SPE-170994-MS

Water - Chemical Treatment and Management

Dr. Adrian J. Wiggett, Baker Hughes
Copyright 2014, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Oilfield Water Management Conference and Exhibition held in Kuwait City, Kuwait, 2122 April 2014.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.


Abstract
Recycling produced water for re-use in gas and oil fields for hydraulic fracturing and re-injection to maintain
reservoir pressure is becoming increasingly important due to the scarcity of this natural resource. This is
especially the case when these activities are not near a readily available source of free water such as seawater
or an aquifer.

This paper considers ways to use water management to lower operational expenditures OPEX by eliminating
freshwater sourcing, transportation, storage and its treatment as well as the storage, transportation, treatment and
disposal of produced or flow-back water.

The water management approach enables operators to re-use produced waters in hydraulic fracturing fluids. Pre-
treatment testing and analysis characterizes the chemistry of the water to ensure an effective fracturing fluid
design and to determine the appropriate water treatment solution for every application. By using a comprehensive
water treatment suite of technologies, we demonstrate that virtually any oilfield water can be treated. Post-
treatment testing confirms the water meets the customer's specific requirements.

Integrating water management service technical expertise with water chemistry and chemical treatments
maximizes hydrocarbon production, minimizes reservoir damage, and reduces the costs of freshwater sourcing by
as much as 90%. The techniques also offer real routes for oil operators to meet regulatory requirements,
mitigating environmental impact.


Introduction
According to the paper Produced Water Volumes and Management Practices published in 2009 from the
Argonne National Laboratory written by C.E. Clark and J. A. Veil of the Environmental Science Division, the USA
state and federal onshore hydrocarbon production contributed to the majority of produced water (more than 20
billion barrels) in the United States. A significant amount of produced water (more than 700 million barrels or
about 3% of the national total) was also generated from federal offshore production activities and from production
on tribal lands.

The five states with the greatest produced water volumes in 2007 were Texas, California, Wyoming, Oklahoma,
and Kansas. The produced water volumes from these states represented nearly 75% of total U.S. production
(onshore and offshore). Texas, with more than 7.3 billion barrels, contributed 35% of the total volume of
produced water generated in the United States in 2007. The contributions from the other five states with produced
water volumes exceeding 1 billion barrels were California (12%), Wyoming (11%), Oklahoma (11%), Kansas
(6%), and Louisiana (5%).
2 SPE-170994-MS
The greatest produced water contributors are not necessarily the greatest producers of oil and gas. While Texas
was the largest gas producer in the United States (nearly 6,900,000 million cubic feet [MMCF] in 2007), federal
offshore production activities provided the largest volume of crude; more than 467,000,000 barrels. Although
federal offshore production generated nearly 27% of U.S. crude oil production, less than 3% of total U.S.
produced water was generated from federal offshore activities.

In addition to total volumes produced, it was useful to consider the water-to-oil ratios (WORs) and water-to-gas
ratios (WGRs) from production activities, as this information could be used to evaluate the relative production age
of resources within the production lifetime. To that end, they asked the agencies to provide produced water
volumes by hydrocarbon types (i.e., crude oil, conventional gas, coal bed methane, unconventional gas, or other)
to the extent of the data available at that level of detail. Most states were unable to break out produced water
volumes for all categories, but some states could provide estimates of produced water from oil production vs.
natural gas production. States that segregated produced water by hydrocarbon type categorized 6,666,144,270
barrels of produced water. Eighty-seven percent (5,770,327,439 barrels) of produced water came from oil
production activities.

These are large water production numbers from only one country, the United States. Consequently, in any
hydrocarbon recovery operation the main consideration should be related to the handling of water as well as the
hydrocarbon. There should be consideration of the amount of water needed, as well as the amount expected.

Water can be seen to be an additional troublesome cost for treatment, but in many cases it is often overlooked as
a valuable resource for many applications such as reservoir pressure maintenance or fracturing.

Water is such a concern that many service providers focus specifically on the subject of Water Management to
enable hydrocarbon producers to fully utilize every last drop of water efficiently.

Water Management
Consideration of water management provides surface water treatment and subsurface water shutoff focus on
reducing operating expenses and improve production from new and mature wells. By integrating these services
with the full breadth of our product and service portfolio, we have addressed the entire water lifecycle of oil and
gas wells.
Oilfield water management upstream operations such as completion, production, stimulation and workover, all
involve water. Whether we like it or not, oil and gas producers are also in the water business. Surface and
subsurface oilfield water management solutions can help reduce water-related costs and improve hydrocarbon
production and/or water-to-oil ratio. Water re-use and limitation can be split into two areas i) Surface and ii)
Subsurface Water Management.

Surface Water Management
Re-use, disposal, storage, and transportation of surface water requires water management services to be
deployed onsite. With these water management services onsite, hydrocarbon operators can be assured that
operational objectives, minimization of operating expenses, and full compliance with regulatory requirements are
met.

There is no need to source the water, treat it and in some cases transport it to site. By treatment of the water
onsite, it is more than possible to fracture with it, collect the flow-back and treat it for the next job. With proper
produced water handling this can lower OPEX and ensure environmental compliance using proven water re-use
solutions.

When necessary, the water has to be disposed of, but the main focus is on total re-use of water. Application of
comprehensive and the most advanced suite of water treatment technologies in the industry are available.
SPE-170994-MS 3

Subsurface Water Management
Subsurface water management service must combine the expertise of reservoir development services with
reservoir conformance and water shutoff technologies, which may be a combination of mechanical and/or
chemical. By combining resources this way it is possible to effectively diagnose, design, and deploy custom
solutions to solve excess water production issues efficiently and economically. This would readily enable
hydrocarbon operators to extend the life and profitability of their producing assets.

Technologies in a variety of disciplines to help improve production have to evolve to meet the hydrocarbon
producer demands. Subsurface production conformance and assurance services can combine technologies for
water avoidance, shutoff, conformance, and production assurance.

We have found that the integration of advanced mechanical and chemical technologies with unsurpassed
geoscience resources allows the detection of water inflow, selection of the best conformance or shutoff solution
and implementation of it in a safe and economical manner. Downhole chemical and mechanical intervention tools
decrease the amount of water produced. These tools include inflow control devices, gels and relative permeability
modifiers. However good the methods are, it is essential to look deeper into the chemistry contained within water,
especially using proven flow assurance techniques.

Flow Assurance
If an operator is to look to re-use of the water for subsurface benefits, then there is a real need to consider flow
assurance issues, which are primarily residual additive effects on the reservoir (for clay swelling prevention, etc.)
and the possibility of mineral scaling in the formation.
In addition, ad-hoc treatments to eliminate contaminants that can damage the wellbore and reservoir face are
usually considered as well as flow assurance services that combine hydraulic fracturing and production chemistry
to help maximize post-fracture production and minimize post-fracture intervention costs from scale, organic
deposition, bacteria, and corrosion. Hydrocarbon operators need to be confident from the first day of production of
flow assurance for the long term, so it is important to get it right from day one.
As an example, a deepwater Gulf of Mexico operator had plans to complete an oil well. The challenges were
offshore, 1,200 foot water depth, a vertical completion of 10,800 feet and high closure pressures of 5,400 psi.

In reviewing potential flow assurance issues, barium scale deposition was identified as a likely problem. This was
due to the fact that the well was designed to be a seawater flood and the connate water was known to contain a
high percentage of barium. Because seawater was high in sulfate, the mixing of this high barium water and the
seawater in the reservoir created a scenario for harmful scale deposition.

Barium sulfate scale is a non-acid soluble scale. Once formed, it is quite difficult to remove. Unlike carbonate
scale, which is soluble in acid, barium scale must be handled in a progressive and expensive manner that
includes chelating chemistry, sufficient downhole temperature, and long periods of soaking. Even under optimum
conditions, barium scale removal often calls for the use of mechanical means such as coil tubing.
A plan was developed to address the issue by proactively treating the well against barium scale. The operator
needed a scale inhibition strategy that provided sufficient inhibition and lasted for a prolonged period. Liquid
chemical alternatives offered good inhibitory service, but tended not to last for extended periods. The operator
decided to use our latest impregnated material offering for injection into the formation/perforations.
The newly modified impregnated material is based on the same concept as the established product line that has
proven effective at providing long-term inhibition in numerous wells since 2005. The new impregnated material
technology combines a high-strength nano-material that is the same size as a proppant and that provides a high
internal and external surface area onto which a robust scale inhibitor is adsorbed. The end result is a proppant-
4 SPE-170994-MS
sized material stronger than an intermediate strength proppant that contains a high amount of an active scale
inhibitor.
The scale inhibitor was mixed with the proppant at 10% loading by weight during a frac-pack operation for the
operator. The well was put on production and immediately flowed oil and water. After two months and two fluid
sample tests, the analysis of the residual scale inhibitor found in the produced water demonstrated that the scale
inhibitor from the new impregnated material was still present and was still inhibiting scale in the formation.
These early results indicated that the impregnated material program proved successful at inhibiting the formation
of barium sulfate scale subsurface.

As another example, a Permian Basin operator was experiencing declining production rates from wells in the
Wolfberry play due to scale. Traditional liquid chemical treatment methods, including acid, chemical squeezes,
and backside continuous injections only provided a partial solution, as scale would build up when the well was
being completed. Most flowback water in Wolfberry is high in iron, and most liquid scale inhibitors have limited
compatibility with iron. Dissatisfied with their current chemical program, the operator sought a reliable, long-term
solution.

Knowing the excellent reputation of impregnated solid inhibitors in addressing long-term scale inhibition, the
customer relied on the flow-assurance services team for assistance. The operator specified that the treatment
needed to last more than 10 months and eliminate scaling issues. The treatment also needed to address
commingled, multi-interval production.

To ensure proper treatment selection, first it was necessary for the services team to verify the scale composition.
Based on this analysis, the team recommended the required solid scale inhibitor that was pumped into the
formation during the proppant stage because it could be tailored to the operators scale-prevention requirements
to provide an economical, long-term treatment.

The impregnated material treatment has proven highly successful at eliminating scale for this operator after
treating more than 120 wells and with eight wells per month still being treated. The solution implemented by us
has eliminated one intervention per well over a two-year period, saving the operator around USD 2 million on the
120 wells treated with the impregnated inhibitor. (The figure for this saving is based on the elimination of
interventions only and does not include any additional revenue received from uninterrupted/increased production.)

The impregnated inhibitor performance continues to be monitored by field specialists with routine wellhead
sampling, which is reported to the operator for evaluation. Ongoing performance evaluations have enabled our
service team to refine future applications to enhance treatments.

According to the operators vice president of operations, the only intervention required has been the replacement
of a single rod pump and parts, and no scale was found on the downhole equipment. The operator plans to
continue completing eight wells per month for the foreseeable future, using the impregnated inhibitor approach.

The benefits were that it saved the operator more than USD 2 million over a two-year period, provided long-term
scale inhibition for 120 wells and increased production with limited downtime.

The challenges dealt with commingled, multi-interval production leading to fracturing water source incompatibility.
There was the issue of limited life of liquid chemical treatments. Our solution was to fracture with special solid
material impregnated with liquid scale inhibitor into the formation during the proppant stage of fracturing. This
eliminated remediation requirements. The chemical residuals were continually monitored and subsequent
treatments have been refined through continuous performance evaluation


SPE-170994-MS 5
Pressure Pumping Fracturing Operations and Produced Water Control
Fracturing operations are high energy and are an integral part of shale gas recovery. Reservoir water
conformance technology must reach deep into natural and hydraulically fractured reservoirs to decrease water
production and extend the commercial life of the well.

Challenges have been predominantly excessive water production in marginally profitable formations, cement
squeezes used for water shutoff that were uneconomical, the formation of low permeability, low porosity and a
naturally fractured system.

A successful solution was to utilize gel systems that achieved penetration into the formation. Timing,
temperature, and pressure of the injections were customized for the application where initial treatments were
completed in 24 hours. Three years later, production is virtually the same in 34 wells.

The methods utilized are summarized in the following sections.

Produced Water Control Subsurface
Middle East operators are increasingly calling on service providers to bring them their knowledge on any
technology/product related to downhole water shutoff and management. Subsurface control of water may involve
any one of the temporary and permanent gel and water-shutoff mechanical or chemical methods. These needs
can be divided into the following categories:
1. Mechanical - Flow management of series of fluid phases (gas, water and oil), reconnecting downhole
technology as operators are facing a lack of wellbore accessibility.
2. Chemical - Total or partial water shutoff in horizontal wells, relative permeability modifiers, gels and/or
near-wellbore cleaning products (polymers and/or surfactants).
Mechanical methods usually require well intervention and workover to install units that can control the water flow
mechanically and permanently in most cases.

However, by using and applying chemical gel systems, hydrocarbon operators have been able to cut water
production by nearly 35% and achieve a 225% sustained rate increase in oil production. The benefit of gels is
that they can be applied easily and also removed if only needed as a temporary measure. Normally, they exist in
the formation controlling the production flow for many years post treatment.

Applying gel systems proved to be a profitable choice for one operator with wells in the Spraberry formation of the
Midland Basin of West Texas.

Wells in the Spraberry formation were marginally economical, so the operator had strict cost controls for any well
intervention procedures. Cement squeezes (a commonly used water shutoff treatment), were uneconomical
because of the volume needed, and the cost of post-treatment drillout of the cement.

The Spraberry formation produces oil from a single sedimentary unit known as the Spraberry Sand. This unit is a
heterogeneous mix of fine sandstone, calcareous, or silicate mudstone and siltstone, all deposited in a deep
water environment distinguished by channel systems.

Oil recovery is adversely affected by low porosity (10%) and permeability (<0.1 md, often less than 0.05 md). The
rocks are naturally fractured, so oil tends to accumulate in strategic traps that also hamper oil flow. The producing
zone is at an average depth of 6,800ft (2100m).

The operators application of our gel systems successfully mitigated the formation challenges, and proved to be a
very lucrative choice. The gels used had a specific gravity similar to water, which helped penetrate the formation.

6 SPE-170994-MS
Alternative methods such as cement would not penetrate as deeply as the gels. The set times for these gels were
time and temperature dependent, but could be accelerated or delayed through the addition of catalysts or
retardants. Injection of these polymers into pressured intervals was extremely controllable. Our experts worked
with the operator to customize the injections, and ensured the success of the application.

The initial treatments were completed in less than 24 hours. The average oil production for these wells increased
225%, from 100 to 325 barrels of oil per day (BOPD). The hydrocarbon production was virtually unchanged three
years later in 34 of the wells. In addition, the gel treatments reduced water production by 35%, from 6,100 barrels
of water per day (BWPD) to 3,950 BWPD, reducing the water/oil ratio (WOR) from 55 to 12.5. The WOR on the
34 wells treated in this case remained flat for at least 3 years. The payout time for the treatment was seven
months and the cost of the gel treatments was 20% less than a cement squeeze.


Fig. 1. Return on Investment from employing chemical treatment methods for water.


Produced Water Control Surface
By combining reservoir knowledge with decades of experience in downstream water treatment and upstream
production chemistry, surface water management solutions have been designed to reduce operators total cost of
operations through 100-percent reuse of produced and flowback water.

Chemical treatment of the water to make it 100% re-useable upon receiving and prior to re-injection may include
any one of the following; biocides, oily water clarifiers, scale inhibitors, oxygen and H
2
S scavenging.

An example of the 100% re-use of water was in New Mexico where an operator needed to complete wells in a
formation that was extremely sensitive to clay swelling. The operator wanted to maintain the formation
SPE-170994-MS 7
permeability by reusing produced water that had high levels of sodium and potassium, to minimize swelling. If the
operator could not reuse the water, an alternative, and more expensive, gas fracturing completion would have to
be used.

Unfortunately, the wells from this area had high levels of hydrogen sulfide (H
2
S) in their produced water. The
operator had collected nearly 25,000 barrels (3975 m
3
) of produced water containing more than 900 ppm H
2
S for
fracturing. The cost of mitigating such high levels of H
2
S safely was a major concern. Traditional H
2
S treatments
cost more than USD 10 per barrel to treat the H
2
S.
Would it be possible to effectively treat the problem and reduce costs? After researching alternatives, we
recommended our patent pending technological service. This service provided operational simplicity and minimal
chemical consumption whilst lowering high H
2
S concentrations and maintaining the water quality required to
make-up fracturing fluid.
This treatment method could also cost-effectively reduce H
2
S oxidizer demand before more expensive and
selective oxidizers would become necessary. While this method was extremely effective in oxidizing H
2
S, our
technology combined a patent pending oxidation-method service to provide the most effective balance of
treatment and economics.
In full-scale treatment, we completely reduced the dissolved H
2
S and maintained the chemistry required for
fracturing fluid makeup. The first 23,000 barrels (3,657 m
3
) treatment was performed on time, with chemical
consumption 15% under target.
Three weeks after the fracture stimulation with the treated water, the operator reported that the well was flowing
as expected, and that the operation was planning to use our treated water technology in at least 32 more of their
wells to be fractured.
In addition, the work area H
2
S alarms were never triggered. The lower explosive limit (LEL) was undetectable, so
the safety concern of headspace was eliminated, and there was a surprisingly low level of H
2
S off-gas just above
the water surface in the reaction tanks. This level of H
2
S in the air was predicted to be in the thousands without
treatment, but it only measured around 10ppm at the reaction tanks water surface.

Prevent Reservoir Souring
As well as dealing with sour water from the reservoir, there is a need to prevent souring of the reservoir by
injection of water. Here we outline the treatment of water by the addition of chemicals to prevent reservoir souring
prior to re-injection of produced or source water.

Our water management service is a cost-effective method to efficiently treat water in tanks, reserve pits,
impoundments, and ponds with a smaller environmental footprint, lower power costs, and reduced manpower
needs compared to alternative solutions. Based on chlorine dioxide (CIO
2
) green chemistry technology that has
been used downhole and in refineries for decades, our service is a highly effective, flexible, on-site system to
neutralize bacteria, hydrogen sulfide (H
2
S), iron sulfide, phenols, mercaptans, and polymers in produced and flow-
back water.

By neutralizing these substances, the water can be reused for downhole operations with no issues related to H
2
S
corrosion and FeS equipment plugging, reservoir damage, or health, safety, and environmental concerns caused
by the presence of H
2
S. The water management service includes pre- and post-water testing to ensure customer
water quality standards. The service quickly breaks down the emulsions and sludges that often form in surface
water through chemical oxidation, allowing the water to separate from residual hydrocarbons, chemicals, and
particulates. The treatment also is a powerful biocide that neutralizes all forms of microbes in the water. Following
treatment, the surface water can be reused with no negative impact to the producing formation or to downhole
equipment, and the residual hydrocarbons can be recovered from the waste water. CIO
2
-based applications are
not pH dependent, so there is no need for costly pre-treatments.

8 SPE-170994-MS

The selective oxidizer CIO
2
is generated onsite via a mobile or permanently mounted generator using three
common liquid precursorssodium hypochlorite, hydrochloric acid, and sodium chlorite. A vacuum-based CIO
2
generator is used in the new service, which dramatically improves system safety.

With the fast chemical reaction time, concentrated solutions, and high CIO
2
generation rates of the service, up to
200,000 BWPD (31,796 m
3
/d water) can be treated with a single unit. Unlike other surface water treatment
options, the mobile CIO
2
generator system can be set up very quicklyoften in just one hour.

The service can also be used to reduce the environmental impact of oilfield operations. CIO
2
, which is used to
treat approximately 30% of U.S. drinking water, does not form any hazardous by-products, and because it is
neutralized by exposure to sunlight, it is not persistent in the environment. Also, by removing H
2
S from the surface
waste water, CIO
2
eliminates the offensive odors and dangerous fumes associated with H
2
S.

Some current service providers can provide an integrated suite of surface and subsurface technologies to solve
specific water management challenges.

The CIO
2
technology uses an acid bleach activation method and features a mobile generator that uses three
common liquid precursors: sodium hypochlorite, hydrochloric acid, and sodium chlorite. Its vacuum-based
generator ensures that CIO
2
is produced only in water and while motive water is flowing. If power and or water
flow is lost, no CIO
2
is produced. For additional safety, CIO
2
is generated at a maximum of 3,000 ppm (0.3%
solution), which is half the saturation level of CIO
2
in water. Our automated system also has inline monitoring and
built-in automatic alarms and auto shutdown features for added safety and reliability.

The flexible, high-volume, mobile or permanent onsite-mixing unit is built with automated gauges, sensors, and
flowmeters to ensure accurate dosage of chemicals, as well as system alarms and appropriate containments for
increased safety. No reaction chamber is needed as the CIO
2
is generated in-situ with the motive water flow. Our
water management service treats fresh, fracturing flowback, and produced water using environmentally preferred
chemistry. The service has a smaller environmental footprint, lower power costs, and reduced labor needs than
competitive water treatments.

Final Comments
As you can see, it is possible to process and re-use this valuable resource using the power of chemical
treatments to enable operators make the best use of available resources whilst limiting the impact on the
environment.