CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. CHAPTER 3.6 CORROSION INHIBITORS - (NEUTRALIZERS) INTRODUCTION In order to meet the basic requirements of a good neutralizer, the product undoubtedly has to be economical but it also must have particular qualities beyond neutralization strength. These important qualities can be described in terms of the following product capabilities: 1. Initial Condensate Point ([.C.P.) Protection 2. pH Buffering 3. Contribution to Fouling Potential 4. Relative Volatility for Distillation 5. Low Hydrogen Sulfide Reactivity 6. Low Salt Deposition Potential 7. Hydrochloride Salt Thermal Stability ‘The need for each capability varies and depends on where the corrosion occurs and the amounts of HCl organic acids and HS present. One fact is certain, if these capabilities are satisfied, the basic requirements of providing a uniform pH profile without undesirable consequences from neutralization will likewise be satisfied. Initial Condensate Point (1.C.P) Protection ‘The region where moisture first condenses in a crude unit overhead system is one of highest acid concentration where the highest corrosion rates are seen, In a crude tower overhead treated with ammonia, the pH of the water just starting to condense is lower than the final pH of that water draw from the overhead accumulator. pi levels as low as 3 4.5 have been documented in the same system that reported a final condensate pil of, 6- 6.5. ‘The factors influencing the low pH at the initial condensate region are complex and not completely defined. Where ammonia is the neutralizer, the primary factor believed to cause the low pH in the initial condensate is that the concentration of the ammonium chloride is highest where water first condenses. Figure 3.6-1 illustrates this point well. The pH of an ammonium chloride solution is inversely proportional to NH4Cl concentration. Thus as more and more water condenses, the NH4Cl concentration decreases and pH increases. ‘An absolutely essential requirement for a neutralizer is the ability to control pH at 5.5 to? during the first stages of water condensation. Our neutralizers are effective at achieving initial condensate protection because they are formulated to condense before or at the water dew point, Moreover, our neutralizers are formulated with amines that have high water/hydrocarbon partitioning coefficients. Boiling point consideration alone is not sufficent to assure adequate pli levels in the initial condensate region. The Betz Process Chemicals’ Vapor-Aqueous Equilibrium Ratio, Kva is of primary importance in predicting the relative condensation profile for Page 1 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.6CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. different neutralizers. Kva is defined as the concentration of a neutralizer in the vapor phase divided by its concentration in the aqueous phase. Kva values are determined by our Research Department. ‘The Kva for hydrogen chloride is very low, approaching zero, Therefore, a low Kva value for a neutralizer assures neutralizer condensation and effective acid neutralization at the first signs of water condensation. A neutralizer Kva value of less than one indicates good initial condensate protection, a value of one provides fair protection and above one provides poor protection, Notice that ammonia has a very high Kva compared with some commonly used neutralizing amines, Therefore, all of the amines shown in Table 3.6-I will provide better corrosion protection at the initial condensate point than does ammonia. pH Buffering Close control of pH in a crude unit overhead condensing system is important for three reasons. Close control of pH reduces system fouling tendency, increases corrosion protection, and assures the optimum neutralizer costs. A buffer is a material which, when added to a solution, resists changes in the pH of the solution, We are concerned about pH control in the 5-7 range. Therefore, for our purposes, buffering is a measure of an amine’s ability to lessen pH fluctuations in this range. The shape of an amine's titration curve is an indication of its ability to buffer. ‘The lower the concentration of natural buffers (HS organic acids and CO.) in the overhead condensate water, the more important it is to neutralize with buffered amines. We will continue to emphasize the need for buffering in sweet systems, Figure 3.6-2 illustrates the buffering effect of 1S versus pil. As the pil of a process condensate increases, the amount of fA, that dissociates to H+ and HS- increases also. ‘Above 6 pl, the dissociation curve is the steepest. Consequently, small changes in pi occur with correspondingly large changes in the degree of hydrogen sulfide dissociation. This explains why it is difficult to elevate pl above 6-6.5 in a sour system. For a given pil increase in this region, a proportionally larger amount of neutralizer must be fed. Figure 3.6-2 is based on a given amount of HS in water, Our Research Department has measured the distribution ratio of HS between hydrocarbon and water. Table 3.6-1 Shows that the hydrocarbon-water distribution ratio (concentration of fyS in the hydrocarbon phase divided by the concentration of H2S in the water ‘phase) is approximately three. Therefore, if pH is increased in the sour system, hydrogen sulfide from the more voluminous hydrocarbon phase transfers to the water phase, which in turn increases the buffering effect, in turn requiring the use of more neutralizer. Fouling Potential All other factors being constant, the fouling potential of a system is proportional to the amount of acid and to the amount of neutralizer injected to neutralize that acid. Let's take a look at a system where ammonia is used for neutralization, Ammonium chloride, a product of neutralization, exists only as a solid. If system temperature is Page 2 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.6CONFIDENTIAL, FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. sufficiently low (or system pressure sufficiently high), ammonia and hydrogen chloride will condense according to the reaction below NA13 (gas) + ACI (gas) = NHC! (olid) Figure 3.6-3 illustrates this. At a given pressure on the ¥ axis, lowering the temperature increases the tendency to form solid ammonium chloride. Figure 3.6-4 shows this same phenomenon represented in a slightly different but more useful way. In Figure 3.6-4, the vapor pressure of the ammonium chloride is expressed in terms of the product of the partial pressure of ammonia and the partial pressure of hydrogen chloride. This is possible because ammonium chloride exists in the vapor phase as discrete molecules of ammonia and hydrogen chloride, If, at a given partial pressure (concentration) of hydrogen chloride and a given temperature, the partial pressure (concentration) of ammonia is increased, then the tendency for solid ammonium chloride to form increases. In a sour system where ammonia is used for pH control, ammonia will react with the amount of hydrogen sulfide that dissociates to H* and HS” in the aqueous condensate. Sufficient ammonia must be available to neutralize the H*, whether it is supplied from the hydrogen chloride or hydrogen sulfide. Then, in order to control pH in a sour system, the concentration (partial pressure) of ammonia must increase compared to a sweet system. Therefore, as the partial pressure of ammonia increases because of the increase of HS concentration, the tendency for solid ammonium chloride to deposit in the system incréases, Also, demand for ammonia can be increased by the organic acids which are significant in most systems, Obviously, increasing the pH at the accumulator in any system by increasing the feed of ammonia also increases the concentration of ammonia (partial pressure) and, therefore, increases, the likelihood of forming NH4Cl which in turn, increases the likelihood of NA4CI fouling. Relative Volatility for Distillation Relative volatility is the tendency of the unreacted neutralizer to change into a vapor and distill overhead. Boiling point is the best measure of neutralizer volatility. Volatility is important when introducing a neutralizer into the crude charge. The unreacted amine should vaporize and condense in the distillation tower top or overhead for proper dew point pH control. Overhead hydrocarbon distillate typically boils between 100-375°F, Our neutralizer products are designed to end up in the overhead (if unreacted) as evidenced by the boiling range of our products (less than 375°F), ‘ydrogen Sulfide Reactivity ‘The reactivity of ammonia with hydrogen sulfide has been discussed earlier. It is important to discuss the reactivity of hydrogen sulfide with various amines. Please refer to Table 3.6-I. which qualifies the HS reactivity of individual amines at one atmosphere pressure, As you can see, amines A through E all have some reactivity with hydrogen sulfide between 100 and 200°F, Amines A through C have a relatively high reactivity with f,S. If we develop an equilibrium amine bisulfide vapor pressure curve for amines A through C, these curves will be located below the ammonium bisulfide curve in Figure 3.6-5. Thus, for certain amines depending on their individual properties, Page 3 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.6CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. amine bisulfide formation is quite likely at temperatures below 20°F. Notice (Table 3.6-Ill) that amine E does not have a formation tendency until 100°F is reached. ‘Amine F does not react with hydrogen sulfide at all, it also should be pointed out that at higher partial pressures the formation temperatures increase. Therefore, depending on the system pressure, one could expect formation of certain amine bisulfides at temperatures above 20°F. Once the amine bisulfide is formed, it can dissociate as the partial pressure is lowered or the temperature is increased. Table 3.6-IV shows the dissociation temperature of various amines at atmospheric pressure. As you can see, generally the amines start to dissociate {form the free amine and f1,S) at temperatures between 100 and 167°F. Complete dis- sociation occurs at temperatiires between 300 and 40°F. The relative reactivity of neutralizer products as well as the ultimate dissociation point must be discussed in terms of neutralizer injection point. 1, OVERHEAD INJECTION POINT Potential fouling and underdeposit corrosion may result before the water condensate point if the neutralizer reacts with HS in “dry” areas. The less reactive a neutralizer is with hydrogen sulfide, the less likely the amine bisulfide will form in these areas, After water condensation, the salts are usually dissolved and washed away. ‘The amount of hydrocarbon present in a crude unit, can be 30-100 times more than the amount of water present. Therefore, it can be possible for the amine salts to form and to be removed from the system via a product draw. This effectively increases the neutralizer consumption because the amount of neutralizer removed with the hydrogen sulfide is not available for acid neutralization, Even more disasterous is the possibility of downstream fouling or corrosion. The amine bisulfide could also return with the reflux and cause deposition, and corrosion problems in the top trays of the crude unit, 2, REFLUX INJECTION POINT HS reaction at low tower top temperatures can cause underdeposit corrosion from salt deposition, This feed location can be intolerable for sour units with low operating temperatures. Heavy liquid salts will accumulate on trays with the chloride salts. Even if the chloride salts are dispersible, the slow sweeping velocity across the trays may not be sufficient to disperse the high salt loading (sulfide plus chlorides). Underdeposit corrosion becomes very likely. Moreover, the salts that are dispersed may be drawn off into the top pumparound to attack pumparound exchangers. Since the salts have some tendency to absorb water vapor, wet chloride salts can combine with wet sulfide salts and an aqueous phase with high chloride and sulfide concentrations form which promotes corrosion. ‘Also as illustrated in Table 3.6-IV, the amine bisulfide stability temperature is higher than its formation temperature. Consequently, salt formed in the overhead condensing system can migrate to lower trays and remain stable at temperatures as high as 40°F. This increases the likelihood of problems in areas where hydrogen sulfide reaction with amines are not expected. Page 4 (05/88) Copyright 1988 - Betz Process Chemicals, Inc, Chapter 3.6CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. sufficiently low (or system pressure sufficiently high), ammonia and hydrogen chloride will condense according to the reaction below NH (gas) + HCI (gas) = NH4CI (solid) Figure 3.6-3 illustrates this, At a given pressure on the ¥ axis, lowering the temperature increases the tendency to form solid ammonium chloride. Figure 3.6-4 shows this same phenomenon represented in a slightly different but more useful way. In Figure 3.6-4, the vapor pressure of the ammonium chloride is expressed in terms of the product of the partial pressure of ammonia and the partial pressure of hydrogen chloride. This is possible because ammonium chloride exists in the vapor phase as discrete molecules of ammonia and hydrogen chloride. If, at a given partial pressure (concentration) of hydrogen chloride and a given temperature, the partial pressure (concentration) of aromonia is increased, then the tendency for solid ammonium chloride to form increases. In a sour system where ammonia is used for pH control, ammonia will react with the amount of hydrogen sulfide that dissociates to Ht and HS” in the aqueous condensate. Sufficient ammonia must be available to neutralize the *, whether it is supplied from the hydrogen chloride or hydrogen sulfide. Then, in order to control pH in a sour system, the concentration (partial pressure) of ammonia must increase compared to a sweet system. Therefore, as the partial pressure of ammonia increases because of the increase of HS concentration, the tendency for solid ammonium chloride to deposit in the system incréases. Also, demand for ammonia can be increased by the organic acids which are significant in most systems. Obviously, increasing the pH at the accumulator in any system by increasing the feed of ammonia also increases the concentration of ammonia (partial pressure) and, therefore, increases, the likelihood of forming NH4Ci which in turn, increases the likelihood of NHC! fouling. Relative Volatility for Distillation Relative volatility is the tendency of the unreacted neutralizer to change into a vapor and distill overhead. Boiling point is the best measure of neutralizer volatility. Volatility is important when introducing a neutralizer into the crude charge. The unreacted amine should vaporize and condense in the distillation tower top or overhead for proper dew point pHi control. Overhead hydrocarbon distillate typically boils between 100-375°F, Our neutralizer products are designed to end up in the overhead (if unreacted) as evidenced by the boiling range of our products (less than 375°F). Hydrogen Sulfide Reactivity ‘The reactivity of ammonia with hydrogen sulfide has been discussed earlier. It is important to discuss the reactivity of hydrogen sulfide with various amines, Please refer to Table 3.6-Ill. which qualifies the HS reactivity of individual amines at one atmosphere pressure, As you can see, amines A through E all have some reactivity with hydrogen sulfide between 100 and 200°F, Amines A through C have a relatively high reactivity with HS. If we develop an equilibrium amine bisulfide vapor pressure curve for amines A through C, these curves will be located below the ammonium bisulfide curve in Figure 3.6-5. Thus, for certain amines depending on their individual properties, Page 3 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.6CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. CHARGE FEEDPOINT Most neutralizers do not react with HS at crude tower flash zone conditions where the temperature is in excess of 650°F. Thus, most of the neutralizer will react with the hydrogen chloride generated by hydrolysis and go out the tower bottom. Certain neutralizers are more volatile under flash zone conditions and a thermally stable salt is not formed. This type of product would offer the advantage of pH elevation in the upper section of the tower where water condensation may occur. Salt properties are the key to obtaining dew point pil protection without salt build-up. Low Salt Deposition Potential Salt formation is the result of any acid + base (neutralizer) reaction. Obviously, the salt should not promote corrosion as a consequence of agglomerating/adhering to the metallic surfaces and picking up water and developing an acid concentration cell below the deposit. L AMINE HYDROCHLORIDE We evaluate our neutralizers on the basis of four areas in order to give an overall non-fouling rating or salt deposition potential. These areas are: - Amine Salt Hydrocarbon Dispersibility - Hygroscopicity = Melting Point - Actual Experience Factor a, Amine Salt Hydrocarbon Dispersibility Amine-HCl salts are evaluated and rated according to their tendency to adhere to a metal surface. Salt dispersibility is checked between 200° - 450°F in a laboratory apparatus under severe conditions. Our laboratory test device ratings correlate with plant data, Products that have a low deposition tendency in the test unit also deliver good plant performance. See Table 3.6-V. b. Hygroscopicity All amine salts are hygroscopic to a degree, which means they can absorb water vapor. The hygroscopicity rating establishes the rate of water vapor pick-up as well as the total amount picked up for that time period, A material that quickly liquefies because of water absorption and becomes very fluid will receive a very positive rating in the hygroscopicity category. In other words, a salt can absorb water and (1) promote underdeposit attack if hygroscopicity is low; or (2) become fluid and very dispersible if hygroscopicity is high, Table 3.6-VI gives some hygroscopic ratings of selected amines, As you can see amine D is the best and NA4Ci is the worst. Page § (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.6CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. c. Melting Point Melting point may be a possible indication of fouling tendency because we generally expect a liquid to be more dispersible. However, some liquid salts can adhere to metallic surfaces causing fouling. In Table 3.6-V neutralizer D melts below 75°F yet is very sticky and adherent. Therefore, melting point alone is not always an indication of non-fouling tendency. ‘The melting point of a substance is defined as the temperature at which the liquid and solid phases exist in equilibrium with one another, If additional heat is added to a solid-liquid mixture at the melting point, no rise in temperature will occur until all the solid has been converted to liquid. (This is uot to be confused with hygroscopicity which can lead to the appearance of melting.) With respect to our neutralizers, they are blended amines and therefore have broader, less defined melting points. Many of our products have amines incorporated into the formula that produce amine HCI salts with low (200°) melting points. In the presence of hydrocarbons, melting point depression of the salt is produced by the introduction of the hydrocarbon impurity. Therefore, amine salts will exhibit lower melting points in the crude tower than in a controlled isolated laboratory environment, 2, AMINE HYDROGEN SULFIDE With respect to amine bisulfide fouling, our approach is to use amine products that have the lowest hydrogen sulfide reactivity in sour systems, Further, the primary products for sour units have liquid salts which are readily dispersible. Hydrochloric Salt Thermal Stability Several Betz ProChem neutralizers can be fed to the crude for charge neutralization. ‘The neutralizer-HCl salts are thermally stable at the elevated temperatures experienced in most crude units. Thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC) have shown that the hydrochloride salts from our neutralizers are thermally stable to at least crude unit flash zone conditions. This has been confirmed by in-plant chloride balance studies using neutron activation analyses. These studies have shown that the amine hydrochlorides largely survived vacuum column temperatures, as most of the chloride salts end up in the vacuum bottoms stream. Refer to the Betz Process Chemicals, Inc. papers “Better Crude Unit Corrosion Control By Adding Proprietary Neutralizers to the Column Feed" and "Neutralizing Amines for Crude Unit Corrosion Control ~ An Update" (copies included in this manual), Page 6 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.6CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. TABLE 3.6 -1 AMINE BOILING POINT VS. VAPOR-AQUEOUS EQUILIBRIUM RATIO, Kva AT ATMOSPHERIC PRESSURE Boiling Neutralizer Point, OF Kea Ammonia -27 19.0 A 248 1.0 B 262 04 c 273 2.0 D 275 1.0 £ 320 On F 325 3.0 G 329 03 a 338 0.08 TABLE 3.6-1 ‘Aydrogen Sulfide: QS in Oil Added Found in Water on HS in Water 352, n 261 2.87 680 158 522, 33 760 170 590 3.46 12 249, 863 3.46 1787 407 1380 34 2508 588 1920 33 4070 1040 3030 291 Hydrogen sulfide partitioning between oil and water Page 7 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.6CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC, TABLE 3.6-It 28 REACTIVITY OF VARIOUS AMINES ‘AT ONE ATMOSPHERE PRESSURE 200°F 150° 100°F A Some All Al B Some Au All c Some All All D Some Some All E None None Slight F None None None TABLE 3.6-1V DISSOCIATION TEMPERATURE °F, OF VARIOUS AMINE HYDROCARBONS AT ONE ATMOSPHERE PRESSURE Complete Start Dissociation A 167 392 B 100 aut c 113 392, D 122 302 Page 8 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.6TABLE 3.6-V CONFIDENTIAL FOR INTERNAL USE ONLY BETZ PROCESS CHEMICALS, INC. AMINE SALT HYDROCARBON DISPERSIBILITY VS. MELTING POINT Amine Hydrochloride Amine Hydrochloride Neutralizer Salt Melting Point, °F ‘Hydrocarbon Dispersibility A 181 Very Good B 140 Very Good c <75 (Liquid) Very Good D <75 (Liquid) Poor z 550+ Good F 367 Fair G 354, Poor a 401 Very Good TABLE 3.6-VI RELATIVE HYGROSCOPICITY OF VARIOUIS NEUTRALIZERS ACI SALTS UNDER AMBIENT CONDITIONS Time Neutralizer Start 15 Minutes, 45 Minutes 4 Hours 24 Hours A Dry bry Dry Dry Some wetting B Dry Wet Very Wet Very Wet Very Wet © Dry Liquid Liquid Liquid Liquid D Wet Liquid Liquid Liquid Liquid Crystals E Dry Some Some Mostly Liquid Wetting Wetting Liquid NHACI Dry Dry Dry Dry Very Slight Wetting Page 9 (05/88) Copyright 1988 - Betz Process Chemicals, Inc. Chapter 3.6oe saydeqy ‘Qu} ‘sfBOIWaYD $se901 219q - BBBL INBUAdOD (98/20) lOBN SB pesseidxy IOH JO Wdd Wdd 00S8S Wdd 0S8S WddS8S WddS8S Wdd S8’s t L L —1_____— J2117/S®1OW OL 201 Ol »-OF H eluowwy Aq JOH JO U0l}ezI/e1]NAN “ou “s[pormey ssa00rg ZIG XINO SSA TYNULNI YOK TVILNGGIANOD 1-9'e aunbiygre soideqy “oul ‘syeoweyd #800014 2199 ~ BBGL WOUAdOD (88/20) ayesuepuo) oul Jo Hd 68 se oe ss 4 so 9 ss ¢ st 7%, 0% +g oo = ° 3 or m4 a 3 109 3. B x ° joe oor uUOT}eIIOSSIg eply[Nns ussoipAH a] ‘s[eoyareqa e8000Ig Ted XINO GSA TVNYSLNI YOd TVIANAGIANOO 2-9 ainbi4CONFIDENTIAL, FOR INTERNAL USE ONLY [Betz Process Chemicals, Inc, Figure 3.6-3 Pa psi 10 10-8 Solid 1 -1974 Vapor 10 105 (C) 80 85 90 95 100 105 110 CF) (176) (194) (212) (230) Temperature Ammonium chloride vapor pressure. (07/88) Copyright 1988 ~ Betz Process Chemicals, Inc. Chapter 3.6CONFIDENTIAL POR INTERNAL USE ONLY Figure 3.6-4 Betz Process Chemicals, Inc. (psi2 107 10° Kp=(PNH3)(PHCI) NH3(g)+HCi(g) <= NH4CI 10° 85 90 95 100 105 110 (°C) (185) (203) (221) = (°F) Temperature Ammonium chloride salt formation. (07/88) Copyright 1988 - Betz Process Chemicals, inc. Chapter 3.6ge saideqg ‘OU ‘SIROIWAYD SS9201q 719G — BEL WU6UAdOD (98/20) d seeibeg ose ost ooL 1 00¢e 1__ oor ose ooe _—___1 —1__ (WLV) d DOT seinssojd Jodea yes wnjuowwy TVILNAGGIANOD