Silbreak* Demulsifiers

for crude oil demulsification

Introduction Product Description
Silbreak demulsifiers are excellent candidates to consider to help overcome these tough demulsification issues. Silbreak demulsifiers are a new class of materials that combine the outstanding surface activity of the siloxane polymer with the water or oil solubility of organic substituents. They contain no added halogens and are based on organically modified siloxane molecules, hence behave significantly differently from polydimethylsiloxanes.

Oil operators are compelled to replenish their crude oil reserves with new oil fields in order to retain their economic position. As most of the easy targets have been identified and are being exploited, the majority of recent field developments and near term exploration are targeting areas previously thought uneconomic or technologically too demanding. Further, enhanced recovery techniques are increasingly being employed to improve the yield of any given well. As a result, the industry has to deal with extreme situations such as heavy or high TAN crudes, oil sands, deep-sea fields and severe sludge. In many of these cases, difficult demulsification problems are encountered, due to the nature of the crude and the presence of mineral and organic solids or surfactants.

Key Features and Typical Benefits

May act as boosters for organic demulsifier formulations at low concentrations Can help improve the clarity of the separated water; practically oil-free water Controlled speed of water separation Reduced sludge, water wetting of solids Effective in most crudes, particularly heavy In many cases, Silbreak demulsifiers are active at lower crude temperatures than organic demulsifiers Low tendency to stabilize foam or emulsions, even at high concentrations Typically, performance increases as concentration increases Easy to handle because of their medium to low viscosities

Momentive Performance Materials provides versatile materials as the starting point for our creative approach to ideas that help enable new developments across hundreds of industrial and consumer applications. We are helping customers

solve product, process, and performance problems; our silanes, fluids, elastomers, sealants, resins, adhesives, urethane additives, and other specialty products are delivering innovation in everything from car engines to biomedical devices.

From helping to develop safer tires and keeping electronics cooler, to improving the feel of lipstick and ensuring the reliability of adhesives, our technologies and enabling solutions are at the frontline of innovation.

Silbreak* Demulsifiers

Typical Physical Properties of Silbreak Demulsifiers

Table 1 shows typical physical properties as well as RSN values and an indication of the molecular weight of the Silbreak demulsifiers. All the Silbreak demulsifiers are soluble in either methanol or xylene at a concentration of 10% by weight.

Table 1: Typical Properties of Silbreak Demulsifiers

Silbreak Demulsifier 320 321 322 323 327 329 400 401 402 559 589 602 603 605 606 609 625 638 639 743 1324 1636 1840 RSN(a) 14.2 8.2 15.3 8.7 7.4 14.9 7.0 8.0 7.9 9.6 8.7 9.2 7.0 8.6 9.7 9.9 9.8 9.4 17.1 8.6 6.6 7.3 12.0 Viscosity (cSt) at 20C 480 2000 720 1700 90 1300 2500 5000 3300 55 1700 430 1850 350 470 130 140 150 200 1700 2400 170 300 Flash Point(d) (C) 115 135 99 89 81 >93 98 143 110 81 135 81 98 77 63 78 63 >80 121 120 98 81 121 Density g/ml at 20C 1.030 1.030 1.050 1.040 0.870 1.047 1.020 1.027 1.027 0.970 1.062 1.009 1.059 0.995 0.999 1.000 0.993 0.962 1.049 1.027 1.020 0.932 1.074 Silicone Molecular Weight (MW)(b) M H M H M M H M H M H H H H M L M H L H H M L Silicone Cloud Point(c) (C) 60 40 58 38 N/A 60 N/A 35 N/A N/A 40 N/A 38 38 58 76 60 N/A 76 40 38 N/A <10

(a) The RSN (Relative Solubility Number) value was determined experimentally based on the method of J. Wu et al. Colloids and Surfaces A: 232 (2004) 229237 (b) L stands for Low: MW<8000 daltons M stands for Medium: 8000<MW<15000 daltons H stands for High: MW> 15000 daltons (c) The cloud point was measured in an aqueous solution of silicone at 1% w/w. N/A indicates material is not soluble in water at 25C (d) Pensky-Martens closed cup ASTM D 93

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Silbreak* Demulsifiers

How to Use
Silbreak demulsifiers are not intended to replace organic demulsifiers. Instead, they should be blended together with organic demulsifiers. Typically, such a blend will contain between 2 and 25% of a Silbreak demulsifier. In certain very difficult crudes, such as high viscosity slops, the Silbreak demulsifier may be the predominant component. These new organic/silicone formulations typically exhibit remarkable synergies and possess exceptional activity in a variety of crude oils and situations. Experienced demulsifier formulators may need little or no instructions on how to run bottle tests and the appropriate methodology to follow. The following short description therefore is intended for those new to the art of formulating (more detailed information is available on request): 1. Run bottle tests using the organic demulsifiers. Rate these demulsifiers based on the requirements of the field, for example, %BS&W and/or speed of separation and/or clean water, etc. 2. Run bottle tests using the Silbreak demulsifiers. Rate them in the same way as the organic demulsifiers. 3. Create a table that ranks the two types of demulsifiers, with the best products at the top: Organic demulsifier Best is product E Second best is product A Third best is product C Silbreak demulsifier Best is Silbreak G Second best is Silbreak B Third best is Silbreak D

4. It is possible that the organic demulsifiers are better than the Silbreak demulsifiers. For example, in the table above, it is possible that Product C is better than Silbreak G. Despite this, it is important to proceed with step 5. 5. Proceed to formulate by blending the best of the organic demulsifiers with the best of the Silbreak demulsifiers. We recommend to start with 90 parts of the organic demulsifier and 10 parts of the Silbreak demulsifier.

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Silbreak* Demulsifiers

How to Use (continued)

6. More complicated blends that involve three or four demulsifiers selected from the organic demulsifiers and Silbreak demulsifiers in the table above may lead to even better results. Blending of Silbreak Demulsifiers in Existing Formulations If the time available for bottle tests is limited, an effective way of identifying the best Silbreak demulsifier may be to replace 50% of the incumbent demulsifier formulation by an equal weight of a 10% solution of a Silbreak demulsifier. It is recommended that the same solvent be used. The concentration of the Silbreak demulsifier can be varied depending on the results. Powerful Synergies with Polyols Organic demulsifiers based on polyol chemistries when blended together with Silbreak demulsifiers typically show exceptional synergies. Polyols can be based on ethoxylated/propoxylated adducts of ethylene diamine, glycerol or others. Product Recommendations There are virtually thousands of different crudes and plant conditions. Therefore while it is difficult to generalize and we strongly recommend that all Silbreak demulsifiers be tested, we have seen that certain Silbreak demulsifiers tend to work better in certain conditions. The following is a summary of our findings: For Heavy Crudes (APIs lower than 15) Silbreak demulsifiers 329, 320, 321, 743, 1324, 603, 625, 400, 401 and 322 For Medium Crudes (APIs between 15 and 25) Silbreak demulsifiers 1840, 320, 323, 1636, 400, 401 and 402 For Light Crudes (APIs greater than 25) Silbreak demulsifiers 1840,1636, 402 and 400. In addition to demulsification, certain Silbreak demulsifiers may also offer foam control and/or de-aeration. Silbreak demulsifiers 638, 320, 323, 327, 329, 589 and 602 may possess such activity. In particular Silbreak 638 silicone demulsifier is inherently degradable in sea-water and has a molecular weight that exceeds 600. Further, Silbreak 638 silicone demulsifier has passed ecotoxicity tests using a variety of aquatic species. It is therefore expected to be approvable for use under European requirements for use and discharge of offshore chemicals. Please refer to separate data sheet for more information on this product.

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Silbreak* Demulsifiers

Case History
An example of powerful synergy between organic demulsifiers and Silbreak demulsifiers can be seen from the following case history.

Table 1: Latin America, API: 23-24, Water Cut: 45%, Initial Tests
Demulsifier Current Control Organic 1 Organic 2 Organic 3 Organic 4 Silbreak 329 Silbreak 320 Silbreak 321 Silbreak 322 Silbreak 323 Silbreak 327 Silbreak 329 Silbreak 559 Silbreak 589 Silbreak 602 Silbreak 603 Silbreak 605 Silbreak 606 Silbreak 609 Silbreak 625 Silbreak 638 Silbreak 639 Silbreak 743 Silbreak 1324 Silbreak 1636 Silbreak 1840 Dose (ppm) 5 250 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 18 8 18 9 20 1 1 2 3 3 5 3 8 5 5 3 3 5 2 10 0 0 1 5 5 7 Separation of water in ml 15 38 10 22 22 25 3 3 7 5 5 8 4 10 6 9 4 7 6 3 11 2 4 3 8 6 8 30 39 16 25 28 28 5 5 8 7 14 9 9 10 8 12 8 10 10 6 18 6 6 12 8 8 9 1h 40 21 29 30 32 6 6 10 8 18 9 10 11 11 14 10 11 11 9 20 8 8 15 10 12 10 2h 41 28 31 30 36 7 7 12 10 18 9 12 12 14 15 15 12 12 10 21 8 9 15 11 14 12 3h 41 30 35 31 39 8 8 13 12 18 9 15 14 16 18 18 15 14 12 21 9 10 15 12 15 13 Water Quality 1 1 1 1 1 4 4 2 4 3 2 2 3 3 3 4 5 4 4 2 3 4 4 3 3 2 Interface Quality 1 1 1 3 2 2 2 2 4 3 3 2 3 3 3 3 3 3 2 2 4 5 5 3 4 3 8 7 14 10 8 3 13 10 14 10 14 12 10 %BS&W 2 17 14 13.6 11

The rating for the quality of water and interface is: 1 = Ideal, clear, 5 = Very poor Note: Test data. Actual results may vary.

The current control was a combination of the four organics listed as Organic 1, 2, 3 and 4 in the table above.

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Silbreak* Demulsifiers

Case History (continued)

Based on these results, several blends of organic and Silbreak demulsifiers were tested with the objective of improving on the cost/performance of the existing formulation. The most successful blends are shown in Table 3.

Table 3: Optimized Blends of Silbreak Demulsifiers and Organic Demulsifiers

Formulation Current Control Organic 2 Silbreak 625 Silbreak 1324 Organic 2 Silbreak 625 Silbreak 603 Organic 2 Organic 1 Silbreak 625 Current Control Organic 2 Silbreak 625 Silbreak 1324 Organic 2 Silbreak 625 Silbreak 603 Organic 2 Silbreak 625 Silbreak 1324 Organic 2 Silbreak 625 Silbreak 603 Organic 2 Organic 1 Silbreak 625 Dose (ppm 250 160 10 17 140 10 35 120 30 50 250 160 10 17 140 10 35 144 9 15 126 9 31 108 27 45 36 40 1 1 0.8 80 38 40 1 1 1.2 78 34 38 1 1 3.4 78 36 38 1 1 0.2 87 36 38 1 1 0.4 87 39 39 1 1 1 100 32 34 1 1 3 89 39 40 1 1 1 87 38 39 1 1 1.6 87 Separation of Water 10mln 38 12h 38 Quality of Water 1 Quality of Interface 1 %BS&W 1.8 Relative Cost 100

Note: Test data. Actual results may vary.

As can be seen from this work, by exploiting the powerful synergy between the Silbreak demulsifiers and the organic demulsifiers, several lower cost formulations were developed with similar or even improved performance.

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Silbreak* Demulsifiers

Patent Status
Protected by US patents 6,001,140 and 6,221815, their foreign counterparts and one or more pending US and foreign applications. Nothing contained herein shall be construed to imply the nonexistence of any relevant patents or to constitute the permission, inducement or recommendation to practice any invention covered by any patent, without authority from the owner of the patent.

Product Safety, Handling and Storage

Customers considering the use of this product should review the latest Material Safety Data Sheet and label for product safety information, handling instructions, personal protective equipment if necessary, and any special storage conditions required. Material Safety Data Sheets are available at www.momentive.com or, upon request, from any Momentive Performance Materials representative. Use of other materials in conjunction with Momentive Performance Materials products (for example, primers) may require additional precautions. Please review and follow the safety information provided by the manufacturer of such other materials.

Limitations
Customers must evaluate Momentive Performance Materials products and make their own determination as to fitness of use in their particular applications.

Emergency Service
Momentive Performance Materials maintains an around-the-clock emergency service for its products. The American Chemistry Council (CHEMTREC), Transport Canada (CANUTEC), and the Chemical Emergency Agency Service also maintain an around-the-clock emergency service for all chemical products:
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Copyright 2003-2007 Momentive Performance Materials Inc. All rights reserved. *Silbreak is a trademark of Momentive Performance Materials Inc. 134-114-00E-GL 11/07