The Risks of HF and Sulfuric Acid Alkylation by Philip Myers, Technica Inc. Krishna Mudan, Technica Inc. Henry Hachmuth, Phillips Petroleum Co. ABSTRACT ‘A comprehensive study of the acute risks posed by current refinery alkylation processes was performed to address concems of the refining industry and the public. The AIChE Chemical Process ‘Quantitative Risk Assessment (CPQRA) technique was utilized to evaluate the Phillips design hydrofluoric acid alkylation process, as well as a process using sulfuric acid as the catalyst. In order to evaluate each of the processes on an equal basis, acute risks due to acid transportation and regeneration were included. The detailed quantitative analyses indicate that there are inherent risks associated with the operation of both sulfuric acid and HF alkylation facilities. Various design modifications were explored and shown to significantly reduce the risk to the public. In the analysis it was also demonstrated that the risks are sensitive to numerous other factors, many of which are site specific. The study indicates that both hydrofluoric acid and sulfuric acid alkylation processes are capable of being operated within risk levels that are generally considered to be tolerable by society.INTRODUCTION The use of hydrofluoric acid (HF) in industry has come under much scrutiny during the past few years. There has been concern on the part of the general public as to the potential hazards that HEF may pose to communities. Public officials and regulatory bodies, in response to the public’s concems, have focused their attention on the use of hydrofluoric acid in processing. The petroleum industry has been the focus of much of the attention, as many refineries utilize an HF alkylation process for increasing the production of gasoline. The refining industry has responded to some of the concerns regarding the use of hydrofluoric acid through the recent API background paper (1]. The Phillips Petroleum Company, being the licensor of one of the primary HF alkylation unit designs, sought to better understand the risks associated with the Phillips design HF alkylation unit. Technica Inc. has worked with the Phillips Petroleum Company to assess the risk associated with the Phillips process design and a sulfuric acid alkylation process as well. BACKGROUND A great deal of activity preceded this risk study. The "Goldfish” spill tests conducted by industry in Nevada (1986) confirmed that hydrofluoric acid did pose a potential hazard, and provided some data for modeling use and validation [2]. In October of 1987, the Marathon accident at ‘Texas City promoted further concern on the part of the public. At this point, regulatory bodies began discussing banning or severely restricting the use of hydrofluoric acid. The South Coast ‘Air Quality Management District (SCAQMD) was particularly active and began evaluating proposed Rule 1410 which suggested such HF bans or restrictions for areas in California within its jurisdiction [3]. In addition, HF alkylation units were coming under scrutiny in New Jersey through the Toxic Catastrophe Prevention Act (TCPA) [4]. Activity at the federal level suggesting restrictions on the use of HF, and possibly a universal conversion in the petroleum industry to sulfuric acid alkylation technologies, further prompted the analysis. STUDY OBJECTIVES ‘The primary objective of the analysis was to scientifically evaluate alkylation process risks, to understand the facts about alkylation as currently known, and to convey this information to regulatory bodies, the public, and industry. This was done to ensure that any decisions made or regulations passed would be on an informed basis. This analysis was also undertaken to quantitatively evaluate the risks associated with the HF alkylation process and the Phillips design alkylation unit, as well as the risks associated with a similar process using sulfuric acid as the reaction catalyst. More specifically, the study was to (1) evaluate the risks from the Phillips design unit and HF alkylation process as presently designed and operated (the baseline risk), (2) evaluate the risks from an alkylation process technology using a sulfuric acid catalyst, (3) identify the major events contributing to risk from the Phillips design alkylation unit, (4) identify and evaluate means of reducing the likelihood or consequences of release for the Phillips design unit, thereby reducing the risk, (5) compare the risks from the HF and sulfuric acid processes studied, and (6) compare the risks to acceptability criteria. One additional objective was to identify the major sensitivities that affect the risks posed by an alkylation process. ‘The goal of this study ‘was, therefore, not to promote the use of the Phillips design HF alkylation unit, to promote the3 use of HF alkylation in general, or to suggest that sulfuric acid alkylation technologies are unsafe. ‘The main objective was to cause industry, regulatory bodies, and the public to become informed and aware of the issues surrounding HF alkylation and make any decisions based on sufficient information. Part of this goal was to create an awareness of the technical need for each process, each technology, and each facility to be evaluated and assessed individually and specifically, rather than in a general mandate. SCOPE OF THE STUDY “The total process risk was evaluated in this analysis for each of the alkylation processes studied. ‘That is, all associated acute risks of various types were taken into account for both the HF and sulfuri¢ acid alkylation processes. For the Phillips design unit, the following were analyzed in evaluating the process: Hydrocarbon feedstock storage and transfer to the unit HF delivery by tanker truck HE storage and transfer to the alkylation unit Reaction On-site HF regeneration Fractionation Similarly, to allow for comparison of the alkylation processes on an equal basis, the following were included in the analysis of the sulfuric acid alkylation process: Hydrocarbon feedstock storage and transfer to the unit Sulfuric acid delivery and spent acid trucking Sulfuric acid storage and transfer to the alkylation unit Reaction Off-site acid regeneration Fractionation Although other alternatives to trucking acid exist, this is one common mode of transportation. Tt should also be noted that for truck transportation associated with either alkylation process, the risk of fatalities due to chemical release and that due to collisions and traffic accidents were ‘considered, although the type of risk is slightly different. What is meant by this is that the perception of risks due to chemical release and due to collision are indeed different. Much less publicity generally surrounds any collision deaths in comparison to deaths attributable to chemical releases. Yet, deaths do result from collisions of acid carrying trucks and should, therefore, be included in an acute risk analysis of each total alkylation process. Inclusion of these risks is especially useful as a means of putting the two types of hazard (collision and spill) into perspective. In addition, both flammable and toxic risks were analyzed for each process. The risks calculated in this study are those to the off-site population only. No attempt was made in the analysis to include on-site risks and other operator safety issues. The emphasis of the study was to carry out an analysis on typical facilities. In order to accomplish this goal, two representative facilities were studied for each process, one site being situated in an urban environment and the other in a rural setting. In this way, the approximate risk could be calculated for sites representative of those in the U.S. and other parts of the world.4 It is important to recognize that certain aspects of the total process risks were not in the scope of this work. ‘The first of these considerations is that chronic risks were not included in the analysis. These risks are due to long term exposure to hazardous materials, causing adverse health effects. Additionally, no environmental risks were quantified. This does not infer that these issues are not important. Rather, the scope of this study was to evaluate acute risks only. In addition, changes to the design of the sulfuric acid alkylation unit for risk mitigation were not addressed. APPROACH The analysis was carried out using the comprehensive Chemical Process Quantitative Risk ‘Analysis (CPQRA) methodology, as recommended in the AICHE publication "Guidelines for Chemical Process Quantitative Risk Analysis" (5), to present the facts as currently understood. Figure 1 depicts, through use of a flow diagram, the risk analysis methodology. Risk is a measure of the impact of an adverse event upon the surrounding population. While a consequence analysis gives the potential magnitude of an accidental release, it is insufficient for the evaluation of risk to the public. Risk is a measure of the magnitude of release, the likelihood of given hazardous events, and the resulting impact on the surrounding population. CPQRA is, therefore, best suited for a study such as this as it provides a tangible basis for making engineering and planning decisions. ‘The hazard identification phase of the project was carried out in two steps. The first step involved specification of potential leaks and ruptures of all equipment items due to various causes. Next, a Process Hazards Analysis (PHA) was utilized to supplement the failures previously identified, Experts in HF alkylation and in sulfuric acid alkylation processes, as well as professional process plant risk analysts and hazard identification team leaders, formed the identification team. Through use of the PHA, failures and concems very specific to these processes were identified. A full representative set of failures was thus created by combining those identified in the first and second steps of the hazard identification phase. The releases identified ranged from minor leaks to catastrophic ruptures. Several hundred failure cases were developed in total to represent possible failures and resultant chemical releases. The failure rates and probabilities were generally taken from Technica’s proprietary data base of industry historical experience. ‘This was supplemented in some cases by other techniques, such as fault tree and event tree analysis, to allow for the features of the specific process equipment studied and the particularly harsh service environment. Technica’s software package SAFETI (Suite for the Assessment of Flammable, Explosive and Toxic Impact), was utilized to carry out the discharge and development zone calculations, the dispersion or consequence calculations, and evaluations of the impact of each event on the off- site population. In performing these calculations, the site specific meteorology, ignition sources, terrain, and population distributions were utilized. The consequences modeled include thermal radiation, explosion overpressures, and toxic dispersions, At the time of this study, the model did not include the effects of oligomerization or reaction of the acid with ambient moisture. It should be noted, though, that the models used in this study were validated using data from the "Goldfish" experiments [6]. In modeling the toxic effects of HF or sulfuric acid releases, the5 Figure 1. Simplified Flow Diagram for Risk Analysis6 probit approach was utilized, which relates the toxicity of a chemical to exposure concentrations and durations (the toxic dose). It was considered highly important that the CPQRA technique be utilized to evaluate the two alkylation processes, Due to the controversy surrounding the use of HF, a comprehensive technique was determined necessary to provide a fair and credible evaluation. In addition, the technique is accepted in countries throughout the world and, in some cases, forms the basis for process safety management and regulation. MAJOR FACTORS POTENTIALLY AFFECTING THE RISK A number of parameters were fixed during the course of the study. These factors are specific to the processes being studied and the siting of the process units. One of the important factors considered was the population distribution used for each site. To evaluate the risks fairly, and to "bound" them, two sites were developed. One of the sites was representative of a densely populated urban area, and one of a more sparsely populated rural location. In addition, other parameters representative of such areas were fixed. These parameters included the surface Toughness, the humidity, the atmospheric conditions, the "buffer zone" between the alkylation unit and the community, the terrain, and potential ignition sources. Additionally, the toxicity of each of the acids certainly affects the outcome of the analysis, Toxicological data from several sources were reviewed to determine toxic levels of HF (6] and sulfuric acid. In these experiments, laboratory animals were exposed to a range of concentrations over various time periods, From the data, a "probit" relationship was derived which relates the toxicity of the chemicals with exposure concentration and duration. There is a level of, uncertainty associated with this toxicological data and the probits derived, as with any such response data. Utilizing these probits, it is possible to determine the probable mortality response for various levels of sulfuric acid or HF acid concentrations and durations. For a one hour exposure, the predicted mortality responses are estimated as follows: Sulfuric Acid HF Acid Response Concentration (ppmv) Concentration (ppm). Near 100% fatality 350 1600 90% fatality 270 1280 50% fatality 200 990 10% fatality 150 760 1% fatality 110 610 Fatality threshold 60 3701 ‘The data indicates the toxicity of HF and sulfuric acid are comparable on a mass basis, Probits were also developed for sulfur dioxide and sulfur trioxide, for use in assessing risk from a sulfuric acid regeneration plant. ‘An additional factor of significant importance in the analysis involved aerosol formation. Under typical alkylation conditions, HIF in the reactor is maintained under pressure as a liquid above its normal boiling temperature. In the event of an atmospheric release, a portion of the HF would vaporize to gas. ‘The rapid formation of gas bubbles acts to break up the remaining Liquid into a fine acrosol. As previously discussed, Technica’s in-house dispersion model was validated by the HF "Goldfish" Nevada test site results. The model predicted aerosol formation as was witnessed in the Nevada experiments, and closely modeled the downwind dispersion for the releases and site conditions. In contrast to hydrofluoric acid, sulfuric acid has a very high boiling point and is maintained at temperatures well below the boiling point in alkylation units. A release of pure sulfuric acid (as found in acid storage facilities) does not present any significant downwind toxic impact. However, this may not hold true for agitated mixtures of sulfuric acid with isobutane, as found in the sulfuric acid alkylation unit. Isobutane is a volatile hydrocarbon that, if maintained above 1i°F, would partially vaporize upon release and could lead to the formation of a sulfuric acid aerosol, Some experimental data on sulfuric acid indicates that it requires only a modest amount of energy to form aerosols. Test data with pure materials indicate the degree of supetheat Gemperature in excess of the boiling point) has a profound effect on aerosol formation. Extension of the Brown and York work [7] to the hydrocarbon/sulfuric acid mixtures indicated, in theory, that sulfuric acid mists could possibly result from releases in the alkylation process where hydrocarbor/sulfuric acid emulsions exist. As there currently is no available data on sulfuric acid/isobutane mixtures from rigorous experimental tests, a range of risks were studied allowing for complete sulfuric acid aerosol formation in one case, and no aerosol formation in another. ‘THE STUDY BASIS ‘A 15,000 bpd alkylation unit was utilized as the basis for analysis of the HF and sulfuric acid alkylation processes studied. Although larger and smaller units of each type can be found, the 15,000 bpd unit was taken as a fair representation of existing units. For the Phillips design HF alkylation unit, only make-up acid is required as regeneration of the acid takes place on-site. It was determined that approximately 0.1 pounds of HF are required per barrel of alkylate produced to replace trace amounts of HF consumed in the process. This resulted in a study basis of 12 tank truck deliveries of fresh acid per year. A 750 mile transportation route was utilized, as often the Phillips design units may be located quite some distance from an HF supplier. Off-site regeneration of spent sulfuric acid was taken as the basis for the transportation risk analysis. Additionally, the acid transportation evaluated was by tank truck to a regeneration facility 45 miles away. An acid consumption rate of 42 pounds per barrel of alkylate was used jn the analysis. ‘Thus, whereas typical HF alkylation processes require about 12 tank truck deliveries per year, the typical sulfuric acid process may require 14 to 15 tank trucks per day.8 The actual usage of acid varies considerably from facility to facility for both HF and sulfuric acid processes, It is dependent upon a number of factors including the type of feedstock, the amount of water in the process, etc, Therefore, the actual acid consumption rate should be obtained for the study of any individual site. The acid make-up or consumption rates presented above have been taken as reasonable, all factors considered. PRESENTATION OF RISK RESULTS Two types of risk results are generally calculated. ‘The first of these is referred to as individual or geographic risk. ‘The individual risk refers to the combined risk level at any given location from all causes originating from a hazardous operation over a one year period. It is presented as the chance of fatality per year to any individual at that location. It is often referred to as geographic risk as the basis for its presentation is exposure for twenty-four hours per day, 365 days a year. Individual risk contours are often overlaid onto a geographic map of the area under study. This allows for visualization of the risk. The contours are presented for decreasing orders of magnitude, Although individual risk contours do not indicate the number of people exposed, they do give an indication of the location of the most exposed individuals and sensitive populations such as schools and hospitals. Another measure of risk is societal risk, which takes into account the possibility of multiple casualties resulting from accidents. It is often presented in the form of a plot of the cumulative frequency (F) of multiple fatalities versus the number of fatalities (N). These are referred to as F-N curves or graphs. The left axis of the plot may be thought of as the frequency of exceedence, or the frequency of surpassing a specified number of fatalities. F-N curves provide useful insight into the nature of risks from a facility to the community as a whole, or society. It may indicate that most of the risk from a hazardous operation comes from high frequency events with low impact, low frequency or rare events with a potentially high impact, or from something in between these. In addition, societal risks can be expressed in the form of various risk indices. The summation of risks from each accident provides an annual predicted fatality rate. This provides an easily understood, single value number to present the acute risk. It is quite useful in comparing various engineering design options. A ranking of the events that contribute most to the total risk is also very useful. It allows the analyst to focus attention on the most critical accidental failures and facilitates efficiency in studying prevention or mitigation options for those events. RISK ASSESSMENT RESULTS ‘The base case study of the Phillips design HF alkylation unit considered it as currently designed today and found at existing sites throughout the world. The results of our analysis of this unit in an urban setting showed that 64% of the risk of off-site fatalities resulted from failures in the reaction section of the unit. Additionally, 34% resulted from risk posed by the on-site HF acid regeneration, and about 2% from the hydrocarbon feedstock storage. The off-site risks from the acid unloading operation, the HF storage, and from fractionation were all much lower in comparison.9 ‘The individual risk posed to the nearest off-site areas was approximately a one in 10,000 chance of fatality per year. That is, the 10* risk contour approximately reached the site boundary. The individual risk from the unit fell to a one in one hundred million (10*) chance of fatality per year at a distance of about five miles, Although the risk levels extended to about the same distances for the rural case, far fewer individuals would acwually be exposed to risks from the HF alkylation unit. ‘The societal risks from the base case unit in a heavily populated urban setting would not be considered acceptable in the Netherlands (which has established a societal risk acceptability criteria). The societal risks from the base case unit in a rural setting would be tolerable by the Netherlands standards for an existing unit, but would require risk reduction before permitting new construction. Also, it was determined early on that the toxic risks completely dominate the total risks from the process. For the more likely events, typical toxic dispersion distances of about 400 feet from the point of release were found. The worst case toxic releases (from the acid coolers) under unfavorable atmospheric conditions resulted in predicted dispersion distances of several miles. Ranking of the highest risk contributors from the base case analysis facilitated the focusing of further modeling efforts and engineering design changes where the greatest risk reduction could be achieved. The top two risk contributors, resulting in over 50% of the baseline risk, were leaks iin the acid coolers. This was primarily due to the large inventory of HF that could be released. The reactor section accounted for more than 60% of the total risk. In addition, a large portion of the total risk was due to a relatively high predicted failure rate of the HF acid pump to regeneration. In general, basic goals in reducing risk relate to accident prevention, release detection and response, mitigation of the consequence of release, and emergency response. Centering on the highest risk contributors from the base case analysis, changes in the design were evaluated that addressed these issues and affected the likelihood of release as well as the consequences and impact on the surrounding off-site population. This part of the study involved conceptual engineering design changes that would reduce the risk, cost benefit analysis not being a consideration. A number of options were explored. The first of these was to add remotely activated emergency shutoff valves in key locations in the unit, to increase the chance of isolation as well as to decrease the time to isolation given an accident. In addition, the unit can operate minus the HF pump to the rerun column. Therefore, this option was explored, as the pump leak frequency was high relative to most equipment failure rates. Another conceptual idea of compartmentalizing the reactor was evaluated. In this option, the unit would operate in the same general way, but the inventory of the unit would be divided into separate working compartments, In this way, the inventory available for release given a failure decreased dramatically. An acid ‘dump system was also considered for emergency situations. Given a failure in the HF containing equipment, the dump system could be remotely activated, sending the HF to a remote dump storage vessel. Through utilization of such a system, the maximum release duration could be limited. In total, five options were considered as variations from the base case analysis of the Phillips design HF alkylation unit as follows: (1) installation of remotely activated shutoff valves at the inlet to the regeneration section, (2) removal of the acid circulation pump to regeneration, (3)10 items 1 and 2 above, plus division of the acid section of the settler into four compartments each with independent reactor legs and acid return lines, (4) items 1 and 2 above, plus installation of an acid dump system for emergency use, and (5) inclusion of all of the above mentioned items in a new modified design. Figure 2 depicts risk reduction achieved through the various options studied. It should be noted that inclusion of all of the risk reducing measures yielded approximately a 90% reduction in societal risk for the current unit design. Additionally, the individual risk for the modified design unit was greatly reduced, with the chance of fatality at about one in 100,000 per year at the site boundary, or an order of magnitude risk reduction. An individual risk level of 10 at the site boundary would normally be considered tolerable in the Netherlands for an existing facility, The F-N results for the modified urban case indicate that some additional risk mitigation should still be taken, though the results for the rural modified design case indicate that additional modifications may not be warranted. ‘The risk of the sulfuric acid alkylation unit and process is uncertain. Whereas flammable risks are fairly well defined, it is unclear whether any off-site toxic effects would result from the sulfuric acid alkylation unit. Sulfuric acid is toxic, but is not volatile in a pure form. As the sulfuric acid forms an emulsion with isobutane (which is volatile) in the process, a sulfuric acid mist could potentially result. If such an aerosol or sulfuric acid mist docs indeed form, then off- site toxic effects could result. In contrast to this, if the acid mist does not form, then a sulfuric acid alkylation unit is not likely to pose off-site fatal toxic effects. Some limited test data is available on the formation of aerosols (or lack thereof) with various pure materials and some mixtures. Most of the test data available to date does not result from the use of materials and experimental conditions representative of emulsions in a sulfuric acid alkylation process. Some of the available data indicates that an aerosol may not form. Yet, other test data indicates that such an aerosol formation may occur. Technica believes that none of the tests conducted to date conclusively support the formation of an aerosol, nor do they rule out the possibility. A more rigorous series of experiments can be envisaged to study whether or not an aerosol is formed. Therefore, all risk calculations for the sulfuric acid alkylation unit studied were carried out for an aerosol and a non-aerosol case, to "bound" the risks. As was done for the Phillips design HF alkylation unit, the sulfuric acid unit was evaluated in both an urban and a rural setting. On the basis that sulfuric acid/hydrocarbon mixtures would completely form an aerosol, the individual risk of fatality at the fenceline was about one in 10,000 per year. This is approximately the same level of risk as that calculated for the base case Phillips design alkylation unit. The 10° risk contour for the sulfuric acid unit stretched to just over two miles from the unit, The total societal risk for the sulfuric acid alkylation unit aerosol case (in an urban environment) was found to be comparable to the risks posed by a Phillips design HF alkylation unit. For this case, the sulfuric acid unit risk was almost entirely from releases of toxic emulsive mixtures from the reaction section. Only a small portion of the total risk was due to the hydrocarbon feedstock storage. With the sulfuric acid alkylation unit in the same siting, but assuming no aerosol formation, yields an individual risk at the fenceline of about 10° per year. This would be considered tolerable in the Netherlands for an existing unit. Siting the unit in a rural setting decreases the exposure of the now much more distant residentiali Figure 2, Societal Risk Reduction for the HF Alkylation Unit (Densely Populated Urban Area) Societal Risk = | & | a YTS Base Valves No Pump Divide Dump All Mitigation Options12 population to minimal levels of individual risk (to about a 10* chance of fatality per year). Further, if the no-aerosol assumption is made, the residential population is exposed to very low levels of individual and societal risk from the alkylation unit alone. In addition to the risks posed by the alkylation units, other acute risks associated with the alkylation processes have been evaluated. One of these such risks is that for acid transportation. ‘The fresh acid catalysts, and the spent acid from the sulfuric acid process, can be transported by tank truck, pipeline, railcar, or barge. Additionally, the spend sulfuric acid can be regenerated on-site. In this analysis, all transportation is taken to be by tank truck with regeneration of spent sulfuric acid taking place off-site, The acute risks due to chemical releases were analyzed as well as the predicted deaths due to traffic accidents. The analysis of the acid transportation by tank truck utilized statistical historical information regarding accident data, spill data, design of tank trucks and considered various transportation routes, The risk due to chemical release of sulfuric acid was determined to be insignificant relative to the other risks studied, Also, the risk due to release of HF from a tank truck is very low. In fact, the combined collision and chemical release risks for HF transportation were predicted to cause about 7x10™ fatalities per year. Due to the greater amount of acid catalyst needed for the sulfuric acid alkylation process, about 14-15 truck shipments of acid may be required each day. With the number of miles logged in transportation of the sulfuric acid catalyst, statistically, these trucks are predicted to be involved in more collisions than HF trucks. The collision risk for transportation of the sulfuric acid equates to about 2x10? fatalities per year, Although this risk may be considered to be a slightly different type of risk, nonetheless additional fatalities do result because of the number of sulfuric acid shipments required. These additional estimated deaths are directly related to the sulfuric acid alkylation process and have, therefore, been included in the analysis. With this collision risk included, the total process associated acute societal risks for the sulfuric acid process (even with no aerosol formation) may be greater than the HF alkylation process risks utilizing the modified Phillips design. This is the case for both the urban and rural environments, The sulfuric alkylation process posed almost a factor of five less societal risk than the HF alkylation process utilizing the base case Phillips design, and assuming that no sulfuric acid aerosols are formed upon release of acid/hydrocarbon mixtures. While the acid regeneration of HF occurs as an integral part of the alkylation process, the regeneration of spent sulfuric acid takes place in a separate acid burning process unit. In this process, spent sulfuric acid is combusted to sulfur dioxide, followed by oxidation to sulfur trioxide, and combination with water to form fresh sulfuric acid. The result of our analysis showed no significant acute risk from producing 98% (non-fuming) sulfuric acid. Chronic risks from the regeneration of spent sulfuric acid were not quantified in this analysis, STUDY CONCLUSIONS The detailed quantitative risk analyses indicate that there are inherent risks associated with the operation of both sulfuric acid and hydrofluoric acid alkylation processes. These risks are due to both the flammable and toxic nature of the chemicals utilized. The risks are sensitive to numerous factors, many of which are site specific. The unit risks, when compared to risk management criteria, indicate that risk mitigation could be undertaken for each type of unit. With the proper design modifications and process safety management, the risk posed by13 alkylation units can be significantly reduced. Further, this study indicates that both the hydrofluoric acid and sulfuric acid alkylation processes are capable of being operated within risk levels that are generally considered to be tolerable by society. The uncertainty associated with the risk posed by sulfuric acid alkylation units suggests that caution be exercised in selecting safe alternative technologies for the alkylation process. FURTHER ADVANCEMENTS Since completion of this study in May of 1990, Technica has continued to improve modeling the risks of both sulfuric acid and hydrofluoric acid processes. To this end, Technica has worked to incorporate recent developments and technology advancements related to alkylation process studies. Recently, Technica has written a new dispersion model for evaluation of sulfuric acid behavior upon release, and is including recent developments in HF dispersion modeling as well. The HF modeling improvements include an oligomerization model, and the thermodynamic effects of the reaction of HF with ambient moisture, Failure data analyses are being performed to include new information recently made available to Technica, and to more specifically address the effects of corrosion and corrosion monitoring programs on the equipment failure rates. ‘Technica is planning and organizing a series of rigorous experimental tests to study and address the issue of aerosol formation with sulfuric acid/nydrocarbon emulsions at conditions representative of those in alkylation units. This is a joint effort, involving several refining companies. Also, Technica is currently working with the Phillips Petroleum Company to survey and summarize the results of risk studies carried out for alkylation units throughout the world. The study will include results obtained for a number of refining companies, and performed by a variety of groups. Finally, Technica has conducted a comprehensive management systems audit on nearly a dozen HF alkylation process units (both of Phillips and UOP designs) to identify key management, maintenance and training attributes that can be utilized to reduce the inherent risk associated with HF alkylation.a] [2] (3) (41 [5] [6] 7 14 Literature Cited American Petroleum Institute, "The Use of Hydrofluoric Acid In the Petroleum Refining Alkylation Process”, April, 1991. Blewitt, D.N., Yohn, J.F., Koopman, RP., and Brown, T.C., "Conduct of AnhydrousHydrofluoric Acid Spill Experiments", Intemational Conference on Vapor Cloud Modeling, November, 1987. South Coast Air Quality Management District, "Rule 1410 - Hydrogen Fluoride Storage and Use", 1991. State of New Jersey, Environmental Protection Division of Environmental Quality, "Toxic Catastrophe Prevention Act", June, 1988. Center for Chemical Process Safety, Guidelines for Chemical ss Quantitative Analysis, 1989, Mudan, K.S., "Use of Toxicity Data in Quantitative Risk Assessment of HF Alkylation Units", AIChE Summer National Meeting, August, 1989. Brown, R., and York, JJ Volume 8, No. 2, pp. 149- "Sprays Formed by Flashing Liquid Jets", AIChE Journal, 53, 1962,