Chemical Process PSAs

Unfortunately chemical process plant PSA have no requirements for public disclosure, consequently examples of their PSAs are hard to find. However the following are some examples from the open literature. They are similar to nuclear PSAs except less elaborate with more empahsis on consequences than on probabilities. 

In addition to these are studies prepared before President Carter stopped the GESMO (Generic Environmental Statement for Mixed Oxide) that addressed the chemical processing of fissionable material for the nuclear fuel cycle. Some references are Cohen (1975), Schneider (1982), Erdmann (1979), Fuliwood (1980), and Fullwood (1983). 

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This chapter overviews the techniques for incorporating external events into a PSA. The discussion was primarily aimed at nuclear power plants but is equally applicable to chemical process plants. The types of external events discussed were earthquakes, fires and floods. Notably absent were severe winds and tornados. Tornados are analyzed as missiles impacting the structures and causing common-cause failures of systems (EPRINP-768). Missile propagation and the resulting damage is a specialized subject usually solved with computer codes. 

As the previous ehapter discussed nuelear power reactor operation and how to perform a PSA on it, this chapter attempts to apply a similar framework to chemical processing. The problem is the diversity of chemical processing that blurs the focus. This chapter begins by showing that accidents in the chemical process industry cost lives and dollars. Descriptions of deadly chemical accidents arc presented to show the chain of sequences that were involved to suggest how their PSA may be structured. Background on selected hazardous chemical process is presented followed by descriptions of how their PSA have structured. The chapter concludes by applying FTAPSUIT to a pressure vessel rupture analysis. 

Table 7.3-2 lists some objectives for performing PSA on chemical process systems. Objective 1 is to determine if a process or plant has sufficient risk to justify a detailed analysis. This scoping analysis may be performed with a HAZOP (Section 3.3.4) or an FMEA (3.3. S) with either... 

It was stated earlier that PSAs for nuclear and chemical processes differ by preceding a chemical PSA with a scoping analysis that is omitted for a nuclear PSA. This is not true. WASH-740 performed this purpose for a hypothetical plant. 

The chemical and physical phenomena involved in chemical process accidents is very complex. The preceding provides the elements of some of the simpler analytic methods, but a PSA analyst should only have to know general principles and use the work of experts contained in computer codes. There are four types of phenomenology of concern 1) release of dispersible toxic material, 21 dispersion of the material, 3) fires, and 4) explosions. A general reference to such codes is not in the open literature, although some codes are mentioned in CCPS (1989) they are not generally available to the public. 

PSAs estimate that the frequency of reactor damage cover about two orders of magnitude from about lE-5/y to lE-3/y. This variation is attributable to plant design, construction, and operation, to site characteristics, scope of the PSAs, and methods and analytical assumptions. Such comprehensive studies of comparable chemical process plants do not exist. 

The nuclear equipment failure rate database has not changed markedly since the RSS and chemical process data contains information for non-chemical process equipment in a more benign environment. Uncertainty in the database results from the statistical sample, heterogeneity, incompleteness, and unrepresentative environment, operation, and maintenance. Some PSA.s use extensive studies of plant-specific data to augment the generic database by Bayesian methods and others do not. No standard guidance is available for when to use which and the improvement in accuracy that is achieved thereby. Improvements in the database and in the treatment of data requires, uhstaiui.il indu.sinal support but it is expensive. 

Nuclear PSAs contain considerable uncertainty associated with the physical and chemical processes involved in core degradation, movement of the molten core in the reactor vessel, on the containment floor, and the response of the containment to the stresses placed upon it. The current models of these processes need refinement and validation. Because the geometry is greatly changed by small perturbations after degradation has commenced, it is not clear that the phenomcn.i can be treated. 

There is a close kinship between the chemical process industry and the nuclear electric power industry. In tact once the physics of nuclear reaction was established the rest is chemistiy and hc.it ii an.sfer. The word "reactor" is from chemistry for the location the reaction takes place.. nuclear reactor consists of a vessel in which a nuclear reaction heats water to make steam to drive a turbine o generate electricity. Thus the primary components are pipes, valves, pumps heat exchangers, and water purifiers similar to the components found in a chemical plant. Following the success of WASH-1400, PSA was used to analyze the chemical proce.ssmg of nuclear fuel and. aste preparation for disposal. 

A leader in applying PSA to other parts of the chemical process industry has been the AlChf. s Center for Chemical Process Safety. A major difference between PSA for nuclear power and PSA for chemical processing has been the lack of government regulations that require risk analysis for chemical processes. A primary impetuous has been the Occupational Safety and Health Administration s (OSHA) PSM rule that defines the application of PSA to the chemical industry for ihc proteciion of the public and workers. In addition, the Environmental Protection Agcrii, . (EPA) regulates waste disposal. 

I am a physicist who switched to nuclear engineering for my Ph D. My introduction to PSA was as an original participant in the Reactor Safety Study in 1972. Material for this book was first gathered in 1974 for a workshop on what to expect in WASH-1400 (the results of the Reactor Safety Study). Materials were gathered over the years for EPRI, Savannah River Laboratory, and other workshops. A culmination was in 1988 with "Probabilistic Risk Assessment in the Nuclear Power Industry" with Robert Hall as coauthor. This book updates these materials and adds material on PSA in the chemical process industry. I prepared the material for printing using a word processor... 

Babicki, M. and A. Hall, PSA Technology Hits the Fast Lane, Chemical Processing Digital Edition, 9/10/2003, available at http //www.chemicalprocessing.com/articles/2003/322.html. 

The PSA process was carried out not by changing the total pressure but by changing the partial pressure of butanone. As the adsorption/desorption process was very slow (chemical process), we thought that the mass transfer did not affect the rate of adsorption or desorption. 

PSA hydrogen recovery will also compete more favorably with cryogenic alternatives In the future Streams of 50 to 100 thousand cubic meters per hour will be processed at pressures up to about 70 atmospheres In addition, as hydrogen becomes more valuable In chemical processes, hlgh-purlty hydrogen via PSA will be used more frequently to minimize vent-stream losses Conversely Impure hydrogen In other vent streams will be a candidate for recovery and cleanup via PSA ... 

Other polymers used in the PSA industry include synthetic polyisoprenes and polybutadienes, styrene-butadiene rubbers, butadiene-acrylonitrile rubbers, polychloroprenes, and some polyisobutylenes. With the exception of pure polyisobutylenes, these polymer backbones retain some unsaturation, which makes them susceptible to oxidation and UV degradation. The rubbers require compounding with tackifiers and, if desired, plasticizers or oils to make them tacky. To improve performance and to make them more processible, diene-based polymers are typically compounded with additional stabilizers, chemical crosslinkers, and solvents for coating. Emulsion polymerized styrene butadiene rubbers (SBRs) are a common basis for PSA formulation [121]. The tackified SBR PSAs show improved cohesive strength as the Mooney viscosity and percent bound styrene in the rubber increases. The peel performance typically is best with 24—40% bound styrene in the rubber. To increase adhesion to polar surfaces, carboxylated SBRs have been used for PSA formulation. Blends of SBR and natural rubber are commonly used to improve long-term stability of the adhesives. 

Even, limited PSAs use and contain much information. This information may come as memos and process reports and flow sheets, equipment layout, system descriptions, toxic inventory, hazardous chemical reactions, test, maintenance and operating descriptions. From this, data and analyses are prepared regarding release quantities, doses, equipment reliability, probability of exposure, and the risk to workers, public, and environment. An executive summary analysis is detailed, and recommendations made for risk reduction. Thus the information will be text, calculations of envelope fracture stresses, temperatures, fire propagation, air dispersion, doses, and failure probabilities - primarily in tabular form. 

The assembly process (Figure 10-1) brings together all of the assessment tasks to provide the risk, its significance, how it was found, its sensitivity to uncertainties, confidence limits, and how it may be reduced by system improvements. Not all PSAs use fault trees and event trees. This is especially true of chemical PSAs that may rely on HAZOP or FMEA/FMECAs. Nevertheless the objectives are the same accident identification, analysis and evaluation. Figure 10-1 assumes fault tree and event tree techniques which should be replaced by the equivalent methods that are used. 

Show the complex iterations between government laws and regulations and the PSA response to not only comply but to protect the process industry. The real impact of the accident at the Three-Mile Island nuclear plant was not radiation, which was within regulations but financial losses to the utility and the acceptance of nuclear electrical f>ower in the United States. The effects of the Bhopal accident were in human life but it also had a profound effect on the chemical industry financially, and its acceptability and growth. Present the mathematics used in PSA in one chapter to be skipped, studied, or relerred to according to the readers needs. 

During the characterization process, hits are typically tested for kinetic solubility and permeability in a model of passive diffusion such as PAMPA [22]. As new compounds are synthesized, additional parameters also need to be considered, such as pZa, chemical and plasma stability, and protein binding. Calculated properties such as MW, clogP, and PSA should also be tracked. 

AUTO-PUREX G A process for removing carbon dioxide from air by PSA, using alumina as the sorbent. Developed by Marutani Chemical Plant Engineering Company, Japan. 

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