Silbreak* Demulsifiersfor crude oil demulsification

Introduction

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.

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.

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.

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

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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 RSN(a) Viscosity (cSt) Flash Point(d) Density g/ml Silicone Molecular Silicone Cloud Demulsifier at 20°C (°C) at 20°C Weight (MW)(b) Point(c) (°C)

320 14.2 480 115 1.030 M 60

321 8.2 2000 135 1.030 H 40

322 15.3 720 99 1.050 M 58

323 8.7 1700 89 1.040 H 38

327 7.4 90 81 0.870 M N/A

329 14.9 1300 >93 1.047 M 60

400 7.0 2500 98 1.020 H N/A

401 8.0 5000 143 1.027 M 35

402 7.9 3300 110 1.027 H N/A

559 9.6 55 81 0.970 M N/A

589 8.7 1700 135 1.062 H 40

602 9.2 430 81 1.009 H N/A

603 7.0 1850 98 1.059 H 38

605 8.6 350 77 0.995 H 38

606 9.7 470 63 0.999 M 58

609 9.9 130 78 1.000 L 76

625 9.8 140 63 0.993 M 60

638 9.4 150 >80 0.962 H N/A

639 17.1 200 121 1.049 L 76

743 8.6 1700 120 1.027 H 40

1324 6.6 2400 98 1.020 H 38

1636 7.3 170 81 0.932 M N/A

1840 12.0 300 121 1.074 L <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) 229–237(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 25°C (d) Pensky-Martens closed cup ASTM D 93

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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 Silbreak demulsifier

Best is product E Best is Silbreak G

Second best is product A Second best is Silbreak B

Third best is product C 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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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 recom-mended 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 (API’s lower than 15°) Silbreak demulsifiers 329, 320, 321, 743, 1324, 603, 625, 400,

401 and 322

• For Medium Crudes (API’s between 15° and 25°) Silbreak demulsifiers 1840, 320, 323, 1636, 400, 401 and 402

• For Light Crudes (API’s 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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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 Dose (ppm) Separation of water in ml Water Interface %BS&W 5’ 15’ 30’ 1h 2h 3h Quality Quality

Current Control 250 18 38 39 40 41 41 1 1 2

Organic 1 100 8 10 16 21 28 30 1 1 17

Organic 2 100 18 22 25 29 31 35 1 1 14

Organic 3 100 9 22 28 30 30 31 1 3 13.6

Organic 4 100 20 25 28 32 36 39 1 2 11

Silbreak 329 100 1 3 5 6 7 8 4 2

Silbreak 320 100 1 3 5 6 7 8 4 2

Silbreak 321 100 2 7 8 10 12 13 2 2 10

Silbreak 322 100 3 5 7 8 10 12 4 4

Silbreak 323 100 3 5 14 18 18 18 3 3

Silbreak 327 100 5 8 9 9 9 9 2 3

Silbreak 329 100 3 4 9 10 12 15 2 2 10

Silbreak 559 100 8 10 10 11 12 14 3 3 8

Silbreak 589 100 5 6 8 11 14 16 3 3 3

Silbreak 602 100 5 9 12 14 15 18 3 3 13

Silbreak 603 100 3 4 8 10 15 18 4 3 10

Silbreak 605 100 3 7 10 11 12 15 5 3 14

Silbreak 606 100 5 6 10 11 12 14 4 3 10

Silbreak 609 100 2 3 6 9 10 12 4 2 14

Silbreak 625 100 10 11 18 20 21 21 2 2 12

Silbreak 638 100 0 2 6 8 8 9 3 4

Silbreak 639 100 0 4 6 8 9 10 4 5

Silbreak 743 100 1 3 12 15 15 15 4 5

Silbreak 1324 100 5 8 8 10 11 12 3 3 8

Silbreak 1636 100 5 6 8 12 14 15 3 4 7

Silbreak 1840 100 7 8 9 10 12 13 2 3 14

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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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 Dose Separation of Water Quality of Quality of %BS&W Relative (ppm 10mln 12h Water Interface Cost

Current Control 250 38 38 1 1 1.8 100

Organic 2 160

Silbreak 625 10 38 39 1 1 1.6 87

Silbreak 1324 17

Organic 2 140

Silbreak 625 10 39 40 1 1 1 87

Silbreak 603 35

Organic 2 120

Organic 1 30 32 34 1 1 3 89

Silbreak 625 50

Current Control 250 39 39 1 1 1 100

Organic 2 160

Silbreak 625 10 36 38 1 1 0.4 87

Silbreak 1324 17

Organic 2 140

Silbreak 625 10 36 38 1 1 0.2 87

Silbreak 603 35

Organic 2 144

Silbreak 625 9 34 38 1 1 3.4 78

Silbreak 1324 15

Organic 2 126

Silbreak 625 9 38 40 1 1 1.2 78

Silbreak 603 31

Organic 2 108

Organic 1 27 36 40 1 1 0.8 80

Silbreak 625 45

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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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 non existence 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:

Location Momentive Performance Materials Products All Chemical Products

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At sea Radio U.S. Coast Guard, which can directly contact Momentive Performance Materials at 518.233.2500 or CHEMTREC at 800.424.9300.

DO NOT WAIT. Phone if in doubt. You will be referred to a specialist for advice.

Copyright 2003-2007 Momentive Performance Materials Inc. All rights reserved. *Silbreak is a trademark of Momentive Performance Materials Inc.

134-114-00E-GL11/07

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