cap and label immediately

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Water Sampling and Analysis

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Water Sampling Water Analysis

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Water Sampling

On-site analysis should be carried out for: O2 (dissolved oxygen) CO2 (carbon dioxide) Alkalinity pH Iron (soluble and total) Temperature H2S (hydrogen sulphide) Turbidity Suspended solids Bacterial enumeration

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Baker Petrolite 1999

Water Chemistry

Baker Petrolite

Measurable Properties of Aqueous Solutions Major Impurities in Oilfield Waters and Associated Problems Water Sampling and Analysis Scaling Tendency Calculations

Baker Petrolite 1999

Scaling Tendency Calculations

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Rely on the calculation of a Saturation Index (SI) SI indicates probability of scale formation e.g. SI > 1 scale formation likely to occur SI < 1 scale formation unlikely to occur SI between 0 and 1 other factors to be considered

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Saturation Index

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Activity of Anion

Activity of Cation

{anion} {cation}

SI = log
KSP

KSP= Solubility Product Constant

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Scaling Tendency Calculations

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Used to be manual calculations: very time consuming

Stiff and Davis

Langlier Skillman et al

Now a wide range of commercial software packages available

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Scaling Tendency Calculations and Predictions

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Calculates the probability of scale formation as Saturation Index (SI) Calculates SI for type of common mineral scale, e.g. barium/calcium,/strontium sulphate and calcium carbonate Calculates a maximum amount for each scale in mg/L and lb/1000bbl Produce results in easily understandable format, i.e. tables and graphs Prediction not absolute

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Shell Scale Prediction Model

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Shell Scale Prediction Model is:

SCALECHEM

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Scale Prediction

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Finally Remember Scale Prediction is:-

Not absolute Only as reliable as your water sample Only as reliable your water analyses Limited to the capabilities of the model

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