Water Technology

Water Technology: Understanding, Interpreting and Utilizing Water Analysis Data
Multi-Chem Production
Chemicals
Module 1
THE IMPORTANCE OF WATER

© HALLIBURTON. ALL RIGHTS RESERVED.
The Importance of Water
 Water is one of the most abundant and important

substances on earth
 It exists as a solid, liquid, and gas over a relatively small
temperature range
 It is known as the “universal solvent”
– Because of this…it can result in challenges to the oilfield
operator
 Water is able to act as an acid, or a base
 Can function as an oxidizer or a reducer

Properties of Water
 Oxidation properties of Water

– Important in the corrosion process
• Corrosion is an oxidation/reduction process
• Requires an electrolyte to transfer the current
– Water serves as that electrolyte
– Oxygen in the water can result in the corrosion of metallic
surfaces
– Oxidation of sulfides results in the formation of iron oxide
– Can happen in sub-surface water medias or in moist soils
– Small quantities of oxygen can be extremely corrosive
• 50 ppb oxygen limitation in sour gas pipelines

Properties of Water
 Water is a polar molecule
– Results in the formation
of “hydrogen bonding”
– This significantly impacts
the properties of water
• High energy content of
water vapor, or steam
• Heat transfer properties
• Causes water to expand
upon freezing – thus
less dense and “floats”
– Since inorganic
compounds are ionic in
nature, they tend to
dissolve in polar solvents
Properties of Water
 When water solvates a substance, it is know as a

solution
 The orientation of water molecules tends to keep ions
from recombining and thus preventing precipitation from
solution.

Water Sources and Types
 “Fresh” water
– Rivers, lakes, streams or shallow water sands
• Generally less than 2000 TDS
– Sea Water
• Salt content of 3.5 %
– Also contains bromine, strontium, sulfate, bicarbonate,
calcium, magnesium
» Frequently used by tide water plants for cooling water
and as a source for water flood projects
» Also utilized for water flood source water for off-shore
platforms
• Sea water also contains varying concentrations of oxygen
(depending on depth), as well as micro-organisms

Uses of Water
 Highest quality: Boiler and potable water

 Largest use of water in Oil Production: Enhanced Oil
Recovery and Fracturing Processes
– Quality varies according to reservoir and/or process
requirements
 Water in vapor phase: Steam flooding
– Fresh, higher quality water

Uses of Water
 Ground water and surface waters come in contact with

rock, minerals
– May dissolve some of them
– The species and concentration of impurities dissolved
in water represent substance with which the water
has contacted
– Water may contain suspended, as well as, dissolved
contaminates

Uses of Water
 Water may also dissolve gases

– Nitrogen (N2), oxygen (O2), Carbon dioxide (CO2),
Hydrogen Sulfide (H2S)
– These gases may affect the water’s ability to solvate
substances
• CO2 will decrease pH, thus water will be more
acidic and dissolve more constituents, ie, calcium
carbonate.

Module 2
WATER ANALYSES
The Water Analysis
 Water, by its nature, will dissolve

and carry many impurities
 These will remain in the water in
equilibrium with each other until
acted upon by an outside force
– Temperature
– Pressure
– pH change
– Component concentration change

Analysis of Waters
 Pure water is not very corrosive to steel

 Addition of salt to the water increases conductivity and
corrosion
 Addition of gases to the water increases the corrosivity
– Therefore, it is important to know WHAT is in your
water!

Uses of Water Data
 Initial step in identifying potential scale problems

 Important in understanding corrosion
 Important in understanding, diagnosing and evaluating
the remediation of pollution
 Identifying production zones
 Identifying casing leaks
 Identifying injection water break through
 Important in understanding solubility of production
chemicals and process additives (Frac/Drilling/Boiler
treatments)

Water Sampling Methods
 Unless proper sampling is performed, the likelihood of

erroneous data is high.
 Standard procedures have been prepared by several
industry accepted authorities to assist in this process
– ASTM
– NACE
– API

Sampling Methods
 Sample volume should be at least 6 ozs. It is best to have

more than the lab will need vs. too little! Ideally, 16 to 32 ozs.
 Rinse the container in the field several times before taking the
sample
 Slowly fill the bottle to the top, letting it overflow
 ALL unstable ions must be determined on-site. These include:
– Carbon Dioxide
– Hydrogen Sulfide
– Oxygen
– Alkalinity
– pH
– Temperature

Sampling Methods
 Time between sampling and analysis should be a short

as possible!
 If a preservative is added to the sample for a specific
test, both the volume and the name of the preservative
must be known!
– The preservative MUST NOT interfere in the
calculation!

Understanding Dissolved Components
 Calcium: Can range  Sodium: A major constituent of

up to 88,000 mg/L and waters but generally does not
result in problems, exception:
can combine with sodium chloride deposits
sulfate or bicarbonate  Iron: Iron can signal corrosion
to form CaCO3 or trends and can result in FeS
CaSO4 deposition in sour or bacterial
influenced fluids
 Magnesium: Much  Barium: Generally will not exist
lower than calcium and in the same water with sulfates.
can form mineral (*) Forms insoluble BaSO4
scales; however, they – (*) Could both be present if
are much more soluble scale inhibitor is being
and less likely to injected to prevent
precipitate deposition

Understanding Dissolved Components
 Strontium: Like Barium  Chloride (cont.): Also, the

and Calcium, it can also higher the chloride, the more
form scales. However, corrosive the water can
these are more soluble in
become.
water and less likely to
precipitate.  Carbonate/Bicarbonate:
 Chloride: A major Buffer the pH of the water;
constituent in oil-field also combine with calcium,
waters. Generally barium to form mineral scales.
combined with the  Sulfate: These ions will also
sodium, thus known as form with Calcium, Barium, to
salinity. Increased
form mineral scales. Scales
chlorides increases the
water’s ability to solvate. are not acid soluble.

Other Properties
 pH  Temperature
– Surface and downhole
– The solubility of mineral
scales, CaCO3 and iron – Increased temperature,
compounds are more increase in corrosion
soluble at lower pH’s and/or scaling
tendencies
– Increasing acid gases
will decrease the pH of  Specific Gravity
the water – Another “check” to
– Decreasing pH will confirm water analysis
increase the corrosivity components are within
of the water range.
– pH can change rapidly – Indicates the relative
with changing “weight” of the water
pressures. Should be  Oxygen
recorded on-site for – Can add to corrosion
accuracy. and bacterial activity

Other Properties (cont.)
 Dissolved Carbon Dioxide

– Adds to the corrosivity of the water
– Will lower pH with increasing amounts
 Sulfide, as H2S
– Adds to the corrosivity of the water
– Will lower pH with increasing amounts
– Can result in FeS corrosion by-product

Other “Informative” Components
 Suspended Solids
– Quantity, size, shape, chemical composition
 Turbidity
– Can be indicative of solids and/or bacterial activity
 Resistivity
– The resistance to electrical flow. An indicator of the total solids
in the water and a tool in predicting the corrosivity of the water.
 Bacterial Population
– Aerobic, anaerobic, sulfate reducing, acid forming

Other “Informative” Components
 Oil Content
– Important in water injection systems; can act as a
plugging agent; affects economics in
production
 Manganese
– Can also be used in conjunction with iron for trending corrosion
• Note: Some shale reservoirs can naturally contain manganese
(Barnett Shale)

What Next?
 A good water analysis is important

– Helps to predict corrosivity
– Helps to predict scale formation
– Can indicate changes in formation waters
– Can indicate casing leaks
 Components in a water can affect
solubilities of applied chemicals and stimulation additives
 Once the data is in place, computer applications can be
applied to predict the conditions (temperature and
pressure) at which scale would be likely to form

Build a “Directory” of Analyses
 Research and record the following:

– County
– Quadrant of the County
– State
– Depth of Well
– Formation(s)
– Secondary/Tertiary Recovery?
 Helps to establish expected baselines in water analyses
– Assists in identifying anomalies/changes in future
analyses

Water Treatment
 Definition: Making water suitable for use by chemical or

physical methods is termed water treatment
 Suitability of water for a specific use is governed by the
end-use requirements
 Any water can be treated to a designated quality for a
specific use
– May not be economical, but is possible

Water Treatment
 Ideally, find a water of suitable quality without treatment,

or with minimal treatment requirements
 Select an economic treatment if quality source not
available
– Ideally, consisting of only one process
 Understand how to determine and monitor acceptable
quality
 Implement quality control measures to ensure quality
over the life of the project

Examples of Water Treatment
 Water Reuse/Recycle facilities

– Frac
– Irrigation
 Drinking water plants
– Lakes
– Refuse water
– Desalination Plants
 Waste Water Plants
 Water Injection Facilities
 Steam Generation Systems
 Gas Plants/Refineries
 Overboard Water Discharge (Off-shore)

 RO filtration (homes/Labs)
 WEMCO Units
 Water softening
– Boiler Feed Water
– Steam Floods
 Cartridge/Sand Filtration
– Waterflood Applications
• Simple wellhead cartridge filters on nominal, or
absolute, micron sizes
– Upflow/Downflow Deep Bed Media Filtration

Module 3
INTERPRETATION OF WATER
ANALYSES
Interpretation of
Water Analyses
What
Does it all
Mean?

Water Analysis Procedures
 There are many different water analysis programs

in use today
 Multi-Chem uses ScaleSoft Pitzer (SSP) as its
primary water analysis interpretation program (with relation to
scaling tendencies)
 It was developed by Rice University and is very thorough in
it’s analysis for scale depositions
 A “Good” Analysis begins with accurate sampling procedures

Standard Collection Process
 Sample various points within a system

– Give you a “snapshot” image of a system
 The sampled system should be operating at normal conditions of
flow rate, pressure, temperature, etc.
– Exception: Unless the sampling purpose is to analyze under abnormal
conditions
 Field tests (pH, temperature, bicarbonates, and dissolved gasses)
must be performed in the field upon sampling
 Samples must be properly preserved in order to yield accurate data
 Samples must be collected in proper containers and shipped to the
laboratory for final processing in a timely manner

Saturation Index (SI)
 SI will predict what scales

are likely to precipitate at a
given location
 SI gives the relative severity
of one location to another for
the same type of scale
 SI and amount of
precipitation (mg/L or PTB)
together will predict if a
scale is likely to cause
issues at a given location

Scaling Tendencies

Understanding Scaling Tendencies
• Each water scale tendency must be reviewed separately

to determine potential scaling problem
– Theoretical amount of precipitation (mg/L or
PTB)
• The higher the SI and PTB - typically the more severe
the scaling problem
• It is possible to have a marginal SI but a high PTB and
have a severe scaling problem – halite (salt), calcium
sulfate
• It is also possible to have a high SI and a very low PTB
and not have severe scaling problem – barium sulfate,
zinc sulfide

Key for Scaling Tendency Values
SI SSP Interpretation
0.0 Under saturated for this scale type (non-scaling) *
0-1.0 Slightly supersaturated; likelihood for scale formation

marginal
1.0-2.0 Scale is likely to occur but should not be severe
2.0-3.0 Scale is almost certain to occur; should be strongly

scaling
>3.0 Severe scaling situation
* Note: a low, or negative SI for a scale could be a reflection of that

particular scale having precipitated downhole – prior to the
sampling of the water. Always know your system.

Densities of “Common” Mineral Scales
 Barium Sulfate, 4.5 g/cm3

– 4500 kg/m3
– 37 pounds/gallon
 Calcium Sulfate, Anhydrite, 2.32 g/cm3
– 2320 kg/m3
– 19.4 pounds/gallon
 Calcium Sulfate, Dihydrate, 2.96 g/cm3
– 2960 kg/m3
 Calcium Carbonate, 2.71 g/cm3
– 2710 kg/m3

Understanding Scaling Tendencies
Notice – ZnS is the highest SI;

but CaCO3 is the highest PTB
Module 4
WATER ANALYSIS -
CONCLUSIONS
Quick Review of an Analysis
 Look at chlorides vs specific gravity

– Should correlate
 Look at sulfates and barium
– High sulfates, water cannot hold but 1 – 2 ppm barium
• Low sulfates, water can carry barium
• Exception: Waters treated with scale inhibitor may carry
barium in the water
 pH value vs HCO3, CO2, CO3 values
 Iron/manganese content – high may signify active
corrosion
– H2S: FeS No H2S: Fe2O3
 Scaling tendencies
 Historical analysis review

Module 5
SUSPENDED SOLIDS IN WATER

Dissolved vs Suspended Solids - Discussion
With water, we just discussed that we have to be concerned

about what
is dissolved in the water…
What about suspended solids?
What issues can suspended solids create for your

Operations?
How do we determine these components….?

Testing for Suspended Particles
 Laboratory
– Coulter Counter
 Field
– Membrane (Millipore) Analyses
• Standard is a 0.45 micron filter size
• For waterflood operations, generally prefer <50 mg
• Allows for quantification and identification of solids
• Allows for particle sizing, via microscopic viewing
• Aids in designing filtration systems
Total Dissolved Solids Total Suspended Solids
0.45
0.45 mµ
Dissolved Suspended
Solids Solids
Particle Size
The difference is important since the remedies are different.
Factors in Suspended Solids
Potential, or experienced, impacts

Quantity
Size(s)
Identification
Origin
Removal Methods
Prevention Methods
Suspended Solids Make a Difference –
Deposits/Sludges
 Interfere with Fracturing Fluids
 Serve as nucleation sites for scale precipitation
 Promote biological activity (farms)
 Consume inhibitors
 TSS * 0.00035 * water injected (BWPD) = lbs. of solids
injected
Suspended
Water Injection Solids Injected Solids Injected
Solids
Well Rate into Formation into Formation
Concentration
bpd Tons/Year Tons/Day
mg/l
90000 100 584 1.6

Membrane Filtration Testing
 Can be used to detect changes in a single water of

interest
 Can be utilized at various points within a system to
detect changes as a result of processing
 Used to compare different source waters
 Can be used to establish tolerances for water quality for
a given project based on history
Membrane Filtration Testing
 Pre-weighed membrane filter (0.45 micron)

 Filter a known volume of water through the filter at apx.
20 psig for a known period of time
– Can take volume vs. time elapsed readings to
develop a “plugging curve”
 Take to laboratory for analysis
– Quantity, particle sizing, particle identification
Membrane Filtration Apparatus – In Field
Membrane
Filtration
Device
Membrane
Filter – Post
Filtration of Membrane
Water Filtration Device –
Connected to
Valves
Illustration of a Typical in-field
membrane testing apparatus, showing
connections and direction of flow
Additional Testing – Plugging Index
 Timed membrane filtration testing

– Record volumes at specific time intervals
 Calculate Flow Rate per time segment
– mLs/ Time (in seconds)
 Plot: Flow rate vs. Cumulative Volume (mLs) [on log paper]
 The more “horizontal” the slope, the lower the plugging tendencies
 Test can be done throughout the system at various locations to
analyze the impact of surface equipment
 Test can also be repeated with the addition of flow enhancement
products (surfactants)
– Ranking of products
– Product and ppm treating level can be determined
– After testing, field trials can commence
 Curve 1: Excellent; no plugging occurred
 Curve 2: Poorer than curve 1; slope indicates some
plugging occurred over the test time
 Curve 3: Poor; Plugging occurred; Flow rate dropped
quickly
Plot on 2-cycle
semi-log paper
(1 cycle/5 inches)
Exercise
Time (seconds) Time Volume (mL)
 Water #1 Data: 60 60 500
120 60 975
180 60 1300
240 60 1550
300 60 1700
360 60 1800
420 60 1850
 Water #2 Data: Time (seconds) Time Volume (mL)

60 60 300
120 60 550
180 60 700
240 60 800
300 60 875
360 60 925
420 60 950
Probable Origins of Suspended Solids
S u sp e nd e d S olids
H yd ro ca rb o ns Iro n C o m p ou n ds C a rb o na tes S u lfa tes In solu b le /Ino rg an ics
O il C a rry o ver Iro n su lfide C a lciu m ca rb on a te C a lciu m su lfa te F o rm a tio n fin es

P a raffins Iro n oxide Iro n carb on a te M a g ne sium su lfa te S and
Iro n carb on a te M a gn e siu m ca rb on a te B a rium su lfa te M icro b es
A sph a lten es
S e p ara tor m alfu nction C o rro sion S ca lin g w a te rs S ca lin g w a te rs In ad e qu ate clea n ou ts
T re atin g sch ed u les In co m p a tib le w a te rs C o rro sion H ig h te m p e ratu res P u m p in take s se t low
C B Ta n k d a m a g ed O xyg e n in tro d uction P re ssu re d ro ps P u m p o utle ts/sh ro u ds B a cte rial a ctivity
E q uip m en t sizing S tim ula tio n b y-p ro d u cts F lu id p rop e rty ch an g es In co m p a tib le wa te rs N a tura l, or in du ced
Water Treatment
 Critical in off-shore applications (discharge permits)

 Addresses the removal of solids, oil and the resolution of
reverse emulsions
 Poor water quality can result in:
– Plugging (surface and downhole)
– Loss of potential oil revenue
– Erosion/corrosion in equipment
– Loss of injectivity and/or increase in injection pressures
Importance of Water Quality in Injection Systems
 Goal is to move the water from injector to producer,

effectively sweeping the formation matrix and recovering oil
– Water MUST NOT damage the formation!
– Injection water MUST be compatible with the formation rock
AND the formation water
 Sub-standard water CAN be used, but must be conditioned
so as to minimize problems!
Option: Water Treatment
 Definition: Making water suitable for use by chemical or

physical methods is termed water treatment
 Suitability of water for a specific use is governed by the
end-use requirements
 Any water can be treated to a designated quality for a
specific use
– May not be economical, but is possible.
Option: Water Treatment
 Ideally, find a water of suitable quality without treatment,

or with minimal treatment requirements
 Select an economic treatment if quality source not
available
– Ideally, consisting of only one process
 Understand how to determine and monitor acceptable
quality
 Implement quality control measures to ensure quality
over the life of the project
Examples of Water Treatment Applications
 Water Reuse facilities

– Frac
– Irrigation
 Drinking water plants
– Lakes
– Refuse water
– Desalination Plants
 Waste Water Plants
 Water Injection Facilities
 Steam Generation Systems
 Gas Plants/Refineries
 Overboard Water Discharge (Off-shore)
 Mechanical Treatment
– RO filtration (homes/Labs)
– WEMCO Units
– Water softening
• Boiler Feed Water
• Steam Floods
– Cartridge/Sand Filtration
• Waterflood Applications
– Simple wellhead cartridge filters on nominal, or absolute,
micron sizes
 Chemical Treatments to improve water quality
– Oxygen scavengers; water clarifiers; surfactants
Removal of Suspended Solids
 Settling Time and Bottoms Removal

 Additional Surface Equipment
– Coagulators; Skimming tanks, hydrocyclones, and/or
chemicals for hydrocarbon removal
 Installation of Surface Filtration Equipment
– Pressure vessel filter
– Well head cartridge filters
Cartridge Filters
 Determine Tolerances
– Reservoir Parameters
– Downhole Equipment Limitations
 Determine Particle Size Distribution
– Coulter Counter
– Membrane Filtration
 Nominal or Absolute Sizing
 Select Filter Material
Typical
Cartridge
Filters
Most can be
ordered nominal
or absolute
Quality Control for Treatment Options
 Must conduct on-site analyses to determine desired

design specifications for filter type
– On “raw” water, perform millipore analyses
• Determine total suspended solids (TSS)
• Determine composition of TSS
• Determine particle sizes of TSS
• Graph the plugging tendency of the water (cumulative
volume vs. time)
– Determine oil carry-over content on “raw” water
Quality Control for Treatment Options
 Consider installation of pilot filtration systems to evaluate

actual performance
– Sample upstream and downstream of the filters
 Once final filtration system designed and installed,
perform the following analyses (preferably quarterly)
– TSS with compositional analysis
– Particle size determination
– Turbidity
– Oil carry-over
Value-Added Services: Periodic Analysis of
Water Quality
 Complete water analysis of injection water (2/year)

 Membrane filtration tests (quarterly)
– Graph volume of water vs. time for plugging tendency
– Run upstream and downstream of mechanical equipment
and/or chemical injection points
– Analyze solids for composition and particle size
 Oil carry over tests (quarterly)
 Oxygen content
 Monitor injection well pressures and volumes (daily)
Oilfield Water
Technology
Conclusions
 We’re in the Oil Industry, but we MUST acknowledge

water and it’s impacts
 We must learn how to manage water and its effects on

our production streams and equipment
 Understand what our analyses are telling us…and what

analyses we need to perform to tell us more!
 Understand what is needed to evaluate and monitor our

systems’ performances successfully.

Water Technology

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Water Technology: Understanding, Interpreting and Utilizing Water Analysis Data

THE IMPORTANCE OF WATER

 Water is one of the most abundant and important

© HALLIBURTON. ALL RIGHTS RESERVED.

 Oxidation properties of Water

© HALLIBURTON. ALL RIGHTS RESERVED.

 When water solvates a substance, it is know as a

© HALLIBURTON. ALL RIGHTS RESERVED.

© HALLIBURTON. ALL RIGHTS RESERVED.

 Highest quality: Boiler and potable water

© HALLIBURTON. ALL RIGHTS RESERVED.

 Ground water and surface waters come in contact with

© HALLIBURTON. ALL RIGHTS RESERVED.

 Water may also dissolve gases

© HALLIBURTON. ALL RIGHTS RESERVED.

 Water, by its nature, will dissolve

© HALLIBURTON. ALL RIGHTS RESERVED.

 Pure water is not very corrosive to steel

© HALLIBURTON. ALL RIGHTS RESERVED.

 Initial step in identifying potential scale problems

© HALLIBURTON. ALL RIGHTS RESERVED.

 Unless proper sampling is performed, the likelihood of

© HALLIBURTON. ALL RIGHTS RESERVED.

 Sample volume should be at least 6 ozs. It is best to have

© HALLIBURTON. ALL RIGHTS RESERVED.

 Time between sampling and analysis should be a short

© HALLIBURTON. ALL RIGHTS RESERVED.

 Calcium: Can range  Sodium: A major constituent of

© HALLIBURTON. ALL RIGHTS RESERVED.

 Strontium: Like Barium  Chloride (cont.): Also, the

© HALLIBURTON. ALL RIGHTS RESERVED.

© HALLIBURTON. ALL RIGHTS RESERVED.

 Dissolved Carbon Dioxide

© HALLIBURTON. ALL RIGHTS RESERVED.

© HALLIBURTON. ALL RIGHTS RESERVED.

© HALLIBURTON. ALL RIGHTS RESERVED.

 A good water analysis is important

© HALLIBURTON. ALL RIGHTS RESERVED.

 Research and record the following:

© HALLIBURTON. ALL RIGHTS RESERVED.

 Definition: Making water suitable for use by chemical or

© HALLIBURTON. ALL RIGHTS RESERVED.

 Ideally, find a water of suitable quality without treatment,

© HALLIBURTON. ALL RIGHTS RESERVED.

 Water Reuse/Recycle facilities

© HALLIBURTON. ALL RIGHTS RESERVED.

© HALLIBURTON. ALL RIGHTS RESERVED.

© HALLIBURTON. ALL RIGHTS RESERVED.

 There are many different water analysis programs

© HALLIBURTON. ALL RIGHTS RESERVED.

 Sample various points within a system

© HALLIBURTON. ALL RIGHTS RESERVED.

 SI will predict what scales

© HALLIBURTON. ALL RIGHTS RESERVED.

© HALLIBURTON. ALL RIGHTS RESERVED.

• Each water scale tendency must be reviewed separately

© HALLIBURTON. ALL RIGHTS RESERVED.

0-1.0 Slightly supersaturated; likelihood for scale formation

1.0-2.0 Scale is likely to occur but should not be severe

2.0-3.0 Scale is almost certain to occur; should be strongly

* Note: a low, or negative SI for a scale could be a reflection of that

© HALLIBURTON. ALL RIGHTS RESERVED.

 Barium Sulfate, 4.5 g/cm3

© HALLIBURTON. ALL RIGHTS RESERVED.