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Dow Corning Oil & Gas Industry Solutions

Dow Corning Corporation

Table of Contents

About Dow Corning...................................................................................................... 3

Oil and Gas Solutions.................................................................................................. 4

Section 1: Oil/Water Separation – Demulsification...................................................... 5

Section 2: Downhole Well Sealing – Repair, Abandonment and Zonal Isolation......... 8

Section 3: Hydrocarbon Foaming.............................................................................. 12

Section 4: Resin-coated Proppants Interface Modifiers............................................. 13

Section 5: Sand/Fines Consolidation......................................................................... 14

Section 6: Antifoams for Oil Production and Processing........................................... 16

How to Contact Us..................................................................................................... 20

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Oil & Gas Industry Solutions

About Dow Corning

Dow Corning Corporation was


established in 1943 specifically to
explore the potential of silicones. It
was created as a joint venture between
Corning Glass Works (now Corning,
Incorporated) and The Dow Chemical
Company. Today Dow Corning
provides performance-enhancing
solutions to serve the diverse needs
of more than 20,000 customers
worldwide. A global leader in silicon-
AV04923 based technology and innovation,
offering more than 7,000 products and services, Dow Corning is equally owned by The Dow Chemical
Company and Corning, Incorporated.

Headquartered in Midland, Michigan, U.S.A., Dow Corning has more than 45 sites worldwide as well as
over 10,000 employees around the globe.

Combining client services and innovation, Dow Corning is also committed to the principles of sustainability.
The company views sustainability as fundamental to its future success in meeting the needs of customers,
employees and local communities. It has made sustainability a corporate value and is implementing
an approach that covers all three dimensions of sustainable development – economic, social and
environmental. The company has long participated in the Responsible Care® program, an international
initiative to advance the safe and secure management of chemical products and processes. Dow Corning
uses Responsible Care as a framework for activities including product development, manufacturing,
transportation, usage and waste disposal.

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Dow Corning Corporation

Oil and Gas Solutions

Dow Corning has had an ongoing commitment to the oil


and gas industry since the early 1970s, resulting in many
product and application innovations.

Recently, new products have extended the application


area for silicones from traditional antifoam into broader
applications.

Dow Corning produces a variety of products for many oil


and gas applications, such as:

• Oil/water demulsification
• Oil well sealing for repair, abandonment and
zonal isolation
• Hydrocarbon foaming
• Sand consolidation
• Proppant modification and processing aids
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• Gas/oil separation foam control
• Delayed coking foam control

Dow Corning’s website, dowcorning.com/oilandgas, has several informative articles and selection
guides covering some of the more established uses for silicon-based technology in the industry, including:

Silicone in the Oil and Gas Industry


Silicone Foam Control for the Oil and Gas Industry
Foam Control Methods in Delayed Cokers

Dow Corning can also offer supportive services and fully integrated solutions tailored to your specific
business needs.

The following sections give more details on some of the newer and emerging applications for silicon-
based technology in upstream oil and gas operations.

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Oil & Gas Industry Solutions

Section 1: Oil/Water Separation – Demulsification

Overview
As high-quality crude oil resources become depleted
and heavy crude oil reserves are tapped, the need for
new, efficient and potent demulsifiers to resolve difficult
water-in-oil emulsions becomes more important.

Dow Corning provides silicone technology for oil


producers and service companies to improve their
current crude oil demulsification process.

The Dow Corning ® DMx line of silicone demulsifiers


represents a range of different structures and molecular
weights that have been proven effective in water/oil
demulsification.

Silicone polyethers exhibit low surface tension (in some


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cases down to ≈ 21 dyn/cm compared to ≈ 30 dyn/cm
for typical hydrocarbon surfactants in water) and low cohesive energy; they are surface active in both
aqueous and nonaqueous media, and show inverse temperature solubility and cloud point. Some
benefits that can be achieved are rapid water drop rate, better interface definition, better water quality,
low-temperature performance and overall improved cost efficiency for demulsification operations.

The effectiveness of silicone demulsifiers has been demonstrated over the years in the field, both as
stand-alone additives and as performance boosters to organic-based formulations, in levels between 10
– 30 wt%, based on formulation active ingredients.

Key Advantages
• Rapid water drop rate
• Sharp interface definition
• Improved water quality
• Low-temperature performance

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Dow Corning Corporation

Case History
Dow Corning worked with a leading oil and gas company to improve their crude oil demulsification
process at their primary offshore platforms in Asia.

The traditional demulsification process involves the use of organic demulsifiers at temperatures of 60 to
70°C to reduce the water content in the oil stream to about 3-5 percent. These organic demulsifiers are
ineffective at lower temperatures. The firm was looking for a solution that would enable them to carry out
the same process at a lower temperature with higher water reduction.

Dow Corning worked with the company’s team on various field trials to screen the DM series. The com-
pany has decided to conduct further bulk trials with one of the DM series products, which enables cleaner
and faster separation of oil and water, and reduces the water content in treated crude up to less than 0.4
percent. In addition, it works effectively at a lower temperature of 40 to 50°C, thus enabling considerable
energy and cost savings to the company.

Oilfields conditions
• ~70 producing wells coming into 4 parallel separators
• Medium oil with some wax (controlled by pigging)
• Average water cut ~60%
• Residence time ~3 min
• Temp: 50 - 60°C
• Pressure: 7-8 kg/cm2

Field Trial Screen Result

Treatment detail Final water content in oil Final oil content in slop water

30 ppm glycol-based 3.0 - 7.2% 100 ppm

~8 ppm Dow Corning ® DM5 1.6 - 3.6% < 25 ppm

18 ppm glycol-based + 1.5 ppm ~2% Optimized < 50 ppm


Dow Corning ® DM5 (Best)

23 ppm glycol-based + 2 ppm 1% Demonstrated < 50 ppm


Dow Corning DM5

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Oil & Gas Industry Solutions

Product Information

Products Viscosity Flash Point HLB*


cSt or mm2/s Closed Cup °C Equivalent

Dow Corning ® DM1 1,750 71.5 6.6


Dow Corning DM2
®
260 113 12.3
Dow Corning ® DM3 280 83.3 6.6
Dow Corning DM4
®
40 101 11.5
Dow Corning ® DM5 310 67.2 9.2
Dow Corning DM6
®
200 80 10.5

*HLB equivalent = (molecular weight of ethylene oxide/molecular weight of total polymer) x 20.

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Dow Corning Corporation

Section 2: Downhole Well Sealing –


Repair, Abandonment and Zonal Isolation

Overview
Cement is a common material used
in downhole sealing jobs, and while
cement is well established and
relatively inexpensive, there are
many cases where cement is either
unsuitable or has potential longer-term
problems. For example, cement can
crack or leave annular gaps upon
curing or during normal operations due
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to changes in pressure, temperature,


mechanical loading or even due to corrosion. Remedial or squeeze cementing operations are difficult or
impossible due to the particle size of the cement.

Dow Corning and Shell Research developed a silicone elastomer system to help with these problems
several years ago. This work was initially described in SPE 39346 “Development of a Novel Silicone
Rubber/Cement Plugging Agent for Cost Effective Through Tubing Well Abandonment” by M. Bosma, et al.

This patented silicone elastomer system has many desirable characteristics. For example:

• Good thermal range – will remain flexible and stable from <0°C to >200°C
• Good chemical resistance
• Cure profile can be varied to give desired working time at job temperature by addition of a
catalyst or cure retarder – for example, to get 3 hours working time for the Dow Corning ® WS
4230 Well Sealant:
- At 30°C, no additives are needed to the base formulation
- at 50°C, you would add 2.5% Dow Corning ® WS 4232D Diluted Cure Retarder or 0.25%
Dow Corning ® WS 4233 Cure Retarder
- at 100°C you would add 6.5% Dow Corning WS 4233 Cure Retarder or 0.2%
Dow Corning ® WS 4234C Concentrated Cure Retarder
- at 135°C you would add 1.3% Dow Corning WS 4234C Concentrated Cure Retarder
• Swell slightly in oil, which can lead to an even better seal
• Cure is not significantly affected by contaminants (oils, muds, etc.), at least up to the 5-10% level

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Oil & Gas Industry Solutions

• Supplied as a liquid, two-part, cure-in-place system. The addition cure chemistry relies on no
outside materials (such as moisture) to initiate cure and doesn’t have any cure byproducts.

It is worth noting that strong acids (sulfuric, concentrated HCl, etc.) or bases (concentrated
KOH, etc.) can degrade the elastomer over time, particularly at higher temperatures. Also
at high temperatures, the elastomer is hydrolytically unstable and can degrade over time.
Since this latter case is quite common downhole, additional work was done to understand this
phenomenon.

Since degradation requires contact with destabilizing material, the rate should be diffusion controlled. A
multiyear study was undertaken to determine the diffusion coefficients and then to validate the theory with
application simulation results. The following chart illustrates the expected degradation rate based on the
diffusion coefficients. Experimental results from the exposure study match up well.

Diffusion-controlled depolymerization

5
4.5
4
3.5
Failure, meters

3 25°C
2.5 100°C
2 200°C
1.5
1
0.5
0
0 5 10 15 20 25
Time, years

Example 2 below illustrates how this can apply in practice to a P&A application.

Example 1 below illustrates a typical operation for secondary/remedial sealing using Dow Corning ® WS
4235UF Unfilled Well Sealant. This is an application where cement has a low success rate due to the
difficulty of squeezing a solids-containing slurry. Note that this operation could also be performed with a
top-down squeeze.

Field trials to date have been a combination of these two examples, most for annular gas to the surface in
previously abandoned wells. All re-abandonments with this system were successful on the first try. More
details on these trials are available.

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Dow Corning Corporation

Example Applications
Example 1: Damaged Casing and Annular Seal (Squeeze Cementing/ Sealing)

A. Damaged casing
B. Through tubing squeeze of Dow Corning ® WS 4235UF Unfilled Well Sealant
C. Circulate or drill out to resume production

Example 2: Theoretical Example of Hydrolytic Degradation over Time in a


Plugging and Abandonment Application

A. Well plugged with 5m of Dow Corning WS 4230 Well Sealant (red) + cement (gray).
Conditions are 100°C, primarily brine with residual oil left in contact with the silicone seal
B. After 10 years, the brine has penetrated about 0.75m into the seal
C. After 20 years, the brine has penetrated just over 1 m into the seal, still leaving almost
4 meters of Dow Corning WS 4230 Well Sealant to act as a positive seal to prevent
fluids migration, even if the cement has cracked or otherwise failed

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Oil & Gas Industry Solutions

Dow Corning WS 4235UF Unfilled Well Sealant


ready to be pumped

Well Sealing System Product Summary


Product Selection
Products Description Specification Application
Dow Corning WS Two-part filled Mixed viscosity is ~2000 cSt Sealing larger spaces,
4230 Well Sealant silicone elastomer such as in plugging and
Specific gravity =1.35 abandonment
Silica filler is nominally 5
micron particle size
Dow Corning WS Two-part filled Mixed viscosity is ~300 cSt Squeeze sealing, such as
4235UF Unfilled silicone elastomer in zonal isolation and
Specific gravity = 0.97
Well Sealant secondary / remedial
“cementing”
Dow Corning WS Cure retarder For use at low - moderate
4232D Diluted Cure temperatures to achieve
Retarder desired working times
Dow Corning WS Cure retarder For use at moderate - high
4233 Cure Retarder temperatures to achieve
desired working times
Dow Corning WS Cure retarder For use at high
4234C Concentrated temperatures to achieve
Cure Retarder desired working times
Syl-Off ® 4000 Catalyst For use at very low
temperatures to achieve
desired working times
Dow Corning ® Cleaning solvent Clean cured/uncured
Q3-3522 silicone elastomers from
surfaces

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Dow Corning Corporation

Section 3: Hydrocarbon Foaming

Overview
There are multiple applications
in the oil and gas industries
that involve the need to
generate hydrocarbon-based
foam, such as oil-based fluids
for underbalanced foam drilling
and gas well deliquification.

Dow Corning technology can


be used to generate foam in a
broad range of hydrocarbons.
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There are technology options
available for pure hydrocarbon systems as well as hydrocarbon/brine systems.

Key Advantages
The key advantages of silicone-based foaming agents:

• Higher temperature resistance than many organic materials


• Ability to create foam in system with up to 100% hydrocarbon
• Non-fluorinated

Product Information
Dow Corning ® 1250 Surfactant is known in patent literature to be an effective foaming agent in oil-based
drilling fluids

Developmental products now available for evaluation:

Dow Corning ® HCF-105 Dev Additive


Dow Corning ® HCF-110 Dev Additive
Dow Corning ® HCF-125 Dev Additive

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Oil & Gas Industry Solutions

Section 4: Resin-coated Proppants Interface Modifiers

Overview
Hydraulic fracturing is a technique
used in gas and oil wells to increase
the permeability of zones to enhance
production. It is a standard practice
used today as wells get older and
permeability decreases or new wells
are being drilled in less permeable
formations. The process includes
creating a fracture, or fissure, in low
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permeable zones, filling the fracture
with proppants that pack and hold the fractures open, all yielding an enhanced permeable pathway to the
wellbore for the oil or gas.

In recent years, resin-coated proppants have seen an increase in usage because they have demonstrated
a higher crush resistance and demonstrated less fines migration, which leads to improved conductivity. As
new proppants develop, resin-coated proppants continue to evolve and become more specialized to
specific wells and the geological conditions downhole. The resin technology is also being engineered to
meet the needs of deeper wells, which translate to higher pressures and temperature environmental
conditions that the proppant must be able to withstand.

Dow Corning provides silicon-based technology that can enhance the performance of the resin technology
used in proppants with targeted benefits in adhesion of the resin and compressive strength enhancement,
as well as processing aids to improve flow and anticaking performance. We supply a wide range of
products with different functionalities to address the needs of our customers.

Our Key Advantages


Dow Corning ® brand proppants additives can enhance the performance of a resin-coated proppant.

• Increase to compression strength of resin and formation


• Compatibility with many resinous matrices
• Improve adhesion between coating and neat proppant
• Lubricity / Anticaking

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Dow Corning Corporation

Section 5: Sand/Fines Consolidation

When hydrocarbons are recovered from subterranean formations, which are comprised of poorly consolidated
or unconsolidated sandstones, free sand and very small particles called “fines” can be carried away with
the hydrocarbons and transported to the surface. This often results in negative effects such as plugging of
the formation’s pores and/or erosion of the equipment. These adverse effects on well productivity and
equipment are costly sources of well damage that are often sought to be mitigated.

Different methods have been developed for preventing or addressing the effects linked to the migration of
fines and the related formation damage, including sand/gravel packing, screens, slotted liners, maximum
sand-free production rate, sand consolidation and various combinations of these methods.

Sand consolidation is a process involving the injection of a reactive chemical into a naturally unconsolidated
formation. The chemical’s purpose is to bind the sand particles that make up the formation matrix while
maintaining sufficient permeability to achieve viable production rates.

Various sets of chemistry have been investigated for sand consolidation, among them organosilanes,
which have demonstrated beneficial effects such as increased compression strength of the formation.
This class of materials can be simply flushed into a formation and due to their ability to rapidly hydrolyze
once in contact with aqueous solutions, organosilanes can easily form in-situ silanol species that will
condensate with each other and with any other hydroxyl sites on the surface of the mineral particles. This
results in a Si-O-Si network that will bind the siliceous material to the formation. Organosilane materials
also have been demonstrated to enhance the adhesion and compression performance of organic resins
used for consolidating sand formations.

In addition, their low bioaccumulation and high biodegradability profile make these chemicals
environmentally acceptable.

Dow Corning provides silicon-based technology that can chemically bind with the particles and provide
and enhance performance. We supply a wide range of organosilanes with different functionalities to
address the needs of our customers.

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Oil & Gas Industry Solutions

Our Key Advantages


• Ease of processing
• Increase the compressive strength of the formation
• Lessens fines migration
• Lessens fines swellability
• Environmentally acceptable

Product Information

Material Functionality Specific Viscosity Resin Compatibility


Gravity at 25ºC (cSt)

Dow Corning ® amino / ethoxy 1.03 5 Novolac and Resol Phenolic


PP-11 Systems**, Furan, Urea
Formaldehyde, Epoxy

Dow Corning ® amino / methoxy 0.946 1.06 Novolac and Resol Phenolic
PP-20 Systems**, Furan, Urea
Formaldehyde, Epoxy

Dow Corning ® glycidoxy / methoxy 1.07 3 Novolac and Resol Phenolic


PP-40 Systems, Furan, Urea
Formaldehyde, Epoxy**

** Preferential Resin System

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Dow Corning Corporation

Section 6: Antifoams for Oil Production and Processing

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Foam is a Problem
From the well head, through refining, processing and even during shipment of the finished product, foam
can cause major problems in the production and refining of oil. Foam robs you of capacity and makes
your production process less efficient. It causes cavitation in pumps and excessive process fouling.
Waste, maintenance costs and processing time go up, while productivity goes down.

Silicone Foam Control is the Solution


Silicone foam control agents from Dow Corning eliminate process foam in production, refinery and gas
processing plants. Eliminating process foam can increase your productivity, reduce your production costs
and, consequently, save you money.

Dow Corning has been involved in foam control for the petroleum industry for more than 50 years and has
a wide range of foam control products available for almost every foaming need. Dow Corning’s website,
dowcorning.com, has several informative articles and selection guides covering some of the more
established uses for silicon-based technology in the industry, including:

Silicone Foam Control for the Oil and Gas Industry


The following are short descriptions of a few applications where silicone antifoams are commonly
used today.

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Oil & Gas Industry Solutions

Gas-Oil Separation – Certain crudes tend to foam while undergoing depressurization to release
entrapped gas. This tendency can severely limit output and is especially severe on offshore rigs where
vessel size is limited and special foaming problems can occur. Using as little as 1 to 5 parts per million
silicone antifoam from Dow Corning can help you maintain maximum separator capacity and well output.

There are many different options of Dow Corning ® brand silicone antifoams that can be used in gas/oil
separators. Most of these neat antifoams are of quite high viscosity and can be supplied as a concentrate
for ease of handling. We can customize a blend of selected silicone-based fluids and solvents to meet
your needs, exactly. Save costs and time by choosing the right blend.

Typical 3-Phase Gas-Oil Separator Unit

The antifoam is typically metered into the crude oil inlet line either upstream (preferred) or immediately
downstream of the choke valve. Continuous addition at low levels is typically the most effective from both
performance and cost standpoints. Whether it’s for typical foam problems in low/medium GOR environments
or a more persistent foaming problem often seen in high GOR or heavy oil situations, the Dow Corning
range of silicone antifoams has proven effective in solving foaming problems.

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Dow Corning Corporation

Gas Scrubbing – Gas scrubbers used to remove CO2 and H2S from gases are prone to foam. Such
processes are commonly used for natural gas, refinery gas, in gas treatment as a part of reforming, in
ethylene production (steam cracking) and in the production of ethylene oxide. Trace impurities, such as
liquid hydrocarbons, well-head inhibitors, corrosion solids and valve greases in the incoming gas can
cause foam regardless of which absorbent (MDEA, DEA, TEA and DGA or carbonate solution) is used.

Foaming can cause poor separation efficiency and reduced throughput, as well as loss of expensive
absorbent by carry-over. The foam can be controlled by feeding Dow Corning silicone antifoam into the
absorber/contactor and regenerator columns.

The antifoam is typically metered into either the column reflux line (after any filters) or into the column
feed line. It is generally preferred to add the antifoam into a reflux stream immediately before a pump to
maximize mixing and dispersion in the system, as shown in the below system diagram. Since some of the
defoamer is removed by the filters, it is usually added to both columns.

Recommended Use of Silicone Antifoams

SWEET GAS ACID


GAS

OUTLET
SCRUBBER REFLUX
ACCUMULATOR

Antifoam
REFLUX
CONDENSER

CONTACTOR
AMINE BOOSTER
CHARGE COOLER PUMP REFLUX
PUMP PUMP
Antifoam
FLASH
GAS REGENERATOR
CHARCOAL
SOUR FILTER
GAS
FLASH TANK
OR SKIMMER
RECLAIMER
INLET
SCRUBBER REBOILER

DRAIN
SOLIDS
FILTER

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Oil & Gas Industry Solutions

Product Information for Gas Scrubbers:


• Dow Corning ® 1410 / DB-110A: Recommended dose: 10 – 100 ppm
• Dow Corning ® 1430 / DB-310: Recommended dose: 5 – 50 ppm
• Dow Corning ® 2-3316 Silicone Organic Antifoam: Recommended dose: <5 – 10 ppm

Delayed Coking – Foam typically occurs during the process of coking heavy oil and asphalt fractions.
This foam builds up in the coke drums, preventing the full use of the drum volume since the last thing you
want to do is carry foam or liquids overhead. The addition of 10 ppm or less of a silicone antifoam directly
to the drum generally controls the foam, thereby increasing the drum runs and reducing coke deposits in
overhead vapor lines and downstream equipment.

Since the most effective silicones are high-viscosity fluids, and since dose rates are so low, they are usually
dispersed in a hydrocarbon fluid before use. Dow Corning can provide a concentrate that can be further
diluted on site to the desired feed composition using coker naphtha or other available hydrocarbon stream.

The paper Foam Control Methods in Delayed Cokers on dowcorning.com/oilandgas has more
information.

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How to Contact Us

Dow Corning has sales offices, manufacturing sites, as well as science and technology laboratories around the globe.
Telephone numbers of locations near you are available at dowcorning.com/oilandgas.

Chat with an expert online.


Live Help is available at: dowcorning.com/content/support
Or contact us at: dowcorning.com/ContactUs

LIMITED WARRANTY INFORMATION – PLEASE READ CAREFULLY


The information contained herein is offered in good faith and is believed to be accurate.
However, because conditions and methods of use of our products are beyond our control,
this information should not be used in substitution for customer’s tests to ensure that our
products are safe, effective and fully satisfactory for the intended end use. Suggestions
of use shall not be taken as inducements to infringe any patent.
Dow Corning’s sole warranty is that our products will meet the sales specifications in
effect at the time of shipment.
Your exclusive remedy for breach of such warranty is limited to refund of purchase price
or replacement of any product shown to be other than as warranted.
DOW CORNING SPECIFICALLY DISCLAIMS ANY OTHER EXPRESS OR IMPLIED
WARRANTY OF FITNESS FOR A PARTICULAR PURPOSE OR MERCHANTABILITY.
DOW CORNING DISCLAIMS LIABILITY FOR ANY INCIDENTAL OR CONSEQUEN-
TIAL DAMAGES.

Front Cover Photo: AV12204


Dow Corning is a registered trademark of Dow Corning Corporation.
Syl-Off is a registered trademark of Dow Corning Corporation.
We help you invent the future is a trademark of Dow Corning Corporation.
All other trademarks or trade names are the property of their respective owners.
©2009 Dow Corning Corporation. All rights reserved.

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