A Publication of BAKER PETROLITE CORPORATION

October 2006

Management Corner
by Jerry Basconi
Vice President and General Manager Worldwide Industrial Operations

Meeting the Challenges of Refineries Today

intensified as the trend continues for refineries to use more difficult to process and heavier crude oils. Baker Petrolite is committed to helping you meet your goals and priorities as you strive to make the most of existing refinery assets. We hope this issue of Downstream will help provide you with some information about the positive benefits of a few of our new programs and technologies. We discuss our new MILESTONE heater fouling control technology that helps reduce heater tube fouling rates and increase delayed coker unit profitability. The VisTec Visbreaker Technology Program has been designed by Baker Petrolite to maximize both conversion rates and operating run lengths of visbreaker units. The Program includes a range of additives that can control fouling and stability when visbreaking severity is increased, and complementary monitoring techniques that have been successfully used to predict stability and fouling tendencies for a wide range of feedstocks over a complete range of processing conditions. Also in this issue,

we provide an update on Baker Petrolite's plan to expand our Prepared to Respond Services, also known as P2R Services, a 24-hour, year-round, worldwide chemical response service for distressed hydrocarbon cargos. Our P2R Services program has been highly successful in the United States and Europe, and we are expanding globally to provide additional support worldwide. Baker Petrolite continues to bring you new and effective solutions. For more than 80 years, the petroleum refining, fuels, distribution and petrochemical processing industries have been the focus of our business. Our success depends on our ability to help you meet these new challenges every day. By introducing new technologies and providing a rapid response to your changing needs, Baker Petrolite can help you solve problems and improve operating margins. For more information about our innovative technology and services, please send us an e-mail to info@bakerpetrolite.com or contact your local Baker Petrolite representative.

Refiners need to continually search for new and improved products and services in order to better respond to evolving industry challenges. Fouling is a leading cause of diminished efficiency and productivity in refineries today, and associated maintenance costs in US refineries alone are in excess of $2 billion1 per year. The problem has

Argonne National Labs, DOE Report 1998/2002

VisTec Technology Maximizes Conversion without Accelerating Fouling or Reducing Run Lengths
Many visbreaker units that were originally designed to reduce residual feed viscosity are now being used to maximize gasoil yield. There are significant financial incentives for operating the unit in this way. For example, a 1% increase in gasoil yield from a typical 200-ton/hour unit can represent a U.S. $2 million increase in annual net profit. Fouling can become a problem, however, when running visbreakers to maximize distillate yield, so effective fouling control becomes essential. yields improve as visbreaker furnace temperatures are increased, this is usually accompanied by a fall in vistar stability as well increased furnace fouling. Unstable vistar also commonly causes increased fouling in the distillation section downstream of the soaker. This impacts the unit's throughput and leads to more frequent shutdowns for cleaning and decoking, which consumes much of the economic benefit generated by the increased distillate yields. The first monitoring method, the VisTec Stability Index (VSI), uses near infrared analysis to calculate vistar stability. The second, the VisTec Coke Index (VCI), uses a patented system to measure physical characteristics of the particulate coke in the vistar downstream of the furnace and soaker to calculate furnace fouling/coking tendency. VisTec additives also allow refiners to extend run lengths by mitigating fouling in critical parts of the visbreaker process. The monitoring technologies that are included in the VisTec Program allow refiners to maximize visbreaker conversion and run lengths within the natural constraints imposed by the feed that is charged to the visbreaker unit. VisTec additives are an integral part of the VisTec Program because they alter the chemical behavior of the feed to the visbreaker as it is processed, and loosen the natural constraints imposed by the feed. In effect, the VisTec additives expand the possible operating envelope, and the VisTec monitoring and software tools allow refiners to operate the visbreaker at the optimum economic position within this new, expanded envelope. Conversion and run lengths are therefore maximized most effectively by the combined use of a customized chemical treatment program that provides extra leverage to the benefits that can be obtained by VisTec monitoring.

Vacuum vistar/stripper Wash Grid Fouling

Furnace

Fractionator

Soaker

Heat Exchangers Pre-heat Exchangers Fouling Column Fouling

Furnace Coking

Figure 1. Fouling as a result of increased severity on visbreaking units

Fouling occurs as a result of thermal cracking reactions leading to the generation of coke particles in the furnace and deposition of unstable asphaltenes from vistar downstream of the furnace; fouling rates are dependent on operating severity (Figure 1). Although distillate

Baker Petrolite's VisTec Visbreaker Technology Program includes a range of additives that can control fouling and stability when visbreaking severity is increased, and two proprietary methods for rapid, reliable assessment of vistar stability and fouling control.

DOWNSTREAM

October 2006

Case Study: VisTec Visbreaker Technology Program Doubles Run Length of Unit and Avoids Two Costly Turnarounds
Problem:
A refinery in Asia suffered severe visbreaker furnace fouling that had limited the unit's run length to about one-and-ahalf months. The longest of the two previous runs lasted just 45 days before the furnace's skin point temperatures reached their maximum safe operating limit of 600C (1112F), and the furnace had to be shut down for cleaning.

in the furnace coil alloy. It was designed to bind with them to form a thin passivating layer on the coil surface to prevent the dehydrogenation reactions that caused accelerated fouling by masking the catalytic sites in the furnace coils' alloy matrix. Baker Petrolite then continued to use the VisTec software simulation to monitor the condition of the passivating layer and the

The

VisTec Program decreased the furnace fouling rate by 70 percent compared to the previous run. VisTec Program extended the run length by 100 percent (three months).

The

VisTec Program allowed the refinery to avoid two 15-day visbreaker shutdowns per year. The VisTec Program delivered an estimated annual net benefit of

The

650

Critical Skin Temperatures Trends

Before VisTec Program

600

Solution:
Baker Petrolite used a proprietary VisTec software simulation tool to analyze heater skin point temperatures over three separate runs and to isolate the true fouling rate from any temperature rises that were caused by changing operating conditions. The software showed that the rate of skin point temperature rise due to fouling was between 2.5 and 6C (4.5 to 10.8F) per day. Baker Petrolite then analyzed the results of the software simulation to identify the dominant fouling mechanism. The analysis showed that the furnace fouling rates were particularly high each time the refinery operators cleaned and restarted the furnace. This finding suggested that the decoking procedure had exposed metals in the furnace's alloy steel coils, which acted as dehydrogenation catalysts and accelerated coking rates. Having identified the dominant fouling mechanism, Baker Petrolite selected a VisTecTM additive that had a natural affinity for the metal elements that were present

T(C)

550 After VisTec Program 500

450

10

20

30

40

50

60

70

days of run
Heater skin temperatures before and after the VisTec Program compares the normalized skin point temperature data from two runs that processed the same feed type under equivalent operating conditions.

true fouling rate, and used this information to optimize and control addition of the VisTec additive.

approximately $2 million to the refiner. This is assuming a $70,000 visbreaker benefit per day.

Results and Benefits

As part of the VisTec Program, Baker Petrolite used the VisTec 600 additive to control accelerated fouling during the initial phase of plant operation. The Program performance delivered value in three key areas. VisTec is a trademark of Baker Hughes Incorporated. Note: This case history is presented for illustration purposes only, as the results may vary between applications.

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October 2006

Prepared to Respond (P2R) Services Continues to Expand Its Global Reach

For more than fifteen years, Baker Petrolite's P2R Services group has provided crucial solutions for a variety of fuel-quality issues to customers worldwide. The P2R Services group brings together a unique combination of bestin-class chemistry, one-of-a-kind logistical capabilities, and a dedicated customer service group to deliver tailored solutions to our customers. In order to meet fuel the Middle East, and to expand our support to owners of distressed cargoes in these parts of the world. We continue to expand P2R services to other parts of the globe. We have the expertise to provide emergency treatment to all types of fuel markets globally. Our goal is to continue to lead the way and to provide services to distressed fuel markets internationally, particularly in the Caribbean, Panama, Bahamas, Singapore, and China. Our customers rely on prevent compromising the quality of the resulting gasoline blend. Baker Petrolite has been called on in numerous cases to treat fuel ethanol with TOLAD 3224 Fuel Additive to neutralize acidity and protect ferrous metal surfaces that come into contact with the ethanol.

Biodiesel:
In Europe and the U.S., biodiesel is blended into the diesel pool to reduce emissions and to extend the diesel supply. Biodiesel can oxidize while in storage and destabilize in its pure form, as well as lower the stability properties of blended diesel fuel. Baker Petrolite has been called upon to treat this fuel in order to improve its storage stability and to ensure that blends of the biodiesel will work efficiently in modern diesel engines.

buyer's specifications, the P2R Services program provides 24-hour, year-round, worldwide chemical response assistance. Servicing cargo and tanker owners, and suppliers for onsite chemical treatment of fuel oil, crude oil, and distillate fuel cargoes, the P2R Services group routinely manages fuel concerns such as:
Pour-point

Silver Corrosion:
Baker Petrolite to provide these services throughout the world and we are committed to expanding our capabilities to meet their needs. In order to meet the U.S. gasoline demand, fuel is often imported from countries that do not have the same quality specifications as the U.S. One problem often encountered with these imported fuels is that they can be corrosive to silver, which is a key element in many fuel-sending units in U.S. automobiles. Resulting corrosion caused by the gasoline can quickly cause failures in these components and can lead to faulty fuel gauge readings. Baker Petrolite's TOLAD Silver Shield corrosion inhibitor is the most effective additive on the market to deal with this problem. Our P2R Services team has been able to quickly and efficiently resolve this serious issue for many fuel marketers in the past few years. Prepared to Respond and P2R are registered service trademarks of Baker Hughes Incorporated.

issues for transporting and offloading crude oils, distillate fuels, and fuel oil, including bunker fuel sulfide (H2S) safety problems for crude oil and distillate products issues for ferrous and non-ferrous applications and odor problems with crude oil, condensates, gasoline, and naphtha distillate specifications for CFPP, cetane, lubricity, and stability

New Treatment Opportunities

The P2R Services group has been treating several new and emerging fuel markets. Two of the latest of these markets are that for alternative fuels and silver corrosion.

Hydrogen

Corrosion

Ethanol:
Alternative fuels, such as ethanol and biodiesel, are capturing small, but increasingly significant, shares of the transportation fuels market in the US and abroad. Much of the ethanol needed to satisfy the United States' alternative fuels requirement is supplied domestically. However, an increasing percentage of ethanol is imported from abroad, most notably from Brazil. Since ethanol is generally quite corrosive, customers wanting to use it in gasoline blends must treat the ethanol with a pH-buffering corrosion inhibitor to

Mercaptan

Meeting

Expanding Global Capabilities

Baker Petrolite's July 2006 acquisition of DBM Oil Chemicals B.V., based in Rotterdam, the Netherlands, has allowed the P2R Services group to more effectively service customers in Europe, Russia, and DOWNSTREAM October 2006

MILESTONE Heater Fouling Control

Control Fouling and Increase Throughput in Delayed Coker Units
heavy crude oils
Reducing Reducing

coil de-coking costs heater fuel consumption

effective in independent pilot scale testing and in commercial applications in thermal conversion units worldwide. Customized MILESTONE fouling control additive solutions are developed using proprietary feedstock characterization, additive selection and dosage testing protocols. Measured feedstock characteristics are also compared to Baker Petrolite's extensive data base of conversion unit feedstock analytical information to help predict fouling potential in the unit and to determine the probable impact of candidate chemical solutions on heater fouling. Baker Petrolite engineers apply on-site experience with heater fouling control application technology to ensure implementation of effective fouling control solutions for each unit.

New MILESTONE heater fouling control technology from Baker Petrolite increases coker unit profitability by significantly reducing heater tube fouling rates. MILESTONE technology is a multicomponent fouling control additive solution that effectively interrupts the key fouling mechanisms identified for specific crude oil residual heater operations and feedstock characteristics. Recent applications of MILESTONE technology in delayed cokers have significantly extended heater run lengths and increased unit throughputs, while reducing the frequency and cost of coil decoking procedures.

Economic benefits, provided through application of MILESTONE technology, are calculated and tracked using a proprietary Baker Petrolite heater fouling economic analysis tool.

A Unique Approach to Heater Fouling Control

MILESTONETM fouling control additives were developed by Baker Petrolite to control heater fouling due to:
Thermal

degradation of oils destabilization

Asphaltene Catalytic

effects of feed metals and equipment surfaces of organic and inorganic solids

Precipitation

MILESTONE Technology Benefits

By controlling heater fouling rates, customized MILESTONE programs can significantly improve refinery profitability by:
Increasing

These additives have been proven

CSI Coker Stability Index

Furnace Feed Stability
1200
Canadian Refiner Furnace Feed Midwest Refiner Furnace Feed West Coast Refiner

thermal conversion unit throughput where unit capacity is heater limited the unit to maintain maximum conversion, where heater outlet temperatures are reduced to maintain target throughput during a run upstream crude units to process higher rates of lower-cost

1000 800 600 400 200 0

Allowing

Allowing

Intensity

50

100

150

200

250

300

CSI
The Baker Petrolite Coker Stability Index is used to evaluate stability of asphaltenes in unit feedstocks.

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October 2006

MILESTONE Heater Fouling Control Case History

Problem
A North American refinery was experiencing accelerated fouling in their delayed coker heater tubes. The fouling resulted in rapid tube skin increases of 5F (2.7C) to 29F (16C) per day. In order to prevent excessive tube skin temperatures, the four individual heater coils had to be cleaned by pigging on a rotating basis about once every 2 weeks. This required reducing production during each pigging operation. As the run progressed, a decision was made to drop the furnace outlet transfer line temperature by 8F (4.4C) in an attempt to maintain the tube skin temperature losses to 10F (5.5C) or less per/day.

losses on all tube passes were often less than 1F (0.5C) per day. After 40 days of continuous operation at normal production rates, all tube skin temperatures and the transfer line temperature remained within the normal range. By the 40th treatment day, the transfer line temperature had actually increased by over 50F (27.7C). It remained at that level for at least the next 38 days. During the entire treatment period, five pigging operations were cancelled, which increased unit production by over 1%. Note: This case history is presented for illustration purposes only, as the results may vary between applications.

P2R Services
Worldwide Headquarters
12645 West Airport Blvd. Sugar Land, Texas 77478 Tel: 1-800-231-3606 Fax: 281-276-7395

Baker Petrolite
Butaanweg 17 3196 KC Vondelingenplaat / Rt. Netherlands Tel: +31 297 523 574 Mobile: +31 6 50506800

A MILESTONE Program Can Work for You!

If your refinery is faced with a delayed coker unit heater fouling problem, a customized MILESTONE fouling control program can help increase unit throughput and improve unit profitability. Contact Baker Petrolite's fouling control experts for a complete evaluation of your unit operations and feedstock, and ask for their recommendation for a MILESTONE program specifically designed to prevent fouling in your heater.
MILESTONE is a trademark of Baker Hughes Incorporated.

Solution
Following a review of unit operations and analysis of the coker feed, Baker Petrolite recommended implementation of a MILESTONE fouling control program. Heater tube skin and transfer line temperature monitoring were continued to determine the effect of the fouling-control program.

Baker Petrolite Singapore

273 Jalan Ahmad Ibrahim Singapore 629150 Tel: +65 6861 0082 Fax: +65 6861 9252

Results and Benefits

During the first 30 days after beginning the fouling control program, temperature

Worldwide Headquarters 12645 West Airport Blvd., Sugar Land, Texas 77478 P.O. Box 5050, Sugar Land, Texas 77487-5050 U.S. Toll Free: 800-231-3606 Fax: 281-276-7395 Internet: www.bakerpetrolite.com
2006 Baker Hughes Incorporated. All rights reserved.

Customer Care: Concerns/Inquiries 1-800-872-1916 8:00 a.m. 5:00 p.m. (CST) Monday Friday Business Days

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October 2006