CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. CHAPTER 3.4 PROCESS SIDE ANTIFOULANTS: Once the mechanisms of fouling have been identified (See Chapter 3.3], then antifoulant chemistry specific to that problem can be selected to retard the fouling. There are five 65) basic types of antifoulant mechanisms: dispersants, inhibitors, metal coordinators, detergents, and coke retardants, Any one, or a combination of, the many types of antifoulant components may be necessary for maximum equipment protection, DISPERSANTS: Dispersants are the most common type of antifoulant component used to retard fouling in process equipment. Dispersants work on the existing particles in the system by surface activity which prevents the agglomeration of these smaller particles to form larger particles, The dispersant takes advantage of the system velocities which can maintain the smaller particles in solution, The formation of larger particles would result in deposition in low velocity areas of the system. Not all dispersants are alike. In fact, hundreds of molecules exist which exhibit various levels of dispersant activity. Appropriate chemistry should be selected based on the nature of the media being dispersed (i.e., FeS (iron sulfide), coke, polymer, etc.). Betz uses two tests to evalute dispersant chemistries, The FeS dispersion test simulates inorganic dispersion performance, The time noted below is related to how long the FeS will remain suspended in a hydrocarbon solution. Examples of various dispersant test results are listed below: Product Time (Hrs) A 7 B 18 c 0 D 24 E 6 F 48 G nm Product A is currently used in the Betz ProChem product line. Carbon black is used to simulate organic dispersion performance. As with the FeS test, the longer the time to settle, the better the product. ‘Time (Ars) cry 18 24 48 2 24 48 A B c D E FE G Page 1 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. The difference between these products in different fouling media is a key point. The order of performance for the FeS test was: G>)F>D> BY EDC For the carbon black test: A>G=D?)F=C>BDE Product G is better on FeS than carbon black. Product C showed no efficacy on FeS but fair impact on carbon black. Particle size studies have also been completed to document the benefit of dispersant chemistry. These studies compare the median population (Figure 3.4-1) size in an untreated and treated system over time, in the untreated system, the median size increases with time, revealing the agglomeration of the particles, In the treated system, the median particle size remains constant. The dispersant chemistry is effectively controlling the particle size to its original condition. The median volume (Figure 3.4-2) of particles in solution can be evaluated to compare the treated and untreated solutions. As before, the effectiveness of the surfactant is represented by the constant condition seen in the treated system over time, The reducing volume median in the untreated mode represents settling out of larger particles as they agglomerate in the solution, INHIBITORS: Free radical inhibitors are used to prevent free radical polymerization. For example, antioxidants react with free radicals which may be formed, thus terminating any chain propagation reactions which lead to the formation of long chain polymers. Free radical inhibitors (phenolic and aromatic amines) react in the following manner to remove radicals (this is just one of many pathways): om eacton Cy Hem OM em . : ra (Reaction 8 o — O'-« Me Ma (Reaction C) Page 2 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. Reaction A is generally non-reversible. The radical can be delocalized, spread over the benzene ring (B) and reaction can occur to destroy the radical (C). Reaction C is just one of many possible reactions to form deactivated radical products from the antioxidant. If Reaction A is reversible, and it can be to varying extents with some inhibitors, then regeneration of R* will be affected and no radical destruction will have taken place. To prevent oxidation of hydrocarbons, initiators and oxygen need to be eliminated. Generally, heat is a variable that cannot be eliminated or changed much. Radicals that are generated by heat would need to be scavenged by inhibitors. Even if oxygen is not present, the generation of radicals by heat can lead to polymerization of unsaturated hydrocarbons and thus fouling. Condensation polymerization, which is a general mechanism used for instance in the formation of nylon, can occur naturally in the hydrocarbon environment and can result in detrimental polymer formation. Condensation polymerization is the result of monomer molecules combining to form a larger molecule with the loss of simple molecules, usually water, The precursors of condensation polymerization reactions are certain carboxylic acids, some amines, pyrrole nitrogen compounds and, in general, hydrocarbons with aldehyde and ketone structures. When a condensation polymerization mechanism occurs, certain inhibitors can be fed to avoid the formation of the long chain polymers and to improve the overall operating efficiency. These inhibitors are generally not the same as those used to retard free radical polymerization. For example, in the fluid below, carbonyls were high and would react by the condensation polymerization mechanism. Additives A, B, and C are strong free radical inhibitors but were ineffective. Additives D, E, and F are condensation polymerization inhibitors and showed low gum levels and good performance. Furnace Oil (290 ppm carbonyls) Additives Gum Level (mg/50 ml) Blank 628 671 2630 «630 382 195, 345 mmoOmD As with the free radical inhibitors, performance varies depending on the additive and the fouling material. The proposed mechanisms of inhibition follow: Page 3 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. 1) Carbony! 70 20 R-C +YZ—»R-C +2ZH ~OH “oY Stable 2) Amine Compounds R’ - NH - R + XOH—*X - NH-R + ROH Stable 3) Pyrrole Nitrogen CH3-€ = CH3 + YZ—®CHS - N 1 H - CH3 + ZH Inhibitors are represented by ¥Z and XOH Page 4 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. METAL COORDINATORS: Metal coordinators chelate metal ions which may be present in the system, The metal complex formed from this reaction is stable and will not catalyze free radical reactions and subsequent polymer formation, Not all metal deactivators are the same and performance varies, The Betz ProChem Metal Deactivator outperforms the best open market product, Du Pont DMD, when tested in the presence of iron, copper, or cobalt. METAL DEACTIVATORS (ML OXYGEN IN 5 MIN.) COPPER BLANK 105 BETZ PROCHEM 2 DU PONT DMD 4 IRON BLANK 68 BETZ PROCHEM 18 DU PONT DMD 81 COBALT BLANK 47 BETZ PROCHEM 0 DU PONT DMD 21 The Betz research test measures the amount of oxygen that reacts with a hydrocarbon fluid. The lower the oxygen (02) generated, the better the performance of the metal deactivator. CORROSION INAIBITORS/DETERGENTS: Corrosion inhibitors are used in those areas where corrosion contributes to fouling or where detergent performance is beneficial. Detergents are surface active agents which can effectively break the bond between equipment surfaces and the foulant material. Some filmers used for corrosion inhibition exhibit these properties. Even though corrosion may not be a problem in terms of metal loss, even a small amount of corrosion contributes bulk to the deposit. Corrosion also introduces metal ions into the hydrocarbon which can catalyze polymer formation. COKE RETARDANTS: High fluid temperatures coking (600°F) cannot be addressed effectively with conventional temperature dispersants and other chemistries. When the problem area is in the high temperature range, certain types of dispersants are effective antifoulants, if amorphous coke deposition is the problem. The following test results from the Betz ProChem Dual fouling apparatus illustrates differences between chemicals at 900°F fluid outlet temperature. Page 5 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. % Protection Product 900° F Testing A 81 B 60 c 47 D 61 The Betz ProChem Thermoflo product line includes Product A chemistry for high temperature dispersancy. At furnace skin temperatures of 1100-1400°F, catalytic coking can occur. In this two step process, the aromatic hydrocarbon constituents undergo thermal cracking and dehydrogenation on the hot tube metal surface. The metal carbides formed by this step are highly reactive and will catalyze the formation of coke. Sometimes dispersants can be effective at controlling the migration of this coke. However, the use of unique Betz coke retardant chemistry can stop the formation of the coke. The Betz product reacts with the metal surface at the skin temperatures noted above. This film interferes with the diffusion of carbon into the tube metal. Thus, the metal carbide cannot form. The test data below is from the Betz High Temperature Fouling Apparatus (HTFA): Chemistry % Protection 1 9 w 55 aw 3 Vv 58 v 67 ‘The range of performance illustrates the variation in the ability of different chemistries to effectively film the metal tube surface at temperatures above 900°F, Betz ProChem formulas currently utilize chemistry V. PRODUCT FORMULATION: The test methods which have been presented and the various inhibitor packages that Betz ProChem uses will result in customized treatment programs. For instance, an antifoulant will generally consist of a blend of inhibitor chemistry which can take advantage of several features currently attainable by our product line, The result is specific chemistry for specific mechanisms: Page 6 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. Problem Product Characteristics Inorganic Deposition Inorganic Dispersant Organic Deposition Organic Dispersant Peroxy Free Radical Polymerization Free Radical Polymerization Inhibitor Oxygen Contamination Oxygen Scavenger Vapor Phase Polymerization Vapor Space Polymerization Inhibitor Carbonyl Polymerization Condensation Polymerization Inhibitor Pyrrole Nitrogen Polymerization Condensation Polymerization Inhibitor Metal Catalyzed Polymerization Metal Coordinator Diene Polymerization Diene Polymerization Inhibitor Furnace Deposition High Temperature Dispersant Variable Fouling Rates Tests For Unreacted Residual The impact on the customer of these features can be dramatic: = Reduce dispersant/detergent demand for a more cost-effective program - Easier to manage the program - Better program performance - Reduce chemical treatment costs = Yield maximum fouling control = Prevent costly overfeed or poor performance = Gives you a safe recommendation PROGRAM INITIATION: Antifoulants are generally applied in concentrations between 5 and 100 ppm based on the process flow rate, Generally, the protection afforded by an antifoulant increases with concentration, as shown by Figure 3.4-3. The shape of this curve and the maximum level of protection possible is different for each antifoulant and each fouling application, If economics permit, the antifoulant should be fed at a concentration slightly greater than the minimum required dosage. If the initial antifoulant dosage is too low, the level of protection it provides may not justify its continued use. Antifoulant pretreatment is often recommended to increase protection at the start of a run when fouling occurs most rapidly. It can be accomplished using various techniques beginning prior to start-up or during the first few weeks of operation. Normally, pretreatment methods are customized according to the individual situation. Pretreatment prior to start-up can be done by dipping, spraying, or filling each shell with a dilute antifoulant solution immediately following cleaning, When these methods are not possible, then an increased (normally double) antifoulant feedrate during the first few weeks of operation may suffice. Antifoulants are designed to reduce the fouling rate on clean equipment surfaces. They are not designed for clean up. Therefore, any antifoulant program should begin immediately after equipment is cleaned with pretreatment recommended as described above. Sometimes the opportunity to treat a dirty system arises. Ideally, it is better to postpone an antifoulant evaluation until the exchangers can be cleaned. However, plant personnel may feel that it is advantageous to start the application to a dirty system. It Page 7 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. should be pointed out to plant personnel that our antifoulants are not designed to clean up fouled equipment. In some cases however, there is a possibility of limited cleanup at several times normal treatment dosages. There is also the possibility that antifoulant performance with a dirty system may not be as good as with a clean system. Antifoulants applied to fouled equipment can hold existing heat transfer levels or reduce the rate of heat transfer decline, but certainly there is very little chance that improvements will be observed. TYPICAL APPLICATIONS There are many areas in the hydrocarbon processing industry where antifoulants have been used successfully. The main treatment areas are discussed below. In a refinery, the crude unit has been the focus of attention, especially because of the recent tremendous increases in fuel cost. Antifoulants have been successfully applied at the exchangers, downstream and upstream of the desalter, on the product side of the preheat train, on both sides of the desalter makeup water exchanger, and at the sour water stripper. Hydrodesulfurization units of all types experience preheat fouling problems. Among those that have been successfully treated are reformer pretreaters processing both straight run and coker naphtha, desulfurizers processing catalytically cracked and coker gas oils, and distillate hydrotreaters. In one case, fouling of a Unifiner stripper column was solved by applying a corrosion inhibitor upstream of the problem source. Unsaturated and saturated gas plants (refinery vapor recovery units) experience fouling in the various fractionation columns, reboilers and compressors. In some cases, a corrosion control program along with the antifoulant program gave the best results. In other cases, antifoulants alone were enough to solve the problem, FCC Unit exchanger fouling, both in the preheat and the slurry loop, has also been corrected by the use of antifoulants. While these are the primary areas in which antifoulants have performed effectively, there are many other fouling problems that can be solved through the proper application of antifoulants, with an increase in plant operating profit. JUSTIFICATION The increased profit possible with antifoulants varies from application to application. It can include an increase in production, fuel savings, maintenance savings and other savings from greater operating efficiency. The classic case is the refinery crude unit where preheat exchanger fouling requires that the crude unit furnace be fired at a higher rate to produce the desired furnace outlet temperature. In a typical case, the increased energy required would be about 27,000 BTU per 1,000 barrels for each degree (Fahrenheit) of temperature loss, Assuming that fuel costs from $2.00 to $6.00 per million BTU, fouling can increase fuel costs as high as a million dollars a year. For example, if a 100,000-barrel-per-day (B/D) refinery loses 60F of preheat temperature in six months, about $660,000 additional would be spent on fuel over the six-month period Page 8 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. (assuming a fuel cost of $4.50 per million Btu). This is money needlessly lost. Production losses can rise even higher. For the furnace-limiting case where a refinery is operating at maximum throughputs, exchanger fouling requires a corresponding reduction in throughput to maintain the same furnace outlet temperature, Generally, throughput must be reduced about three barrels per day per 1,000 barrels of charge for each degree of furnace inlet temperature loss. In the example cited above, approximately $1,600,000 would be lost in six months (assuming $1.00 profit per barrel of crude oil). Antifoulant Justification Sample The incremental fuel cost is a function of the energy demand increase caused by fouling and the replacement cost of the fuel. Cost of Fouling = Excess Fuel Consumed x Fuel Cost jurnace Efficiency This logic assumes, however, that the excess furnace heating capacity is available. If this is not the case, then production losses must be considered. Cost of Fouling = Excess Fuel Consumed x Fuel Cost Furnace Efficiency + Production Loss x Throughput Incentive Other penalties include equipment maintenance which can increase with cleaning frequency. This cost should include the actual cleaning expense plus the energy and/or production lost during maintenance. Cost of Maintenance = Cost of Cleaning (S) + Fuel Loss x Fuel Cost Furnace Efficiency + Production Loss x Throughput Incentive ‘Additionally, fouling can potentially result in equipment loss and costly catalyst damage. ‘The following example illustrates a simple energy-justified crude preheat program. The graph (Figure 3.4-4) shows the performance of the Betz ProChem Program. The benefits calculations below illustrate an ROI of 166%. ECONOMICS OF fi-1 INLET TEMPERATURES (Adjusted for Exchanger Cleanings) Current Run Average Temperature = 488.7°F Clean Exchanger Adjustment =9.8°F Current Run Adjusted Average Temperature = 478.9°R Previous Run Average Temperature = 466.1°F Page 9 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. Onit Data: Nominal Charge Rate 200 MBPD APL = 33.0 (301.2 Lb/BBL) Cp = 65 BTU/Lb/°F Furnace Efficiency = 80% Energy Cost $5.50/MMBTU/Hr Calculation M CP AT) in Year Time x (Estimated Cost/Furnace Efficiency) (200 M) (301.2) (365) (.65) (478.9 - 466.1) x (5.50 x 10 - 6 / .80) $1.258 MM/Year RETURN ON INVESTMENT FOR BETZ PROGRAM Return on Investment = Energy Savings - Chemical Cost x 199% ‘Chemical Cost Energy Savings = $1,258,000/Year Chemical Cost: Basis 75 GPD Ave, Unit Cost $17.25/Gallon Cost = 75x 17.25 = 365 = $472,200/Year ROL = 1,258,000 - 472,200 x 190% 472,200 a 166.4% The second example illustrates the benefit of an antifoulant program in terms of a capacity increase on an HDS Unit. The problem consisted of a Distillate HDS Unit where heat transfer had been lost and pressure drop was a serious constraint in the preheat system. After 3 to 4 months, the charge was reduced and a shutdown was required after about 5 months. A polymerization inhibitor previously used showed minimal improvement in performance. Characterization of the two major feeds revealed that the bromine number was extremely low and filterable solids was extremely low. The low bromine number indicated that free radical polymerization inhibitors would most likely not be appropriate. The presence of carbonyls in significant levels implied that a different polymerization mechanism should be addressed. Tests with various additives were performed using the Betz ProChem reflux fouling equipment. The Betz ProChem additive performance was tremendous in reducing washed gum levels over the no additive situation. It should be pointed out that testing of free radical inhibitors showed essentially no benefit on this feedstock. The program was initiated in the plant and the run was extended to well beyond six months with minimal increase in pressure drop and no charge rate reduction, No premature unit shutdown was required to clean the preheat exchangers as a result of the charge rate reduction. Page 10 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY Betz Proces FIGURE 3.4-1 Particle Size Population Median (Micrometers) 0 15 30 FIGURE 3.4-2 Volume Median (Micrometers) (07/88) Chapter 3.4CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. Estimated Program Benefit ‘Charge Penalty 0-3 months 0 MBPD 3-4 months 6 MBPD (Avg.) Value of Capacity $B Performance Savings = 360 MB/5 months or $360,000/5 months Chemical Cost = $165,000/5 months Savings to Plant $195,000/5 months Return on Investment 360,000-- 166,000 100% = 118% 5 Page 11 (05/8 Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4(99/20) we saydeqy ‘uy ‘SJBOWOUD Ss80014 7198 - BBG! I BAIND DjSHEJOBIBYD SOUBWOJJeg JUBINOSUY eve ainbi4 UO1}BIJUBOUOD jUBINOSNUY U0N}9e}01d % ‘OU “E[eoTuIeyD ssV001g 29H XINO JS TWNYSLNI YOd TVILNAGGIANODre rrdeqy “buy ‘syeoqway9 sss0014 2199 ~ 961 IYBUAdOD (98/20) (imonae-25d) 89/¢ “DN STVOWGHO $S300Ud 7130 wopesedo jo keg ose 00s osz 002 Ost OL OS 0 lOSb O94 OLY 08+ qO6Y 00S uny uney weYdold 208 ‘BNOACld aunyesodwia) yOu] |-H Pez!/ewsON UU] ‘speoTuIey) sse00rg 230g -v'E BUND XINO SSM TVNUGLNI 4od IVILNGGIAGNOOCONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. METAL COORDINATORS: Metal coordinators chelate metal ions which may be present in the system, The metal complex formed from this reaction is stable and will not catalyze free radical reactions and subsequent polymer formation, Not all metal deactivators are the same and performance varies, The Betz ProChem Metal Deactivator outperforms the best open market product, Du Pont DMD, when tested in the presence of iron, copper, or cobalt. METAL DEACTIVATORS (ML OXYGEN IN 5 MIN.) COPPER BLANK 105 BETZ PROCHEM 2 DU PONT DMD 4 IRON BLANK 68 BETZ PROCHEM 18 DU PONT DMD 81 COBALT BLANK 47 BETZ PROCHEM 0 DU PONT DMD 21 The Betz research test measures the amount of oxygen that reacts with a hydrocarbon fluid. The lower the oxygen (02) generated, the better the performance of the metal deactivator. CORROSION INAIBITORS/DETERGENTS: Corrosion inhibitors are used in those areas where corrosion contributes to fouling or where detergent performance is beneficial. Detergents are surface active agents which can effectively break the bond between equipment surfaces and the foulant material. Some filmers used for corrosion inhibition exhibit these properties. Even though corrosion may not be a problem in terms of metal loss, even a small amount of corrosion contributes bulk to the deposit. Corrosion also introduces metal ions into the hydrocarbon which can catalyze polymer formation. COKE RETARDANTS: High fluid temperatures coking (600°F) cannot be addressed effectively with conventional temperature dispersants and other chemistries. When the problem area is in the high temperature range, certain types of dispersants are effective antifoulants, if amorphous coke deposition is the problem. The following test results from the Betz ProChem Dual fouling apparatus illustrates differences between chemicals at 900°F fluid outlet temperature. Page 5 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.4