AkzoNobel Surface Chemistry in the oil industry

Inside:
A broad product range for a wide spectrum of oilfield applications Solutions for production applications Demulsifiers Corrosion inhibitors Scale inhibitors Paraffin control Biocides Water clarifiers/deoilers Asphaltene inhibitors Foamers Solutions for drilling applications Oil-based mud additives (chart) Water-based mud additives (chart) Oilfield cleaning 2-4 5-22 7-8 9-10 11-12 13 15 17 19 21-22 25-29 26-27 28-29 31-34

A broad product range for a wide spectrum of oilfield applications

AkzoNobel Surface Chemistry has the global experience, expertise and sustainable solutions to help the oilfield industry enhance its production, drilling and stimulation processes. Our portfolio of products with advanced functionalities allows our customers to select the solution that best fits their specific needs in any particular oilfield application.

Our commitment to innovation for the oil industry

We have dedicated oilfield technical teams working tirelessly to understand the performance characteristics of our existing product portfolio so that we can recommend the best possible candidates to address our customers technical needs. We also have dedicated research and development scientists developing the next generation of products for application in the uniquely challenging oilfield environment. Our strategic intent is to provide bestin-class performance while reducing the environmental impact of oilfield operations. Specifically, we aim to replace toxic chemistries used in the market today with more benign materials or to find more environmentally friendly versions of products from our own porftolio. In this brochure, you will find our innovative offerings developed specifically for production and drilling applications . You can quickly scan and select the best products based on your needs.

AkzoNobel Surface Chemistry in the Oil Industry

Surface Chemistry is a business unit of AkzoNobel, the largest global paints and coatings company and a major producer of specialty chemicals. Based in Chicago, USA, our business unit operates in 50 countries, employing over 1,500 people. With regional marketing centers, manufacturing and R&D facilities worldwide, we are a leading supplier of specialty surfactants and synthetic and bio-polymer additives.

Manufacturing Chattanooga, USA Houston, USA Ft. Worth, USA Itupeva, Brazil Mons, Belgium Morris, USA Saskatoon, Canada Salisbury, USA Singapore Stenungsund, Sweden Stockvik, Sweden Yokkaichi, Japan Osaka, Japan Shanghai/Zhangjiagang, China

R&D Centers Bridgewater, USA Croton River, USA Chattanooga, USA Houston, USA Ft. Worth, USA Mexico City, Mexico Deventer, the Netherlands Itupeva, Brazil Mumbai, India Singapore Osaka, Japan Shanghai, China Stenungsund, Sweden

Headquarters Chicago, USA Bridgewater, USA Stenungsund, Sweden Sempach, Switzerland Shanghai, China Singapore

For a sustainable future:

Sustainability is at the heart of everything we do at AkzoNobel.
Were committed to reducing our impact on the planet by delivering more sustainable products and solutions to our customers. Thats why we have integrated sustainability into every area of our business for the benefit of our customers, our shareholders, our employees, our communities, and the world around us. As a result, we have been ranked in the top three on the Dow Jones Sustainability Index for five years running.

AkzoNobel Surface Chemistry in the Oil Industry

Solutions for stimulation

AkzoNobel Surface Chemistry also offers a variety of technologies that can be used in oilfield stimulation activities including cementing, fracturing and acidizing. Some of the technologies mentioned in this brochure can be applied to stimulation, but certainly not all. Stimulation application conditions have their own unique requirements and challenges. Especially when it comes to controlling the rheology of the applied fluids, water-based or oil-based.

Viscoelastic surfactant (VES) technologies are another essential class of chemistries produced by AkzoNobel Surface Chemistry. These products form worm-like micelles in depleted acids and saline brines which viscosify the various waterbased fluids required for fracturing and acidizing. These materials, sold under the Aromox and Armovis trade names, provide significant performance benefits over conventional nonsurfactant-based systems.

Additionally, we have secondary additives to help formulate fracturing and/or acidizing systems including foamers, corrosion inhibitors, organic viscosifiers and spacer additives. We also produce products that can be used in other oilfield applications, including enhanced oil recovery, shale-gas, pipeline and refinery. Contact our sales representative in your region for in-depth technical data sheets (TDS) that are available for these products, with descriptions of their performance characteristics and enduse properties.

AkzoNobel Surface Chemistry in the Oil Industry

Solutions for production applications

The production, separation and purification of crude oil and gas constitute a complex task that needs to be achieved not only safely but also quickly, economically, and in compliance with the regulatory restrictions of the operator's environment. Advances in understanding the characteristics of produced fluids, improvements in engineering design and materials science, as well as a greater appreciation of the mechanisms and conditions that promote production problems have all led to immense strides forward in the scale and speed of production. However, the task remains complex, and there is a continuing need in the industry for specialty chemical products to help meet productivity targets. AkzoNobel Surface Chemistry has worked for many years to develop an extensive range of products that can address most of the compelling issues that the production engineer and service provider face on a daily basis. Our product line for production applications includes demulsifiers, corrosion inhibitors, scale inhibitors, paraffin control, biocides, water clarifiers and deoilers, asphaltene inhibitors, and foamers.

Solutions for production applications

AkzoNobel Surface Chemistry in the Oil Industry

Solutions for production applications

AkzoNobel Surface Chemistry in the Oil Industry

Demulsifiers

Demulsifiers

During the production of crude oil, a multi-phase fluid is produced. Co-produced with the oil are natural gas and an amount of water, usually saline, which as the reservoir is depleted, can be present in quite large proportions.
During the production process, the fluids experience significant shearing in different locations, including the perforated zone, the downhole pump and the wellhead. Emulsifying agents naturally present in the crude oil, such as asphaltenes and the soaps of linear and aromatic organic acids, along with solids such as clays, sand and scale, stabilize the crude oil/water interface and make the emulsions difficult or slow to separate. In most oilfield applications, the initial crude is an oil-continuous emulsion that, upon treatment, can invert to become water-continuous, requiring the use of deoilers, which are covered separately. Due to the high throughput requirement of most oilfield separation systems, gravity separation of the emulsions is insufficient, particularly if the relative gravitational difference between hydrocarbon and water is negligible e.g., steam-assisted gravity drainage (SAG-D). Therefore, assistance is required to achieve satisfactory throughput. To achieve optimized demulsification, natural gas needs to be removed from the fluids to encourage quiescent coalescence of the emulsion. This is physically aided through heating of the oil and/ or the emulsion pad. This helps melt waxes and reduces the crude oil's viscosity, allowing the water droplets to settle out more quickly. However, by far the most common treatment to help break the emulsion is the addition of formulated chemical demulsifiers. These chemical additives are usually injected at the wellhead to achieve adequate mixing prior to the separator so that the demulsifier can reach the target interface and function effectively. To reach the surface of the emulsified water droplets, the demulsifier blend must have the right solubility. The chemical demulsifier is attracted to the emulsifying agent through differences in polarity. Once at the target, it neutralizes the effect of the emulsifying agent,

allowing the finely dispersed water droplets to coalesce upon contact. As the water droplets increase in size, they tend to settle, separating the water from the oil. The stability of an emulsion is unique to each reservoir, and may vary from well to well. As such, it is necessary to develop demulsifier blends specifically targeted at fluids produced. Witbreak demulsifier products should be considered as concentrated raw materials, or intermediates, for the preparation and/or formulation of oilfield demulsifiers and dehydrating chemicals. Field demulsifiers are usually blends of two or more intermediates, selected on the basis of their performance in bottle tests and centrifuge tests, the methods of which can be found in separate publications. These tests help identify the products that produce the maximum amount of water and the cleanest oil. The samples should be examined for fastest water drop, sludging, quality of the interface, and quality of the water. The best-performing candidates should have bottle tests repeated using different combinations and concentrations until eventually the best performance blend is found. Relative solubility number Another useful guide in formulation is the Relative Solubility Number (RSN), which helps eliminate some of the trial-and-error involved in formulating demulsifier blends. The value assigned to each product indicates its relative solubility in water.

As the numerical value increases, water solubility increases. Generally, products with a solubility number below 13 are insoluble in water. Products with solubility between 13 and 17 are dispersible in water at low concentrations and form gels at high concentrations. Products with values of 17 and above are completely water-soluble. The following are general guidelines for the RSN system: For crude oil emulsions, a demulsifier formulation should have an RSN between 8 and 15. The RSN values combine algebraically. For example, a 50-50 blend of a product with an RSN of 10 and a product with an RSN of 20 will yield a blend RSN of 15. In general, synergistic action between intermediates makes demulsifier blends better than single-component formulations. Demulsifiers with either very low or very high RSN values are seldom used individually; their properties can be best utilized by blending. Due to synergism, blends of intermediates from different chemical groups make better demulsifiers than blends using intermediates from the same family of compounds. Some demulsifier bases have special properties that give them very good blending characteristics. This is the case with highly oil-soluble (low RSN) polglycols. When blended with oxyalkylated resins, some

AkzoNobel Surface Chemistry in the Oil Industry

Demulsifiers

excellent demulsifier formulations have been developed for the oil industry. Other effective combinations include oxyalkylated resins blended with polyols, diepoxides or polyacrylatebased intermediates. To dehydrate crude oil to a sufficient level to achieve export quality, a combination of water droppers and oil dryers need to be used in the final demulsifier blend. While the droppers may work very quickly due to flocculation of large droplets, usually the base sediment and water (BS+W) will be greater than 1 percent - not sufficient
Table 1: Demulsifiers General information Product Witbreak DGE-169 Witbreak DPG-40 Witbreak DPG-481 Witbreak DPG-482 Witbreak DRA-21 Witbreak DRA-22 Witbreak DRA-50 Witbreak DRB-11 Witbreak DRB-127 Witbreak DRB-271 Witbreak DRC-163 Witbreak DRC-168 Witbreak DRC-232 Witbreak DRE-8164 Witbreak DRI-9010 Witbreak DRI-9026 Witbreak DRI-9030 Witbreak DRI-9037 Witbreak DRI-9045 Witbreak DRL-3124 Witbreak DRL-3134 Witbreak DRM-9510 Witbreak DTG-62 Witbreak GBG-3172 Description Glycol Ester Poly Glycol Poly Glycol Poly Glycol Resin Oxyalkylate Resin Oxyalkylate Resin Oxyalkylate Resin Oxyalkylate Resin Oxyalkylate Resin Oxyalkylate Resin Oxyalkylate Resin Oxyalkylate Resin Oxyalkylate Resin Ester Diepoxide Diepoxide Polyacrylate Polyacrylate Amine Oxyalkylate Resin Oxyalkylate Resin Oxyalkylate Polyacrylate Polyoxyalkylene Glycol Resin Oxyalkylate Type Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic

to complete the job. Drying demulsifiers help reduce the water content further via coalescence of the fine emulsion droplets, but this function usually takes longer. A balanced formulation of droppers and driers is usually required to achieve target. Typical dropper/drying characteristics of individual demulsifiers are given. Desalting Another important demulsifier application occurs at the refinery and is referred to as desalting. The imported crude oil arriving at the refinery contains up to 1 percent water, which will

contain significant amounts of dissolved salts. The refining process relies heavily on catalysts that will be poisoned if they are contacted by such salts, so the import crude is mixed with freshwater to remove these salts. The coalescence of the resulting emulsion is encouraged using an electrostatic grid and specialty desalting demulsifiers that yield crude suitable for refining. The following product lists (Tables 1 & 2) present AkzoNobel Surface Chemistry's portfolio of solutions for demulsifier applications.

Solubility (as 10% product) RSN 8.2 32 18.4 17 14.9 20.2 8.4 11.5 8.9 9.6 14.9 20.5 14.3 7.5 5 5.7 7.5 7.8 16 12.5 13.5 7.9 23.4 10.6 Isopropanol Kerosene S S S S S S S S S S S S S D S S D S S S D S D S D I D I D I D I D I I S D I S S I I D D D I I I Water I S S S D S I I I I I I I D D I I I S I I D D I

Function Aromatic 150 Water Dryer dropper S S S S S S S S S S S S S S I S S S S D D S S S

Application Wetting Water-in-oil demulsifier Waste oil demulsifier Desalter

* * *

BEST

* - secondary function, but when so, very effective. Products may be not be immediately available in all regions. Contact our local offices for more information.

Table 2: Secondary demulsifier additives Product Witconol NP-100 Witconate 708 Witconic AN Acid Petro IPSA Witconic 1298H Witconic 1298S Description Nonylphenol Ethopxylate Alkylaryl Sulfonate Alkylaryl Sulfonate Alkylaryl Sulfonate Branched DDBSA Linear DDBSA Type Nonionic Anionic Anionic Anionic Anionic Anionic Slug treater Wetting agent

Products may be not be immediately available in all regions. Contact our local offices for more information.

AkzoNobel Surface Chemistry in the Oil Industry

Corrosion inhibitors

Unlike typical iron corrosion, oilfield corrosion generally does not occur as a result of a metal's reacting with oxygen to produce rust.
Produced multiphase fluids are usually oxygenfree reductive environments. But due to the predominant use of mild steel in the construction of production pipework, acid gases dissolved in the produced water when in contact with the steel can lead to corrosion. For corrosion to occur, a galvanic cell must be established. Small variations within the body of the pipework or across weld sections create an electric potential. The galvanic circuit can be completed if water touches the iron surface, which itself is reduced as the iron is oxidized. Under acidic conditions typical of oilfield production, the cathodic reaction leads to the addition of electrons to aqueous protons producing hydrogen atoms. At the anode, iron is oxidized to ferrous (II) ions, leading to iron dissolution. Two types of corrosion occur in the oilfield: Carbon dioxide (CO2)-induced - called "sweet corrosion" - which is ubiquitous Hydrogen sulfide-induced corrosion - called "sour corrosion" - which is less common but more damaging. Sweet corrosion The severity of sweet corrosion will depend upon the conditions of production, but is usually worse at high pressures, due to the presence of higher concentrations of dissolved CO2 in the water (present as carbonic acid), and at higher temperatures (increased rate of reaction). Carbonic acid can continue to react directly with the iron surfaces, but under the right conditions can form a protective iron hydroxide film. However, if this is displaced, corrosion will continue. Sweet corrosion is characterized by the presence of closely grouped, smooth-edged pits. Rates of metal loss are usually lower than with sour corrosion. Sour corrosion Sour corrosion is more aggressive than sweet corrosion. Hydrogen sulfide (H2S) reacts directly with the iron surface. A protective film of ferrous sulfide (FeS) can form at the corrosion site;

however, even low fluid flow rates are sufficient to abrade the surface, enabling severe corrosion to continue. A further issue with sour corrosion is the poisoning of the hydrogen diatomization process. The hydrogen atoms diffuse into the metal where they can cause blistering, embrittlement and cracking in weak steels. Hydrogen sulfide can also be generated locally by sulfate-reducing bacteria (SRB). These SRBs are often most active under scale deposits in the production system, which can lead to severe localized pitting corrosion. Various methods of corrosion control are employed in the field, but continuous-dose, film-forming corrosion inhibitors are one of the most commonly employed. The mechanism of action is disruption of the galvanic cell. The film-forming surfactants

have a delta-positive charge that attracts them to the delta-negative pipe surface. The hydrophobic tails of the surfactants pack together to create a hydrophobic layer, minimizing contact between the water and pipe and reducing the corrosion potential. The schematic illustrates film formation and the protective nature of the film. AkzoNobel Surface Chemistry has developed a broad range of products that can be used to tackle oilfield corrosion (see Table 3). They can provide corrosion inhibition in a variety of forms, including oil-soluble, oil-soluble/water-dispersible and watersoluble. Guidance regarding formulation and inhibitor selection can be found in separate documentation.

Corrosion inhibitors

Figure 1: Film-Forming Corrosion Inhibitor

AkzoNobel Surface Chemistry in the Oil Industry

10

Table 3: Corrosion Inhibitors General information Solubility (c,f) Chemistry Molecular % primary % total weight amine active Appearance Minimum Pour point (F) Isopropanol amine number (mgKOH/g) Paste Solid Liquid Liquid Solid Liquid Liquid/paste Solid Liquid Liquid Liquid Liquid Solid Liquid Liquid Liquid Liquid Liquid Liquid Liquid/paste Paste Solid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Paste Liquid/paste Liquid/paste 165 202 275 281 207 207 206 210 NA NA NA NA NA NA NA NA NA 409 409 320 303 334 ND 144 ND 112 193 133 65 159 116 160 116 61 70 18 18 43 18 24 35 11 0 <0 <-1.1 32.8 3 <0 <0 <0 21 21 21 33 44 <0 ND -8 -15 8 -6 -4 16 7 32 13 5 S S S S S S ND S ND ND ND S S S S ND ND S S S ND S S S S S S S S S S S S S Kerosene Water Aromatic 150 HLB Davis scale 21 6.8 10.3 10.3 8.2 8 8 8.2 ND ND ND ND ND ND 23 21 21 17.5 17.5 15.6 15.6 15.6 ND 23.7 24 24.5 12.2 13.3 16.8 10 11.1 10.1 11.2 14.7 Product

Corrosion inhibitors

Armac C Armac HT Prills Armeen C Armeen CD Armeen HT Armeen OLD Armeen S Armeen TD Armohib CI-28 (d) Armohib CI-31 (e) Armohib CI-41 Armohib CI-209 Armohib CI-210 Armohib CI-219 Arquad C-50 Arquad O-50 Arquad S-50 Duomeen C Duomeen CD Duomeen O Duomeen S Duomeen T

Acetate salt of cocoalkylamines Acetate salt of hydrogenated tallow alkylamines Coco alkylamines Coco alkylamines, distilled Hydrogenated tallow alkylamines Oleylalkylamine, distilled Soyaalkylamines Hydrogenated tallow alkylamines, distilled Proprietary surfactant blend Proprietary surfactant blend Mixed polyamine + TOFA imidazoline Tall oil imidazoline Tall oil amidoamine DETA + TOFA imidazoline Cocoalkylatrimethyl ammonium chloride Oleylalkyltrimethyl ammonium chloride Soyaalkyltrimethyl ammonium chlroide N-coco-1,3-diaminopropane N-coco-1,3-diaminopropane, distilled N-oleyl-1,3-diaminopropane N-soya-1,3-diaminopropane N-tallow-1,3-diaminopropane

200 263 200 200 263 265 264 262

ND ND 95 98 97 98 97 98

98 98 99.5 99.5 99.5 99.5 99.5 99.5 ND ND ND ND ND 72 50 50 50 89 89 90 89 92 97 97 98 98 97 98 98 97 97 97 98 99

S P S S I S ND S ND ND ND S S S S ND ND D S S ND P S S I I S S I S S S S I

S P P P P P ND P ND ND ND I I I I ND ND P D D ND D D S S S D S S D S D S S

S P S S I S ND S ND ND ND S ND ND S ND ND S S S ND D S S I I S S I S S S S I

750-800 (a) ND ND ND 208-222 187-200 359 (b) 278 344 344 257 257 322 322 319 185-215 265-272 410-450 485-515 275-300 410-435 830-890 342-362 470-495 340-360 470-495 ND ND ND ND ND <2 <2 <2 43 45 45 43 45 <2 <2 <2 <2 <3 <2 <1 <3 <3 <3 <2 <1

Ethoduomeen C/13 Ethoxylated (3) N-coco-1,3-diamine propane Ethoduomeen T/20H Ethoxyated (10) N-tallow-1,3-diamine propane Ethoduomeen T/22 Ethoxyated (12) N-tallow-1,3-diamine propane Ethoduomeen T/25 Ethoxyated (15) N-tallow-1,3-diamine propane Ethomeen C/12 Ethomeen C/15 Ethomeen C/25A Ethomeen S/12 Ethomeen S/15 Ethomeen T/12 Ethomeen T/15 Ethomeen T/25 Ethoxylated (2) cocoalkylamines Ethoxylated (5) cocoalkylamines Ethoxyalted (15) cocoalkylamines Ethoxylated (2) soyaalkylamine Ethoxylated (5) soyaalkylamine Ethoxylated (2) tallowalkylamines Ethoxylated (5) tallowalkylamines

Ethoxyalted (15) tallowalkylamines 890-950

(a) Neutralization equivalent (b) Imidazoline content (c) Of 10% product in solvent (d) Inhibits mineral acids (e) Inhibits organic acids (f) some high melt solids required warming/shaking and cooling for observation ND = not determined, NA = not applicable S = soluble/clear, D = dispersible/turbid, I = insoluble/phase separation, P = Paste/Gel Products may be not be immediately available in all regions. Contact our local offices for more information.

AkzoNobel Surface Chemistry in the Oil Industry

11

Scale inhibitors

During the production of crude hydrocarbons, water is co-produced with oil and gas. It needs to be separated from the oil and gas to allow the hydrocarbon to meet the refinery specifications for export or sale.
As well as being a waste product, the produced water usually tends to precipitate inorganic salts during production, due to modification of environmental conditions encountered as the fluids are extracted. This occurs due to the physical changes experienced by the water as it is produced into the well, is mixed with other fluids and passed through the separation train. The severity and type of scale(s) that occur depend upon the unique chemistry of the formation water and the physical processes of temperature and pressure change experienced during production and separation of the produced fluids. The two most prevalent oilfield scales are calcium carbonate and barium sulfate. Most formation brines are saturated with respect to calcium carbonate due to the presence of an excess of the mineral in almost all reservoirs. Barium sulfate is commonly encountered when highly sulfated seawater or surface waters are injected into a reservoir to maintain pressure. Mixing with high-barium formation waters can lead to rapid scaling due to the very low solubility of barium sulfate in water. Unlike remedial treatment of calcium carbonate with acid, barium sulfate dissolver treatments are difficult to perform and seldom successful. Other common scales include strontium sulfate, iron (II) carbonate and calcium sulfate. Other less common, or exotic, scales include calcium phosphate, sodium chloride and the sulfides of zinc, iron and lead. Supersaturation of brine to any particular inorganic salt creates the potential for precipitation, and if precipitation occurs, this scale can lead to problems with the well, either through impairment of reservoir productivity by restricting the fluid pathways in the near well bore or by restricting fluid flow in the production tubulars and/or

separators. In addition to restricted production, safety and operational concerns arise due to scaling of critical monitoring and safety equipment as well as the potential accumulation of low specific activity scales due to co-precipitation of radium sulfate. A number of different approaches to tackling the problem of scale formation are employed in the field, preventative and remedial. One of the most widely used preventative option is the continuous injection or squeeze treatment of chemical threshold scale inhibitors into the production and/ or water injection system. Scale inhibitors are typically either phosphorouscontaining molecules or water-soluble polymers. The method of action of scale inhibitors depends on type. It is thought that the phosphorouscontaining molecules bind to the crystal growth sites preventing further growth, allowing microfine crystallites to be flushed from the system. For the polymers, molecular adsorption onto the meta-stable crystallites destabilizes them back

into solution and prevents the initial formation of scale. The performance and action of all scale inhibitors depend greatly upon the conditions of application, and it is suggested that scale inhibitors be screened under representative field conditions. AkzoNobel Surface Chemistry has developed a wide range of specialized scale inhibitors that allow the treatment of all common scales in a range of production conditions (see Table 4). We have assessed the performance of these products under a series of standard conditions to give indicative performance, as well as providing indicative physical property characteristics for these materials. The product portfolio includes green products made using our patented hybrid technology platform. Accurate residual scale inhibitor detection methods for our scale inhibitor products are available. These methods use either ICP-AES or wet chemistry methods and have detection limits to a few parts per million.

Scale inhibitors

AkzoNobel Surface Chemistry in the Oil Industry

12

Table 4: Scale Inhibitors General information Product Description Physical form Typical properties Approximate Typical pH Typical Calcium Barium Other molecular solids (%) carbonate sulfate scales weight perfomance 1 performance 2 3,000 800 7,500 5,000 600 15,000 10,000 15,000 5,000 10,000 5,000 5,000 245 20,000 20,000 2.5 3.5 4.3 4.5 <2 4.4 3.5 3.5 3 8 4 4 4.5 7 7 50 40 44 40 50 44 35 38 33 35 40 95 62 95 25 Brine Methanol Ethylene tolerance 3 tolerance (%) 4 glycol compatibility (%) 5

Alcoflow 100 Alcoflow 250 Alcoflow 260 Alcoflow 270 Alcoflow 275 Alcoflow 300 Alcoflow 750 Alcoflow 880 Alcoflow 895 Alcoflow 920 Narlex LD54 Narlex D54 Versa-TL 3 Versa-TL 4

Polyacrylic acid Polycarboxylate Multipolymer Multipolymer Polcarboxylate Multipolymer Multipolymer Hybrid polymer Hybrid polymer Sulfonated copolymer PPCA PPCA Sulfonated styrene copolymer Sulfonated styrene copolymer

Aqueous solution Aqueous solution Aqueous solution Aqueous solution Aqueous solution Aqueous solution Aqueous solution Aqueous solution Aqueous solution Aqueous solution Aqueous solution Dry powder Aqueous solution Dry powder Aqueous solution

CaSO4 CaSO4 CaSO4 CaPO4 NaCl CaSO4 CaSO4 CaSO4 Iron scales Iron scales

100 50 20 20 100 80 100 20 100 100 20 20 20 50 50

100 100 50 50 100 50 100 100 100 50 100 100 100 100 100

Armohib SI-3065 Phosphate ester

Scale inhibitors

Product Alcoflow 100 Alcoflow 225 Alcoflow 250 Alcoflow 260 Alcoflow 270 Alcoflow 275 Alcoflow 300 Alcoflow 750 Alcoflow 880 Alcoflow 895 Alcoflow 920 Narlex LD54 Narlex D54 Armohib SI-3065 Versa-TL 3 Versa-TL 4
1 Standard NACE test method.

Key characteristics High solids, superior carbonate inhibitor, limited brine tolerance. Unique biodegradable polymer. Iron tolerant. Great Carbonate inhibitor. Limited brine tolerance. Superior Barium Sulfate inhibitor. Ultra-brine stable. High solids. Broad scope scale inhibitor - high pH. Broad scope scale inhibitor - high pH. Superior Barium Sulfate inhibitor. Ultra-brine stable. Good brine tolerance. Calcium Phosphate inhibitor. Patented methanol tolerant scale inhibitor. Excellent multiscale control. Biodegradable hybrid polymer - North Sea compliant. Biodegradable hybrid polymer - North Sea compliant. Unique Sodium Chloride inhibitor. Phosphonated polymer suitable for squeeze/residual determination. Dry powder product for use as a squeeze inhibitor in cold climates. High performance topside and squeeze inhibitor. Range limited to 240F/115C. Unique ultra high temperature stable inhibitor/dispersant - >260C/500F. Unique ultra high temperature stable inhibitor/dispersant - >260C/500F.

= MIC 6ppm or less, = MIC 7-9ppm, = MIC 10-15ppm, = MIC>16ppm, MIC based on finished product. 2 50:50 Forties FW:SW, 80C (176F), 2 hours. = MIC 25-50ppm, = MIC 50-100ppm, = MIC 100-150ppm, = MIC>150ppm, MIC based on finished product. 3 Polymer stable in the following brines overnight at 95C (203F). = North Sea seawater, = 2500ppm Ca, 25000ppm Na, = 25000ppm Ca, 50000ppm Na. 4 Neat polymer stable upon addition of x% methanol
5 Neat polymer stable upon addition of x% ethylene glycol Products may be not be immediately available in all regions. Contact our local offices for more information.

AkzoNobel Surface Chemistry in the Oil Industry

13

Paraffin control

Paraffins are naturally occurring >C18-saturated linear and branchedalkane molecules that are found in most liquid crude hydrocarbons. These components are completely soluble in the hydrocarbon under virgin reservoir conditions.
The paraffinic components are not discreet molecules, but rather occur as a mixture of n-alkane-saturated hydrocarbons in the order of C18-C40, and even higher carbon chain lengths when branched. The presence of paraffins does not indicate the potential for a paraffin problem, and most paraffinic crudes are produced without precipitation or the need for chemical or physical treatment. Paraffins can become problematic when the fluids are subjected to various physical changes required to produce and separate the crude oil or condensate. Three physical processes in particular encourage precipitation of paraffinic fluids: Pressure change - this causes the light ends of the crude oil to vaporize, reducing the overall solubility of the high MW paraffins in the remaining liquid hydrocarbon, which can lead to precipitation. Strong pressure changes occur at the formation face, chokes/valves, the wellhead and separators Temperature change - cooling of the crude oil reduces the solubility of the paraffins, which start to associate with themselves and crystallize from solution, observed as a cloud point. Particularly problematic locations can be oil storage vessels and flow lines, especially long-distance sub-sea tiebacks. Turbulence - perhaps due to temporary degassing of fluids and impingement of wax crystallites on pipe walls, high turbulence flow areas are also known to be problem areas for paraffin deposits. Typical examples can be downhole pumps, treatment vessels, wellheads and chokes.

Paraffin begins by forming needle-like or plate-like structures, and is initially observed as a cloudpoint in the produced fluid. These deposits can be very different in nature from system to system. Some form mushy, readily dispersed deposits, others hard waxy deposits - the latter being more problematic from a remediation perspective. In general, the latter waxy-type forms from the higher C-chain length linear alkanes - typically >C25 n-alkanes and above. These problem highmolecular-weight paraffins are more prevalent in crude oil than condensates. The principal concern with paraffin deposits is the restriction of fluid production rates. This may be due to paraffin deposition in the near-wellbore,

restricting flow of hydrocarbon into the well, or more often deposition in production pipe work leading to restriction of diameter and therefore flow rate. Also the paraffinic crystallites, if precipitated in the bulk hydrocarbon, can increase the viscosity of the fluids, reducing pipeline throughput. At worst, if the paraffin crystal network is allowed to continue to grow and fuse, such as during a shut-in, wax gelling can occur and it may be impossible to re-initiate fluid flow, causing the pipe to be abandoned. Paraffin control regimes can be either remediative or pre-emptive. Modern reservoir developments design the production system to minimize the physical factors that can induce paraffin

Paraffin control

AkzoNobel Surface Chemistry in the Oil Industry

14

formation. However, paraffin formation may still be an issue. Paraffin remediation techniques include soaking the deposits with an appropriate solvent, often including a dispersant. Preemptive treatment involves the continuous injection of dispersants, inhibitors, pour point depressants, or combinations thereof. AkzoNobel Surface Chemistry has developed high-performance chemical additives to help tackle even the most challenging paraffinic crudes and condensates either in paraffin remediation or continuous treatment regimes. These products fall into three categories: Paraffin dispersants - surfactants used either in solvent treatments of pre-existing deposits or in continuous application to keep paraffin crystallites suspended in the solvent/crude and flushed out of the system without redepositing Paraffin inhibitors - oil-soluble polymers that reduce the temperature of appearance of the cloud-point, inhibiting the formation of paraffinic deposits Pour point depressants - used to limit wax gelling, usually induced by cold temperature exposure, by interfering with the crystallization process and keeping the bulk fluid mobile.

Table 5: Paraffin control

Paraffin control

General information Product Armohib PC-105 Armohib PC-150 Armohib PC-205 Armohib PC-308 Witconate 93S Witconate P10-95 Description Copolymer inhibitor/crystal modifier Proprietary blend Amine alkylarylsulfonate Copolymer inhibitor/crystal modifier Amine alkylarylsulfonate Amine alkylarylsulfonate

Paraffin dispersant

Paraffin inhibitor

Pour point depressant

Products may be not be immediately available in all regions. Contact our local offices for more information.

AkzoNobel Surface Chemistry in the Oil Industry

15

Biocides

Biocides

A virgin hydrocarbon reservoir is free of biological life before it is drilled or produced. However, as soon as contact is made with the surface, the potential for biological contamination exists.
Due to the relatively harsh environment downhole, only a limited number of organisms are able to survive and adapt if they make it to the reservoir. But once in place, these organisms will find an environment free of competition, with all the nutrients they need to grow and multiply. The biggest risk factors for contamination during the production process occur when surface fluids are injected directly into the reservoir, typical examples of which are produced water re-injection (PWRI), scale squeeze and other remediation or stimulation treatments of the wellbore. It is under these circumstances that extreme care should be taken to biologically decontaminate the fluids, which is usually achieved by using a suitable chemical biocide. Downhole colonization of the reservoir has a number of negative impacts. Slime-forming sessile bacteria can block pore throats and reduce the injectivity of water injection wells. Most damaging, however, is contamination with sulfate reducing bacteria (SRB) such as desulfovibrio. These bacteria metabolize the sulfate from surface injection waters into hydrogen sulfide gas. This acid gas level builds over time and causes enhanced corrosion, increased production costs (due to necessary H2S scavenging) and health and safety concerns. These bacteria are extremeophiles and are able to survive in the highsalinity, high-pressure, elevated temperatures and moderate pH levels typical of many reservoirs. Once bacterial colonies are established, it is practically impossible to disinfect a reservoir. The only true method to control the downhole environment is to ensure adequate biocide use topside. AkzoNobel's Biocides: Highly effective Due to the toxicity of many biocides to both the environment and to those handling the products, regulatory restrictions on biocides and their use have become more stringent in recent years.

The following listing of AkzoNobel Surface Chemistry biocides is specific to the regulatory body that approves the biocide for use. In countries where a similar regulatory structure is not in place, the adoption of the best practices of foreign regulators may be suitable. The biocides offered by AkzoNobel Surface Chemistry are non-oxidizing surface-active organic types. They disrupt the typical function of the cell by their adsorption onto cell walls. While this kill mechanism may not be as fast as

with oxidizing biocides, these biocides are less corrosive to production pipework, and can in fact act as corrosion inhibitors, particularly the quaternary ammonium compounds. Selecting the right biocide depends upon the target organisms to be treated, the regulatory approvals applicable and the type of treatment regime proposed. Many of the biocide chemistries mentioned become inactive once they reach the surface environment and are readily biodegraded to benign metabolic products.

AkzoNobel Surface Chemistry in the Oil Industry

16

Biocides

Table 6: Biocides Product Aquatreat DNM30 Aquatreat KM Arquad 2.10 Arquad MCB Armohib B101 Armohib B654 Duomeen C (intermediate) Description Dithiocarbamate Dithiocarbamate Didecylmethylquat Methylbenzylcocoquat Cocodiamine diacetate Cocodiamine diacetate Cocodiamine Physical form 25C Aqueous solution Aqueous solution Liquid Liquid Liquid Liquid Liquid Biocide registering authority US EPA / Canada DSL US EPA EU Biocidal Product Directive EU Biocidal Product Directive US EPA / Canada DSL Canada DSL US EPA / Canada DSL

Registrations and permitted use scenarios for biocides are complex. Please contact your sales representative. Products may be not be immediately available in all regions. Contact our local offices for more information.

AkzoNobel Surface Chemistry in the Oil Industry

17

Water clarifiers/deoilers

Demulsification and separation of the hydrocarbon phase during primary separation of produced fluids does not usually leave an aqueous phase sufficiently free of hydrocarbons to meet the discharge limits required for water disposal. Depending on the geographic location, these limits can be from 40 ppm residual oil in water, to as low as 10 ppm. Environmental regulations will continue to press for reduction of these discharge limits, particularly in marine environments.
Typically, a separation system will have equipment for treating the waste water to encourage the further separation of the oil droplets from the water. This equipment includes hydrocyclones, flotation tanks, filtration units, and centrifuges. The performance of these devices can be significantly improved through the use of chemical flocculating agents. The flocculants are referred to interchangeably as deoilers (due to the removal of the oil) or water clarifiers (due to improvement in water quality). The emulsion droplets that have not been removed by the primary separating system will be significantly stabilized from further coalescence due to two mechanisms. The first is mutual charge repulsion of emulsion droplets. As fluids are processed, the decreasing pressure allows the pH of the water to rise, resulting in the deprotonation of naturally occurring fatty and naphthenic acids present in the crude. These salts provide a negative charge to the emulsion surface and actually repel other oil droplets that would coalesce upon interaction. In high TDS brines, calcium soaps of fatty/ naphthenic acids can form, creating a solid phase at the water interface, making coalescence even

slower. This is similar to the second stabilizing mechanism whereby organic and/or inorganic solids adsorb to the emulsion oil/water interface, effectively sealing it from exposure to other emulsion droplets and impeding the coalescence mechanism. If the emulsion droplets are sufficiently

small, Brownian motion will keep the emulsion stable indefinitely. Effective deoiling can be achieved using polyelectrolytes that encourage flocculation of the emulsion droplets into larger collections, which are then more readily acted upon by the physical

Water clarifiers / deoilers

AkzoNobel Surface Chemistry in the Oil Industry

18

Water clarifiers / deoilers

separation equipment in the water treatment process. The preferred polymers neutralize the repulsive charges developed on the emulsion droplets, and if of sufficient size, can also bridge between the droplets collecting then together into flocculated groups where coalescence may occur due to close proximity. Flocculants are designed to function in the high salinity brines common in produced waters.

AkzoNobel Surface Chemistry's products include a range of natural and synthetic materials to meet the performance and environmental needs of the market. We also manufacture dithiocarbamate products, which are also known to form temporary insitu, iron-linked pseudo-polymer complexes that function as effective oilfield deoilers.

Table 7: Water clarifiers/deoilers General information Product Alcoclear CCP-II Flocaid 19 Flocaid 34 Witbreak RTC-330 Nsight A1 Nsight C1 Nsight H1 Description Polycationic Polyamphiphile Polyamphiphile Polycationic Anionically modified starch Cationically modified starch Hydrophobically modified starch Typical properties Physical form aqueous solution aqueous solution aqueous solution aqueous solution aqueous solution aqueous solution aqueous solution pH 4.5 4 4.8 4.5 12 12 6 Solids (%) 6.2 27.5 27.5 70 30 30 27 MW 1,000,000 100,000 100,000 ND 5,000,000 5,000,000 5,000,000

Products may be not be immediately available in all regions. Contact our local offices for more information.

AkzoNobel Surface Chemistry in the Oil Industry

19

Asphaltene inhibitors

Asphaltenes are some of the highest-molecularweight organic fractions to be found in crude oil. They consist of heteroatomcontaining polycyclic aromatic groups with aliphatic arms. The specific structure of asphaltenes varies from crude to crude, but where present, can be the source of major fouling and disruption to production. Asphaltenes can be a problem downhole as well as topside.
Asphaltenes are widely defined as those hydrocarbon materials that are soluble in aromatic solvents such as benzene, but not soluble in aliphatic solvents such as n-pentane. The presence of such asphaltenic components in a crude oil need not necessarily lead to asphaltene problems. However, precipitation of asphaltenes, when it occurs, is usually the result of the solubility of these high-molecularweight components destabilizing in the oil. The sources of destabilization are typical of production conditions e,g., pressure decline, pH change, crude mixing, etc. If non-chemical techniques cannot be employed to eliminate an asphaltene problem, then chemical inhibitors are required. AkzoNobel Surface Chemistry has recently developed Armohib AI-1000, a specialty inhibitor product to help with this specific production problem.

Table 8: Asphaltene inhibitors General information Product Armohib AI-1000 Description Ampoteric surfactant Typical properties Physical form Liquid/paste Pour point (F) 35C Solubility (25% or more) Isopropanol, benzene, mineral oil

Products may be not be immediately available in all regions. Contact our local offices for more information.

Asphaltene inhibitors

AkzoNobel Surface Chemistry in the Oil Industry

20

Asphaltene inhibitors

AkzoNobel Surface Chemistry in the Oil Industry

21

Foamers

In the production of crude oil and gas, foamers have a number of important applications. These include the deliquification of low-pressure gas wells by creating a stable foam that can slowly lift those heavy liquids from the wellbore that would otherwise slowly choke off the flow of the well, eventually killing it.
Foamers are also used in enhanced oil recovery (EOR) either as blocking and diverting agents to restrict unwanted flow or by improving the sweep characteristics of the mobile phase by reducing its mobility. Many of the products described here are also used in foamed drilling and stimulation applications (including fracturing, cementing and acidizing) where the use of foam can reduce the total chemical cost and/or improve the performance of the operation. Foamers work by preferentially adsorbing at the air/water interface, resulting in incorporation of significant volumes of air into the fluid. The fraction or percentage of air that is incorporated into the foam is referred to as the foam quality and is usually in the range of 75-90 percent, but can be as high as 97 percent. Foam quality will vary as a function of pressure and temperature and the chemistry of the water in the aqueous phase. Foamers need only be dosed at low concentrations to give significant results. During the unloading of gas wells, foamers can reduce the overall Specific Gravity (SG) of the fluid column in the well, allowing the reservoir to eject the water blockage. Treatments may be done by slug injections of liquid surfactant to the wellbore, or continuously through the use of a slowly dissolving foam stick. In EOR applications, it is the rheological characteristics of the foam flowing in a porous media that provide the desired mobility modification and fluid diversion. Foams are more resistant to flow than either the aqueous phase or the gaseous phase in such a medium, and this can be advantageous so long as the bubble size is designed properly.

A wide range of anionic surfactant chemistries is available from AkzoNobel Surface Chemistry. Selection will require consideration of the conditions of application and the environmental requirements. Laboratory evaluation of performance is recommended. Of the families of products available, the most environmentally friendly materials are the ether sulfates. These materials are somewhat brine tolerant, but are prone to hydrolysis in strongly acidic or alkaline conditions or at high temperature. As with many surfactant applications, synergism is observed with foamers, and we recommend blending ether sulfates with sulfonate products to boost performance.

The sulfonates and naphthalene sulfonate products are more robust than the ether sulfates. They have higher foaming performance and are more temperature-, brine- and pH-stable. But they can also be more environmentally persistent. Certain products can be made to be solvent and oil dispersible, and in a specific case can be used to foam non-aqueous media. Linear alpha-olephin sulfonates seem to offer particularly desirable properties as foamers in oilfield applications. On the next page, you will find AkzoNobel Surface Chemistry core products for foamers applications. Contact our local sales representative for more information on products and regional availability.

Foamers

AkzoNobel Surface Chemistry in the Oil Industry

22

Table 9: Foamers General information Product Description Appearance Typical properties Activity (%) 39 80 88.5 53 32 53 pH Freshwater Brine foamer foamer Gas well Soap unloading stick Foamed EOR Foam booster Non-aqueous and stimulation by blending foamer applications

Witcolate 1247H Witcolate 1259 Witcolate 1259FS Witcolate 1276 Witcolate 3220 Witconate 708

Ammonium C6-C10 Alcohol Ether Sulfate (3EO) C6-C10 Alcohol Ether Sulfate (3EO), IPA salt C6-C10 Alcohol Ether Sulfate (3EO), IPA salt Ammonium C10-C12 Alcohol Ether Sulfate (3EO) Surfactant blend Cyclohexylamine Salt of Disopropyl Naphthalene Sulfonic Acid in Naphthalene TEA-Dodecylbenzene Sulfonate Linear Sodium Dodecylbenzene Sulfonate Linear Isopropylamine Linear Dodecylbenzene Sulfonate Sodium C14-16 Alpha Olephin Sulfonate Sodium C14-16 Alpha Olephin Sulfonate Sodium C14-16 Alpha Olephin Sulfonate Sodium C12 Alpha Olephin Sulfonate Sodium Alkyl Napthalene Sulfonate Sodium Alkyl Napthalene Sulfonate

Liquid Liquid Liquid Liquid Liquid Liquid

7-8.5 (a) 7-8 (a) 7-8.5 (a) 7-8 (a) 8.8 (a) 6 (b)

Witconate 79S Witconate 90 Flake Witconate 93S Witconate 96A Witconate AOK Witconate AOS Witconate AOS-12 Petro BAF Petro P

Liquid Solid flake Liquid Liquid Solid flake Liquid Liquid Liquid Liquid

52 90 92 39 90 39 40 (g) 50 50

6.5-8 (c) 6.5-8.7 (d) 4-5 (e) 6.8-8.5 (d) 7-10 (d) 8-10 (f) 8-10 (a) ND 7.5-10

(a) 5% aqueous solution (b) 5% in 75% IPA solution (c) 5% in 25% IPA solution (d) 10% aq solution (e) 20% aq solution (f) 12.8% aq solution (g) % solid Products may be not be immediately available in all regions. Contact our local offices for more information.

Foamers

AkzoNobel Surface Chemistry in the Oil Industry

23

Solutions for drilling applications

Solutions for drilling applications

AkzoNobel Surface Chemistry in the Oil Industry

24

To access the hydrocarbons contained in an oil or gas reservoir, a well must be drilled to connect the reservoir with the surface. This will allow the crude fluids to be conveyed via the well to the surface for separation and refining. Rotary drilling techniques are used to create the well. A drill bit is mounted on a tubular drill string, which is turned by rotary action. The weight of the drill string on the rotating drill bit is sufficient to grind the rock and allow penetration toward target.
Solutions for drilling applications
A critical component of the success of a drilling operation is the use of drilling fluids. The most obvious need is for the fluid to carry the rock cuttings to the surface and out of the well to prevent them from clogging the drill bit and hindering further drilling progress. To do so, clean drilling fluids are injected into the hollow drill string. The fluid emerges from nozzles on the drill bit and flushes the cutting head and rock-face, lifting the ground rock away and sweeping the cuttings toward the surface through the annulus. Control of the viscosity of the mud and the fluid flow rates ensure adequate cuttings removal. The density of the mud also helps to create buoyancy for the cuttings. At the surface, the cuttings are physically separated using screens, and the cleaned fluids are returned to the well for pumping. Lifting the cuttings out of the well is not the only function that a drilling fluid must complete. Further critical functions include: Controlling formation pressure. Balancing the pressure of fluids in the drilled zones will ensure that either no fluids or a controlled flow of fluids will enter the well during drilling, thus enabling effective rheological control of the drilling fluid to be maintained. Sealing permeable formations. Many of the rock strata penetrated by the drill are permeable and will accept liquid from the mud. If allowed to continue, this will cause unacceptable mud thickening. The drilling mud is designed to develop a thin, low-permeability filter cake from the solids it contains. This seals the permeable zones from further fluid loss and allows drilling to continue. Suspending cuttings. While the drilling fluid's rheology is important in dynamic conditions, it is also important during periods of low annular velocity, such as a shut-in or the addition of a new pipe to the drill string. Drilling fluids are

designed to be thixotropic, developing high low-shear viscosity that maintains suspension of the cuttings and the weighting agents, thus minimizing any sedimentation or sag that might occur. The fluid should require minimal energy input to return to dynamic flow conditions. Maintaining wellbore stability. Erosion of the wellbore due to dynamic abrasion or an osmotic expansion of in-situ shales can be problematic. Brine chemistry and effective mud design can limit these issues.

Allowing effective removal of cuttings. Shale shakers are used to mechanically remove cuttings. However, if the mud thixotropy is insufficient, solids can be left in the mud. Upon reinjection, these particles break down further and can impact the rheology (of shales especially) and many other design characteristics of the mud. Lowering solids and plastic viscosity through the use of dispersants and deflocculants will help in this regard. Cooling and lubricating the drill bit. Due to the abrasive forces at play during drilling, the drill bit temperature can rise significantly. The drilling fluid helps reduce this. Water-based systems cool most efficiently although oilbased muds lubricate the most. Minimizing formation damage. The penetration of either mud fines or brine into the near-wellbore can permanently reduce the productivity of the reservoir. Remediation is possible, but avoidance through mud-design is preferred. Minimizing environmental impact. Lowertoxicity products have been developed to reduce the environmental burden of the drilling fluids in case of exposure or spill. Drilling muds are required to perform an extensive list of tasks. In addition, as regulatory and drilling performance requirements become increasingly challenging, these fluids are becoming increasingly complex and sophisticated, utilizing a variety of specialty chemical products to push performance boundaries. Satisfying all

AkzoNobel Surface Chemistry in the Oil Industry

25

requirements can be a challenge, especially when the fluid selected provides a compromise of performance, cost and the specifications of the reservoir being drilled. To help achieve the optimum balance of properties to meet drilling engineers' specific requirements, many different mud types have been developed, all of which fall into two fundamental drilling mud types: water-continuous fluids, also known as water-based muds (WBMs), and oil-continuous fluids, often referred to as oil-based muds (OBMs). WBMs use water as the continuous phase. They are thickened using bentonite or polymers and are usually weighted by dissolving salt into the water and/or dispersing sized inorganic minerals such as barium sulfate to counter the pressure from fluids in the formation and eliminate mud contamination. Due to the cheapness of the fluid base, WBMs are often preferred where their use is permitted by performance requirements. Water-based systems have until recently been limited to lower-temperature applications due to the poor rheological stability and high fluid loss characteristics at high temperatures. However, the development of high-temperature stable additives have allowed WBMs to be utilized in the most extreme drilling environments. From an environmental perspective, WBMs are also preferred because they contain lower-toxicity components. OBMs use either crude oil or a refined hydrocarbon (diesel) as the continuous phase. They too are thickened using bentonite

hydrophobically-modified, in this case. Their lubricating and fluid loss characteristics are much preferred over WBMs, but the toxicity of the base fluid can be a concern. Recently, "green" synthetic hydrocarbons have been developed, and are referred to as syntheticbased muds (SBMs). These materials, which are non-aromatic, usually contain a sacrificial chemical link to encourage biodegradation and have been used in environmentally sensitive areas. These mimic the characteristics of conventional hydrocarbon OBM bases in many ways, but the chemical additives used to complete the fluid may need to be adapted due to the aliphatic nature of the base. While this family of oil-continuous fluids (OBMs and SBMs) may be referred to as oil-based muds, in most cases these fluids are invert emulsions containing a high proportion of water in the internal phase. The emulsion provides viscosity to the fluid, and the internal phase is usually weighted with highly salinity brine (CaCl2 is most common) to increase the fluid density. To maintain the stability of the invert emulsion, high-performance emulsifiers are required. These materials are usually a formulation of various components to optimize performance. One of the key benefits of using OBMs is the ability to maintain an oil-wet surface to the reservoir, which inhibits shales, improves fluid loss and minimizes formation damage. To ensure the oil-wet character is maintained, wetting agents are also incorporated into the formulation. Other chemical additives utilized are dispersants, lubricants and foamers.

AkzoNobel Surface Chemistry has a full range of surfactant- and polymer-based additives to help our customers develop both high-performance and basic oil-based and water-based drilling mud formulations. Our research staff continues to develop novel products that address some of the key challenges facing the drilling market today, including products for high-temperature applications and materials to reduce the environmental impact of drilling. On the following tables (10 & 11) you will find our core products for oil-based and water-based muds. Advice and guidance on the chemistry can be provided through interaction with our sales and technical staff.

AkzoNobel Surface Chemistry in the Oil Industry

26

Oil-based mud additives

Table 10: Oil-based mud additives

General Information Product Description Type Typical properties Physical form at RT Liquid Liquid Liquid Liquid Paste Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid
* = not specified

Solubility pH Brookfield viscosity at RT 850 1300 2030 200 55 430 125 25 1750 70 65 50 65 50 2500 100 175 * 350 Pour point (F) Isopropanol

Amadol 511 Amadol 1017 Amadol CDA Armohib 209 Arquad 2HT-75 Arquad 2C-75 Arquad HTL8-MS Berol 840 Ethoquad 18/25 Ethylan 1008 Witcomul 1844 Witcomul 3020 Witcomul 3158 Witcomul 3241 Witconate 605A Witconate AOS Witcolate 1247-H Witconol NP-40 Witconol NP-100
S = soluble/clear,

Alkanolamide Modified Alkanolamide Alkanolamide Imidazoline Tallow Dimethyl Quat Coco Dimethyl Quat 2-Ethyhexylhydrogenatedtallowalkyl methyl sulfate Narrow range alcohol ethoxylate Octadecylamine (15 EO) Quaternary Ammonium Salt C10 Alcohol (8 EO) Ethoxylate Surfactant blend Surfactant blend Surfactant blend Alkanolamide Calcium Alkylaryl Sulfonate Sodium Alpha-olephin Sulfonate Alcohol Ether Sulfate Nonyl Phenol (4 EO) Ethoxylate Nonyl Phenol (10 EO) Ethoxylate
D = dispersible/turbid, I = insoluble/phase separation,

Nonionic Nonionic Nonionic Cationic Cationic Cationic Cationic Nonionic Cationic Nonionic Nonionic Nonionic/Anionic Nonionic/Anionic Nonionic Anionic Anionic Anionic Nonionic Nonionic
ND = not determined

8.6 9.5 9 11 7 7 7 7 8 7 7 6.5 7 6.5 6 7.7 7.5 7 7

<0 32 32 <0 40 <0 * * * 54 <0 18 <0 18 10 30 5 * *

S S I S S S S S S S S S ND S D D D S S

Products may be not be immediately available in all regions. Contact our local offices for more information.

AkzoNobel Surface Chemistry in the Oil Industry

27

General information Typical function Product Kerosene Water Aromatic 150 I I I S I S D S I S I S ND S S D I S S Drilling mud primary emulsifier Drilling mud secondary emulsifier Emulsion stabilizer Drilling mud lubricant Stuck pipe additive Surfactant Drilling mud detergent Wetting agent Dispersant Foaming agent

Amadol 511 Amadol 1017 Amadol CDA Armohib 209 Arquad 2HT-75 Arquad 2C-75 Arquad HTL8-MS Berol 840 Ethoquad 18/25 Ethylan 1008 Witcomul 1844 Witcomul 3020 Witcomul 3158 Witcomul 3241 Witconate 605A Witconate AOS Witcolate 1247-H Witconol NP-40 Witconol NP-100

S S I D I D S I S S I S ND I S D I I S

D S S D S S I S I S S D ND S I S S S I

AkzoNobel Surface Chemistry in the Oil Industry

28

Water-based mud additives

Table 11: Water-based mud additives General information Product Alcodrill HPDL Alcodrill HPDS Alcodrill SPDL Alcodrill SPDS Alcoflow 300D Narlex D72 VersaTL 3 VersaTL4 VersaTL 70 VersaTL130 VersaTL 501 VersaTL 502 Aquatreat DNM30 Aquatreat KM Arquad S50 Armohib 209 Arquad 2.1070 HPF Witcolate 1247 H Witcolate 1259 FS Witcolate 1276 Witconate 3203 Witconate AOK Witconate AOS Witconol NP100 Witconol NP120 Witconate 93S Amadol 1017 Witconate 605A AG 6202 AG 6206 AG 6210
(a) 5% in 3:1 IPA/H2O

Typical properties Description Sulfonated Polycarboxylate Sulfonated Polycarboxylate Polycarboxylate Polycarboxylate Sulfonated multipolymer Sulfonated Styrene Maleic Acid Copolymer Sulfonated Styrene Maleic Acid Copolymer Sulfonated Styrene Maleic Acid Copolymer Sulfonated Polystyrene Sulfonated Polystyrene Sulfonated Polystyrene Sulfonated Polystyrene Sodium Dithiocarbamate Blend Potassium Dimethyldithiocarbamate Soyaalkyltrimethyl Ammonium Chloride Tall Oil Imidazoline Didecylmethylquat Ammonium C6C10 Alcohol Ether Sulfate (3EO) C6C10 Alcohol Ether Sulfate (3EO), IPA salt Ammonium C10C12 Alcohol Ether Sulfate (3EO) Specialty Sulfonate Sodium C1416 Alpha Olephin Sulfonate Sodium C1416 Alpha Olephin Sulfonate Nonyl Phenol (10 EO) Ethoxylate Nonyl Phenol (12 EO) Ethoxylate Isopropylamine Linear Dodecylbenzene Sulfonate Modified Alkanolamide Calcium Alkylaryl Sulfonate Alkyl glucoside Alkyl glucoside Alkyl glucoside
(b) 5% in 1:1 2propanol:H2O

Charge Anionic Anionic Anionic Anionic Anionic Anionic Anionic Anionic Anionic Anionic Anionic Anionic Anionic Anionic Cationic Cationic Cationic Anionic Anionic Anionic Anionic Anionic Anionic Nonionic Nonionic Anionic Nonionic Anionic Nonionic Nonionic Nonionic

Physical form Aqueous liquid Water soluble powder Aqueous liquid Water soluble powder Water soluble powder Water soluble powder Water soluble powder Aqueous liquid Water soluble powder Aqueous liquid Aqueous liquid Water soluble powder Aqueous liquid Aqueous liquid Liquid in propylene glycol Liquid Aqueous liquid Aqueous liquid Aqueous liquid Aqueous liquid Aqueous liquid Flake Aqueous liquid Liquid Liquid Liquid Liquid Organic liquid Aqueous liquid/paste Aqueous liquid Aqueous solution

pH 6.5 6.5 8 8 7 7 7 7 7 6 7 7 11.5 13 7 11 (a) 7 (b) 7.8 (d) 7.5 (d) 7.5 (d) 7.5 8.5 (e) 8.5 (e) 6.5 (f) 6.5 (f) 4.5 (g) 9.5 (a) 6 (h) 7 (i) 7 (j) 6 (i)

Typical solids % (c ) 45 95 40 95 95 95 95 25 95 30 25 95 30 50 51 99 70 65 80 53 50 90 39 99 99 93 99 60 65 75 61
(e) 10% aqueous solution

Typical polymer molecular weight 3,500 3,500 3,000 3,000 15,000 15,000 20,000 20,000 75,000 200,000 1,000,000 1,000,000
(f) 1% in 62.5% IPA

(c ) Polymers as % total solids, surfactants as % actives

(d) 5% aqueous solution

Products may be not be immediately available in all regions. Contact our local offices for more information.

AkzoNobel Surface Chemistry in the Oil Industry

29

General information Product Alcodrill HPDL Alcodrill HPDS Alcodrill SPDL Alcodrill SPDS Alcoflow 300D Narlex D72 VersaTL 3 VersaTL 4 VersaTL 70 VersaTL 130 VersaTL 501 VersaTL 502 Aquatreat DNM30 Aquatreat KM Arquad S50 Armohib 209 Arquad 2.1070 HPF Witcolate 1247 H Witcolate 1259 FS Witcolate 1276 Witconate 3203 Witconate AOK Witconate AOS Witconol NP100 Witconol NP120 Witconate 93S Amadol 1017 Witconate 605A AG 6202 AG 6206 AG 6210
(g) 20% aqueous solution

Typical function Deflocculant Fluid loss additive Rheoloogy stabilizer Biocide Corrosion inhibitor Foamer Emulsifiers Lubricant Dispersant/ detergent Wetting agent Saltwater/ freshwater SW SW FW FW SW SW SW SW SW SW SW SW SW/FW SW/FW SW/FW SW/FW SW/FW SW SW FW SW FW FW SW/FW SW/FW SW/FW SW/FW SW/FW SW SW SW Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes High temperature stable

(h) 5% in 75%IPA

(i) 1% in water

(j) 2% in water

AkzoNobel Surface Chemistry in the Oil Industry

30

AkzoNobel Surface Chemistry in the Oil Industry

31

Oilfield Cleaning

There are a large number of applications within the oil and gas exploration area where cleaning and wetting are important for the success of oilfield operations. Many of these applications have been covered already in preceding sections of this brochure, but there are other applications in the oilfield where the need for cleaners is also critical in achieving performance requirements. These applications are diverse and include subjects such as cleaning and degreasing of all kinds of rig equipment, tank cleaning, drill-cuttings cleaning, cement-spacer cleaning, wellbore-cleaning spacer systems, removal of screen blockage and wellbore emulsions, reservoir rock cleaning, and reservoir wettability changes, to name a few.

Oilfield cleaning

AkzoNobel Surface Chemistry in the Oil Industry

32

Developing sustainable products from natural sources

AkzoNobel Surface Chemistry (ANSC) has a long history of producing highly efficient surfactant-based cleaning products for a variety of markets. These products are sold in the oilfield under the Armoclean brand name.
Oilfield cleaning
This history, when combined with the strength of being one of the worlds largest surfactant manufacturers (particularly in the area of fatty amine-based surfactants) and having an experienced and dedicated oilfield technical service team, makes our product portfolio particularly strong. A key differentiator of the ANSC portfolio is our development of sustainable products from natural sources with a low impact on the environment. During the last decade, our company has led the way in introducing alkyl glucoside technologies and other cutting-edge greener and water-based cleaning solutions. No company is more motivated to meet the present and future challenges in this

area than AkzoNobel. Our focus in this area has already been recognized, with AkzoNobel being ranked in the top-3 in the Chemicals sector of the Dow Jones Sustainability Index for the last five years. Developing performance advantage through specialty surfactant blending As is often the case with surfactants, the development of a multi-component performance blends frequently elicits the highest performance products, particularly in oilfield applications where the challenging variables of temperature, high electrolyte concentration, variable hydrocarbon chemistry (including naturally occurring surface active agents), high-shear environments and suspended solids can make for some very challenging and dynamic treatment regimes. ANSC offers singlecomponent additives for customers to develop their own specialty blends for the oilfield. Our scientists have also developed a number of formulated blends specifically for the oilfield which we also offer to the market, delivering excellent performance-in-use and saving our customers the time and expense of developing their own formulations. Typically, scientists designing a performance blend would measure surface tension, surface charge (zeta potential), contact angle and wetting to determine the optimized products. However, in the

oilfield, interfaces can be created and modified very rapidly with physiochemical conditions changing as fluids are being produced, injected downhole or introduced into the reservoir. As such, there continues to be an amount of art rather than scientific method that goes into the creation of formulations that work in the field. Having said that, knowing what the functional characteristics that each component brings to a blend is important in being able to design the optimized multi-component blend. Our surfactants can be grouped into a number of different categories: Hydrotropes. These are compounds that increase the solubility of a surfactant in a formulation, achieving a much higher aqueous concentration of a primary surfactant or allowing its utility in a wider temperature range e.g., increasing cloudpoint. Hydrotropes may also be referred to as co-surfactants or secondary surfactants. In general, hydrotropes are rather poor surfactants by themselves, but are highly valuable in that they can help to include/dissolve poorly water-soluble molecules, such as low-HLB* nonionic cleaning surfactants, into water-based formulations and at the same time boost their performance. Our hydrotropes cover a range of uses and are widely used in producing high-performance formulations.
*Hydrophilic-Lipophilic Balance (low values = oil soluble molecules, high values = water soluble molecules.

Table 12: Oilfield cleaning

Product name Surfactant type Chemistry Properties low foaming ARMOCLEAN 1000 ARMOCLEAN 1025 ARMOCLEAN 1100 ARMOCLEAN 2000 ARMOCLEAN 3000 ARMOCLEAN 4000 ARMOCLEAN 4100 ARMOCLEAN 4150 ARMOCLEAN 4200 ARMOCLEAN 4330 ARMOCLEAN 4350 ARMOCLEAN 4380 ARMOCLEAN 6000 ARMOCLEAN 6040 ARMOCLEAN 6060 ARMOCLEAN 6100 ARMOCLEAN 6250 Nonionic/cationic Nonionic/cationic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Nonionic Cationic Cationic Specialty Specialty Specialty Specialty Amide Alkoxylate Alcohol Alkoxylate Alcohol Alkoxylate Alcohol Alkoxylate Alcohol Alkoxylate Alcohol Alkoxylate Alcohol Alkoxylate Alcohol Alkoxylate Glucoside Glucoside Glucoside Quaternary Quaternary medium foaming high foaming hydrotrope wetting dispersing emulsifying

BEST

AkzoNobel Surface Chemistry in the Oil Industry

33

Wetting agents. These are sometimes of major value, and can be used to alter the polarity of the solvent which will wet its surface in a mixed solvent system. An oilfield example is reservoir-relative permeability modification, which can be used to enhance the rate of oil production. Surfactants, being amphiphilic in nature, are characterized by their tendency to concentrate at an interface. Wetting agents alter the free energy of contacted surface, modifying its polarity. Wetting surfactants can render hydrophilic surfaces oil wet or hydrophobic surfaces to water wet. Surface wettability modifications are extremely useful for many oilfield applications. Emulsifiers. These allow two immiscible liquid phases to be compounded into micro or macro-phase mixtures. When oil and water are mixed, the created emulsion is thermodynamically unstable, and the two phases will re-separate over time. Depending on the properties of organic and aqueous phases to be emulsified, and upon the type and concentration of surfactants present, a stable micro-emulsion or a semi-stable macroemulsion can be formed. The surfactant (or emulsifier) acts by adsorbing at the interface and reducing the interfacial energy. (It is the existence of this interfacial energy that is essentially responsible for the instability of an

emulsion, since the large increase in interfacial area upon the formation of the emulsion droplets will cause an increase in the free energy of the system.) Emulsification in oilfield cleaning is mostly the dispersion of oil droplets in water. An oily substance in the form of an emulsion or micro-emulsion can be removed by aqueous phase solutions. Microemulsions are thermodynamically stable systems (they do not separate with time) with a very low interfacial tension between the oil and water phases. Solubilizers. Solubilization is a phenomenon that is of major importance in oilfield cleaning applications as it can remove oily material by incorporating these water-insoluble substances into the interior of a thermodynamically stable water-based solution (micro-emulsion) or a semi-stable macro-emulsion system. Once solubilized into the hydrophobic interior of the micelle, the soil will be removed from the surface and transported away from its source in a continuous phase in which it would otherwise be insoluble. One area of growth in recent years has been to move away from solvent-based cleaning formulations. While effective, these formulations were not pleasant to work with, had low flashpoints and were relatively toxic to humans

Product name

Physical characteristics Electrolyte stability Requires hydrotrope Indicative thermal stability (C) >150 >150 Short term stability >150 >150 Short term stability >150 >150 >150 >150 >150 >150 >150 >150 Short term stability >150 Short term stability >150 Short term stability >150 >150 >150

Application Acid cleaner Alkaline (pH<12) High alkaline (pH>12) Waterbased degreasers Solvent based cleaners Microemulsions Quick-break effect

ARMOCLEAN 1000 ARMOCLEAN 1025 ARMOCLEAN 1100 ARMOCLEAN 2000 ARMOCLEAN 3000 ARMOCLEAN 4000 ARMOCLEAN 4100 ARMOCLEAN 4150 ARMOCLEAN 4200 ARMOCLEAN 4330 ARMOCLEAN 4350 ARMOCLEAN 4380 ARMOCLEAN 6000 ARMOCLEAN 6040 ARMOCLEAN 6060 ARMOCLEAN 6100 ARMOCLEAN 6250

good good excellent good good when formulated when formulated when formulated when formulated when formulated when formulated when formulated excellent excellent excellent good good

150 C = 300 F

AkzoNobel Surface Chemistry in the Oil Industry

34

and the environment. Today, a few active percent of surfactant in aqueous solution can deliver the same performance as the previous high-volatile organic compound (VOC) formulations. Success has been achieved by selecting the right primary surfactant to perform the desired function on the target deposit, whether that be dispersion, emulsification or wetting. For oily soils, these primary surfactants are often themselves very hydrophobic and can have limited water solubility. Hydrotropes are required to solubilize the primary surfactant into aqueous solution, raising the cloudpoint of the solution to acceptable levels. Inorganic particulates may also be present in soils, and in this case a more hydrophilic surfactant may need to be introduced as a component in the final cleaner blend to target this type of soil. These surfactants may be more hydrophilic than those targeting the oily soil. A combination of primary surfactants and a hydrotrope may be required in the final formulation. The mixed micellar aqueous solution delivers the primary surfactant(s) to the target deposits surface and allows it to perform its function. There are also a number of synergistic components that can be added to further improve the performance of the formulation. If the target deposit is a tough organic solid such as bitumen, wax, tar or asphalt, aqueous surfactant solutions may not be powerful enough cleaning agents to effectively remove the target soil. In such cases, solvent-based cleaners or micro-

emulsions may be used. Here the formulation is optimized based on the removal of the soil from the substrate and allows the surface to be wet by the preferred solvent aqueous or organic. In the case of cold degreasers, a critical function of the formulation is the emulsifier, which keeps the lifted soil away from the surface and keeps it in solution and flushable from the surface. Micro-emulsions exhibit special properties because the solution provides such high surfactant concentrations, but exhibit properties mid-way between aqueousand organic-based cleaners. Because these solutions are so highly built, their higher cost must be justified against the performance benefits exhibited. AkzoNobel surfactants specially designed for refining and optimizing cleaner formulations Our product portfolio contains a variety of surfactant types to allow the formulator to refine and optimize the cleaner formulation. They include: Alkyl glucoside products, which provide performance properties such as low or very low foam, good wetting, dispersion, solubilization, very high electrolyte tolerance and temperature insensitivity. These products are ideal as hydrotropes to manage your complex formulations and are, together with a number of other products in our offering, fully approved for use in the North Sea.

Narrow-range fatty alcohol ethoxylate products are produced using narrow-range technology, resulting in a peaked distribution of the added ethylene oxide units. This gives a low content of unreacted alcohol, resulting in low odor, lower foaming tendency and improved cleaning efficiency. Quick-breaking surfactants are designed to form semi-stable emulsions which effectively clean their target surface. However, the produced effluent emulsion will separate quickly if left quiescent in a holding tank, separating into an organic and an aqueous phase. The clean water can be decanted and disposed of, allowing recovery and re-use of the organic layer. This is an optimized physical effect, rather than a chemical cleaving mechanism, requiring no secondary treatment. Cold degreasers are a powerful form of formulated emulsifier in an organic solvent that enables penetration and removal of difficult oily soils even at low temperature, where previously hot solvent cleaning was required. The emulsifying agent holds the dispersed soil in solution during the secondary aqueous flush, ensuring that the soil is not re-deposited on the freshly cleaned surface. For advice on formulation development and use of our oilfield cleaner products, please contact your local sales representative.

USA Head Office Akzo Nobel Surface Chemistry LLC 525 West Van Buren Street Chicago, IL 60607-3835, USA Telephone: +1 312 544 7000 Fax: +1 312 544 7320 Customer Service Telephone: +1 800 906 9977 Technical Service Akzo Nobel Surface Chemistry LLCc281 Fields Lane Brewster, NY 10509 Telephone: +1 845 276 8200 Fax: +1 845-277-1423 Canada Akzo Nobel Chemicals Ltd 1, City Center Drive Suite 318 Mississauga, Ontario, L5B M2 Telephone: +1 905 273 5959 Fax: +1 905 273 7339 South America Akzo Nobel Surface Chemistry LLC Rodovia Akzo Nobel 707 Bairro So Roque da Chave P.O.Box 32 Cep 13295-000 Itupeva S.P. Telephone: +55 11 45918938 Fax: +55 11 45911744 Mexico, Central America and Caribbean Akzo Nobel Chemicals SA de CV Av, Morelos No. 49 Col. Tecamachalco CP 56500 Los Reyes la Paz, Edo. de Mexico Telephone: +52 (55) 5858-0756 Fax: +52 (55) 5858 0703 Middle East Akzo Nobel Surface Chemistry International Paint (Gulf) LLC PO BOX 290 Dubai United Arab Emirates Telephone: + 971 (0)4 347 2491 Fax: + 971 (0) 4 947 2339 Russia Akzo Nobel Rep. Office Ulitsa Smolnaya 24 D125445 MoscowRussia Telephone: +7 (495) 960 28 90 China Akzo Nobel Surface Chemistry The Exchange, TongRen Road 299200040 ShanghaiChina Telephone: +86 21 2216 3600 Products mentioned may not be available in all countries. AG, Alcoclear, Alcodrill, Alcoflow, Amadol, Armac, Armeen, Armohib, Arquad, Berol, Duomeen, Ethoduomeen, Ethomeen, Ethoquad, Ethylan, Floc aid, Narlex, Nsight, Petro, Versa-TL, Witbreak, Witcolate, Witcomul, Witconate, Witconic and Witconol are registered trademarks in the USA. 2011 Akzo Nobel Surface Chemistry LLC, all rights reserved

www.akzonobel.com/surface AkzoNobel is the largest global paints and coatings company and a major producer of specialty chemicals. We supply industries and consumers worldwide with innovative products and are passionate about developing sustainable answers for our customers. Our portfolio includes well known brands such as Dulux, Sikkens, International and Eka. Headquartered in Amsterdam, the Netherlands, we are a Global Fortune 500 company and are consistently ranked as one of the leaders in the area of sustainability. With operations in more than 80 countries, our 55,000 people around the world are committed to excellence and delivering Tomorrow's Answers Today. 2012 Akzo Nobel N.V. All rights reserved.Tomorrows Answers Today is a trademark of AkzoNobel N.V.