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Paper No.

00446

CORROSION

2000

R E F I N E R Y C H E M I C A L CLEANING: C R I T E R I A FOR DETERGENT S E L E C T I O N

Chris Spurrell Chevron Products Company 324 W. El Segundo Blvd. El Segundo, CA 90245 Mialeeka Bibbs Chevron Products Company 324 W. El Segundo Blvd. El Segundo, CA 90245 Abstract Mechanical equipment in the oil processing industry can operate for years between shutdowns. During this time there is often a tendency for scale, debris and sludges to form within this equipment. During the shutdowns these fouling materials have to be removed before mechanical work or even entry can be allowed. Detergents have been developed to speed the cleaning and decontamination of equipment. These detergents alone or in combination with other chemicals such as oxidizing agents have reduced the need for caustic and acid washing of refinery equipment. Detergents, however, can interfere with the subsequent reprocessing of the oil removed. And they may have adverse effects on the refinery's water effluent system. Several criteria for detergent selection and field test methods are presented. Introduction Oil processing equipment has long been known to accumulate fouling materials while in operation. These can range from polymeric sludges, sometimes called coke, to various corrosion derived materials, such as iron sulfide, and scale forming mineral deposits formed from calcium, magnesium, barium, and silica among others. There are also components of the crude such as benzene which can permeate the equipment and must be removed to meet OSHA requirements. And, of course, flammability must be reduced. For many years the techniques of caustic washing and acid washing have addressed many of these concerns. However, the generation of hazardous wastes from high or low pH washes has prompted the development of detergent cleaners which can remove or mitigate many of the expected foulants without generating hazardous or "listed" wastes. Further, a careful selection of detergent qualities can provide the

Copyright
@2000 by NACE International.Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE International, Conferences Division, P.O. Box 218340, Houston, Texas 77218-8340. The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarily endorsed by the Association. Printed in U.S.A.

99 HARVEY UNIVERSAL INC. in order to provide a rational basis for selecting a cleaner to use during shutdowns. In order to arrive at a detergent selection criteria the Chevron E1 Segundo refinery embarked on a series of tests.: Harvey's Power Grease & Tar Cutter . Energy W.best cleaning during turnarounds while minimizing troublesome reprocessing of the recovered oil and water solutions. Many detergent formulations have been offered to the petroleum processing industry as "environmentally friendly heavy duty degreasers. how much oil and grease will the detergent put into the effluent water? How toxic is the detergent to the microbes in the effluent system's activated sludge plant? How much foam will be generated in the drains and effluent system. Gobble CHEMCO: Citrifresh. APC DIANA INDUSTRIES: HS-1000. Jump Start. these terms are hardly quantifiable. Knockdown. EP680AC. GRAINGER: Ball-o-Solv. Fairly objective measurements like the Hydrophilic / Lipophilic Balance fail to answer the necessary questions of cleaning ability and subsequent processing impacts. mostly field expedients. Citrus EP680AC WEST PENETONE: Citrikleen HD-CH UNITED LABORATORIES: Zyme flow RAMCO: Pac Attack PROCTOR & GAMBLE: Joy DOW: Fantastik CHEMISOLVE: US 1600 CA RECYCLING CENTER: D . especially in the Induced Air Flotation (IAF) systems? 4) 5) SOAPS TESTED JAYNE PRODUCT: JPX." While noble in word and goal. R. The main concerns of widespread use of detergent / surfactant materials around the refinery were: 1) 2) 3) How well does it clean? How much emulsion will it form in the effluent system? In contact with other hydrocarbon streams. Synthene. Red Eye. Energy Plus Red.

emulsion forming tendency. The majority of cleaners had an emulsion band of 2 mL.) Rather. While we never investigated the active materials in these cleaners. EMULSION TEST For an emulsion test the emulsion thickness was measured after the above-mentioned test. FOAM TEST For a foam test a 100 mLs graduated cylinder was filled with 90 mLs of tap water. This test is not believed. etc.g. CLEANING ABILITY TEST In order to rank the various soaps cleaning ability we coated thin carbon steel strips (corrosion coupons) with residuum (from SJV crude) and then exposed the treated strips to a 160 Deg. Oil and Grease contribution in the presence of hydrocarbon. The test displayed Oil and Grease values ranging from 1000 to 6000 PPM (See Figure 5). OIL & GREASE TEST After the above visual measurements were taken we transferred the test solutions to a 4 oz sample bottle which was left undisturbed for one hour.We chose these detergents to represent a broad spectrum. and toxicity towards Refinery activated sludge bio organisms. enzyme-based cleaners as well as commercially available household cleaning formulations. None of the cleaners in this test were effective at 1%. this test is designed to use Refinery acclimated bio organisms in order to evaluate a given chemical's potential to cause an Effluent Treatment Plant upset. TOXICITY TEST The toxicity test used was developed at the E1 Segundo Refinery to test the toxicity of Refinery chemicals towards their activated sludge. their advertising and characteristics indicated that we had examples of citrus or terpene based cleaners.9 mL of soap. The test used consisted of a Freon extraction followed by an infrared absorbance using the Foxboro Oil and Grease analyzer. and the initial amount of diesel used. The solution was allowed to settle for 10 minutes before measurements were taken. The cylinder with the solution was stoppered and shaken vigorously ten times. 2 mLs of diesel fuel. and an oxidation / reduction potential indicator. F stirred water solution which contained 10% of the various soaps. to correlate with traditional effluent toxicity tests which are performed on higher organisms (e. A one mL sample was taken from the middle of the bottle and tested for Oil and Grease content. The residuum percent removal (by weight) was then recorded. The toxicity test is based on respirometry wherein a bioculture is sealed in a flask along with nutrients. The chemical cleaners exhibited emulsion ranges from 2 to 3 mL (See Figure 4). The Redox indicator changes color (blue to pink to clear) with the microorganisms' consumption of the oxygen. Only the terpene based cleaners were effective under these conditions (See Figure 1). and 0. Only Q and C retained their effectiveness at 5% (See Figure 2). test chemical. Foam ranged from 0 to 35 mL (See Figure 3).. Daphnia. Rainbow Trout. EFFLUENT IMPACT TESTS In order to evaluate the impact on Refinery effluent systems and potential environmental impact we measured the soaps foaming tendency. These cleaners were then tested at 5% and 1%. or intended. The test flask oxygen uptake is . which was equal to the blank.

then compared to that of a blank. disposal and reprocessing options. Toxicity or inhibition is measured by the additional time taken by the organisms to consume oxygen compared to the blank. We used two different concentrations 1. CONCLUSION We were able to find quantifiable differences in the cleaners tested. can be used to select the best detergent for and oil processing facility's needs. Because of the differences in foulants.000 PPM and 10. we focused only on those cleaners." As a result there is environmental impact information but no cleaning performance information on products. Likewise other cleaners have been shown to remove benzene even though their effectiveness on heavy oils is poor by comparison. which was not addressed. effluent treatment facilities.0-% soap solutions is shown in Figure 7. which relate to both the cleaning effectiveness and environmental impact. Another aspect. These differences. these tests are best viewed as a point of reference from which an intelligent detergent selection can be made. was the ability of the cleaners to reduce LEL and benzene. which can truly function as "heavy duty degreasers. The toxicity test was based on a scale of 0 to 6 with zero being best (See Figure 6). E V A L U A T I O N SCOPE LIMITATIONS In this study.000 PPM for the chemical dosage. . We have field experience here going back several years that the terpene based cleaners are effective at removing benzene when added during a steam out or water wash. which may be effective as general purpose cleaning agents. while we performed tests on a variety of cleaners. pH The pH of 1.

Little effed ci 10% i i m C 2 1.eL E A N I N G AB IL IT Y 3.20% or less effedrNeat 5% 0 .5 Raling 3.Abo.Top Cleaners .60-95% effective ~ 5% 1 .e 95% at 5 2 .5 0 Q C J K O R A P H D E F M B G L N I U V S T DE T E R GE NT FIGURE 1 .5 1 0..5 3 2.Cleaning Ability T op 5 Chemi cal el eaner s 120% 100% 80% m O 60% 40% 20% 0% m O K J Q C DE T E R GE NT FIGURE 2 .

.4 E v 25 20 E I.Average Emulsion .AVE RAGE FOAM 35 30 A .I...5 v 2 1.5 21 0..5< 3 2.Average Foam AVE R AGE E MU LS ION 3.5 0 Z Z DET E RGE NT FIGURE 4 . 15 0 1o 0 ~- ~ Z CL ~ ~ ~ 0 -- DE T E R GE NT FIGURE 3 .

AVE RAGE OIL AND GR E AS E 7ooo T 6OOO ASO00 1~ 4000 v m 3000 2OOO 1000 Z DE T E R GE NT F I G U R E 5 .00 Best 6 = Worst 0 = I1• .Toxicity Test .00 1.~ | m iniB 4.00 R E B I A F P D N L G C O H Q M J K X 0 I~ DE T E R GE NT FIGURE 6 ..00 5.A v e r a g e Oil a n d G r e a s e T oxi ci ty T es t 6.00 O 2.00 3.00 0.

.5 10 ~j: Q.pH 11. 9.5 9 8.pH .5 7 S M H V J Q T D C B O I N L A P R K F G E DE T E R GE NT FIGURE 7 .5 11 10.5 8 7..