Inherent safety has been recognized as a design approach useful to remove or reduce hazards at the source instead of controlling them with add-on protective barriers. However, inherent safety is based on qualitative principles that cannot easily be evaluated and analyzed, and this is one of the major difficulties for the systematic application and quantification of inherent safety in plant design. The present research introduces the use of fuzzy logic for the measurement of inherent safety by proposing a hierarchical fuzzy model. This dissertation establishes a novel conceptual framework for the analysis of inherent safety and proposes a methodology that addresses several of the limitations of the methodologies available for current inherent safety analysis. This research proposes a methodology based on a hierarchical fuzzy model that analyzes the interaction of variables relevant for inherent safety and process safety in general. The use of fuzzy logic is helpful for modeling uncertainty and subjectivities implied in evaluation of certain variables and it is helpful for combining quantitative data with qualitative information. Fuzzy logic offers the advantage of being able to model numerical and heuristic expert knowledge by using fuzzy IF-THEN rules. Safety is traditionally considered a subjective issue because of the high uncertainty associated with its significant descriptors and parameters; however, this research recognizes that rather than subjective, "safety" is a vague problem. Vagueness derives from the fact that it is not possible to define sharp boundaries between safe and unsafe states; therefore the problem is a "matter of degree". The proposed method is computer-based and process simulator-oriented in order to reduce the time and expertise required for the analysis. It is expected that in the future, by linking the present approach to a process simulator, process engineers can develop safety analysis during the early stages of the design in a rapid and systematic way. Another important aspect of inherent safety, rarely addressed, is transportation of chemical substances; this dissertation includes the analysis of transportation hazard by truck using a fuzzy logic-based approach.

Inherent safety has been recognized as a design approach useful to remove or reduce hazards at the source instead of controlling them with add-on protective barriers. However, inherent safety is based on qualitative principles that cannot easily be evaluated and analyzed, and this is one of the major difficulties for the systematic application and quantification of inherent safety in plant design. The present research introduces the use of fuzzy logic for the measurement of inherent safety by proposing a hierarchical fuzzy model. This dissertation establishes a novel conceptual framework for the analysis of inherent safety and proposes a methodology that addresses several of the limitations of the methodologies available for current inherent safety analysis. This research proposes a methodology based on a hierarchical fuzzy model that analyzes the interaction of variables relevant for inherent safety and process safety in general. The use of fuzzy logic is helpful for modeling uncertainty and subjectivities implied in evaluation of certain variables and it is helpful for combining quantitative data with qualitative information. Fuzzy logic offers the advantage of being able to model numerical and heuristic expert knowledge by using fuzzy IF-THEN rules. Safety is traditionally considered a subjective issue because of the high uncertainty associated with its significant descriptors and parameters; however, this research recognizes that rather than subjective, "safety" is a vague problem. Vagueness derives from the fact that it is not possible to define sharp boundaries between safe and unsafe states; therefore the problem is a "matter of degree". The proposed method is computer-based and process simulator-oriented in order to reduce the time and expertise required for the analysis. It is expected that in the future, by linking the present approach to a process simulator, process engineers can develop safety analysis during the early stages of the design in a rapid and systematic way. Another important aspect of inherent safety, rarely addressed, is transportation of chemical substances; this dissertation includes the analysis of transportation hazard by truck using a fuzzy logic-based approach.

This thesis describes research into a methodology for the systematic development of engineering line diagrams (ELOs) from process tlowsheets with a particular emphasis on safety, health and environmental (SHE) and operability issues. The current approach to the consideration of safety in design is largely reactive, relying on design reviews such as the HAZOP. If design safety is to be improved, then a comprehensive system, incorporating both proactive and reactive methods, must be adopted. The facility to develop proactive safety systems relies upon the presence of a systematic design procedure. Since design at this stage seems generally to be rather haphazard, there is a need to introduce structure to the design task before any progress can be made in the improvement of safety. Introducing structure to the design task not only provides a framework for the incorporation of SHE and operability issues, but should also improve the effectiveness of the overall design and the efficiency with which it is completed. More specifically, fewer good design opportunities should be lost due to poor information handling and thc amount of rework arising from misunderstandings between different disciplines should be minimised. In addition, learning how to perform the design task should become easier for new recruits. Relevant work in the fields of process design, process safety, engineering drawings and ELO development is discussed. An analysis of perceptions of the design task within industry is presented. The generation of a systematic method by iterative case study work with designers is described. The structural features of this method are explained. Some examples of the application of the method are given and the results of a trial within industry are discussed. This research has shown that there is no existing work which captures the logic for the order in which decisions for developing a first ELO are made. Neither is there a complete analysis of the activities and issues contributing to ELO development. A novel method for the systematic generation of ELOs has been produced and used as a framework for the incorporation of SHE and operability issues into design. Trials of the method within industry have shown it to be successful.

The catalytic N-oxidation of alkylpyridines, a reaction which uses hydrogen peroxide as the oxidizing agent and the water soluble phosphotungstic acid as the catalyst, is a reaction employed in the pharmaceutical industry. The safety concerns of this process revolve around the decomposition of hydrogen peroxide and the liquid-liquid phase separation of the reacting mixture. The decomposition of hydrogen peroxide is an undesired reaction parallel to the desired N-oxidation and is responsible for: 1) a high potential for runaway due to the condition sensitivity of the peroxide group, 2) a potential over-pressurization of the reaction vessel during a runaway due to the production of oxygen, and 3) the enrichment with oxygen of the flammable alkylpyridine environment. The presence of an organic phase and an aqueous phase occurs in a wide range of conditions and results in: 1) a dramatic reduction in the reaction selectivity, and consequently in the efficiency, due to the additional mass transfer constrains imposed by the phase separation, and 2) the safety of the process being seriously compromised because most of the catalyst remains in the aqueous phase, excessively promoting the decomposition of hydrogen peroxide over the N-oxidation. With these concerns in mind, this research aimed to determine conditions for an inherently safer and more efficient N-oxidation reaction and focused on three key targets: i) the possibility of reducing the extend of the decomposition of hydrogen peroxide, thus leading to an inherently safer process, ii) the study of phase equilibrium so as to enable the identification of conditions that increase the efficiency of the N-oxidation and reduces the hazards, and iii) the evaluation of safety parameters that will allow for the control of a potential runaway reaction. Two alkylpyridines were considered: 2-methylpyridine which represents the case of a homogeneous reacting mixture and 2,6-dimethylpyridine to study the two-liquid phase separation effects. The methodology employed calorimetric studies to assess the runaway behavior and to determine the conditions that favor the N-oxidation, and for the N-oxidation of 2,6-dimethylpyridine, thermodynamic studies were incorporated to evaluate the conditions for phase separation.

In the area of process safety, many efforts have focused on studying methods to prevent the transition of the state of the system from a normal state to an upset and/or catastrophic state, but many unexpected changes are unavoidable, and even under good risk management incidents still occur. The aim of this work is to propose the principles and factors that contribute to the resilience of the chemical process, and to develop a systematic approach to evaluate the resilience of chemical processes in design aspects. Based on the analysis of transition of the system states, the top-level factors that contribute to Resilience were developed, including Design, Detection Potential, Emergency Response Planning, Human, and Safety Management. The evaluation framework to identify the Resilience Design Index is developed by means of the multifactor model approach. The research was then focused on developing complete subfactors of the top-level Design factor. The sub-factors include Inherent Safety, Flexibility, and Controllability. The proposed framework to calculate the Inherent Safety index takes into account all the aspects of process safety design via many sub-indices. Indices of Flexibility and Controllability sub-factors were developed from implementations of well-known methodologies in process design and process control, respectively. Then, the top-level Design index was evaluated by combining the indices of the sub-factors with weight factors, which were derived from Analytical Hierarchical Process approach. A case study to compare the resilience levels of two ethylene production designs demonstrated the proposed approaches and gave insights on process resilience of the designs.

Yes / Process safety has drawn increasing attention in recent years and has been investigated from different perspectives, such as quantitative risk analysis, consequence modeling, and regulations. However, rare attempts have been made to focus on inherent safety design assessment, despite being the most cost-effective safety tactic and its vital role in sustainable development and safe operation of process infrastructure. Accordingly, the present research proposed a knowledge-driven model to assess inherent safety in process infrastructure under uncertainty. We first developed a holistic taxonomy of contributing factors into inherent safety design considering chemical, reaction, process, equipment, human factors, and organizational concerns associated with process plants. Then, we used subject matter experts, content validity ratio (CVR), and content validity index (CVI) to validate the taxonomy and data collection tools. We then employed a fuzzy inference system and the Extent Analysis (EA) method for knowledge acquisition under uncertainty. We tested the proposed model on a steam methane-reforming plant that produces hydrogen as renewable energy. The findings revealed the most contributing factors and indicators to improve the inherent safety design in the studied plant and effectively support the decision-making process to assign proper safety countermeasures.

Incorporating consideration for safety issues while designing solvent processes has become crucial in light of the chemical process incidents involving solvents that have taken place in recent years. The implementation of inherently safer design concepts is considered beneficial to avoid hazards during early stages of design. The application of existing process design and modeling techniques that aid the concepts of ‘substitution’, ‘intensification’ and ‘attenuation’ has been shown in this work. For ‘substitution’, computer aided molecular design (CAMD) technique has been applied to select inherently safer solvents for a solvent operation. For ‘intensification’ and ‘attenuation’, consequence models and regulatory guidance from EPA RMP have been integrated into process simulation. Combining existing techniques provides a design team with a higher level of information to make decisions based on process safety. CAMD is a methodology used for designing compounds with desired target properties. An important aspect of this methodology concerns the prediction of properties given the structure of the molecule. This work also investigates the applicability of Quantitative Structure Property Relationship (QSPR) and topological indices to CAMD. The evaluation was based on models developed to predict flash point properties of different classes of solvents. Multiple linear regression and neural network analysis were used to develop QSPR models, but there are certain limitations associated with using QSPR in CAMD which have been discussed and need further work. Practical application of molecular design and process design techniques have been demonstrated in a case study on liquid-liquid extraction of acetic acid-water mixture. Suitable inherently safer solvents were identified using ICAS-ProCAMD, and consequence models were integrated into Aspen Plus simulator using a calculator sheet. Upon integrating flammable and toxic hazard modeling, solvents such as 5-nonanone, 2-nonanone and 5-methyl-2-hexanone provide inherently safer options, while conventionally-used solvent, ethyl acetate, provides higher degree of separation capability. A conclusive decision regarding feasible solvents and operating conditions would depend on design requirements, regulatory guidance, and safety criteria specified for the process. Inherent safety has always been an important consideration to be implemented during early design steps, and this research presents a methodology to incorporate the principles and obtain inherently safer alternatives.

Further development of ideas discussed at a joint workshop sponsored by the United Nations Environment Programme Industry and Environment Centre (UNEP/IE) and the Organization for Economic Cooperation and Development (OECD) in Paris, 7-8 June 1993.

This thesis is devoted to the investigation of passivesafety and inherent features of subcritical nucleartransmutation systems - accelerator-driven systems. The generalobjective of this research has been to improve the safetyperformance and avoid elevated coolant temperatures inworst-case scenarios like unprotected loss-of-ow accidents,loss-of-heat-sink accidents, and a combination of both theseaccident initiators. The specific topics covered are emergencydecay heat removal by reactor vessel auxiliary cooling systems,beam shut-off by a melt-rupture disc, safety aspects fromlocating heat-exchangers in the riser of a pool-type reactorsystem, and reduction of pressure resistance in the primarycircuit by employing bypass routes. The initial part of the research was focused on reactorvessel auxiliary cooling systems. It was shown that an 80 MWthPb/Bi-cooled accelerator-driven system of 8 m height and 6 mdiameter vessel can be well cooled in the case of loss-of-owaccidents in which the accelerator proton beam is not switchedoff. After a loss-of-heat-sink accident the proton beam has tobe interrupted within 40 minutes in order to avoid fast creepof the vessel. If a melt-rupture disc is included in the wallof the beam pipe, which breaks at 150 K above the normal coreoutlet temperature, the grace period until the beam has to beshut off is increased to 6 hours. For the same vessel geometry,but an operating power of 250 MWth the structural materials canstill avoid fast creep in case the proton beam is shut offimmediately. If beam shut-off is delayed, additional coolingmethods are needed to increase the heat removal. Investigationswere made on the filling of the gap between the guard and thereactor vessel with liquid metal coolant and using water spraycooling on the guard vessel surface. The second part of the thesis presents examinationsregarding an accelerator-driven system also cooled with Pb/Bibut with heat-exchangers located in the risers of the reactorvessel. For a pool type design, this approach has advantages inthe case of heat-exchanger tube failures, particularly if wateris used as the secondary uid. This is because a leakage ofwater from the secondary circuit into the Pb/Bi-cooled primarycircuit leads to upward sweeping of steam bubbles, which wouldcollect in the gas plenum. In the case of heatexchangers in thedowncomer steam bubbles may be dragged into the ADS core andadd reactivity. Bypass routes are employed to increase the owspeed in loss-of-ow events for this design. It is shown thatthe 200 MWth accelerator-driven system with heat-exchangers inthe riser copes reasonably well with both a loss-of-ow accidentwith the beam on and an unprotected loss-of-heat-sink accident.For a total-loss-of-power (station blackout) and an immediatebeam-stop the core outlet temperature peaks at 680 K. After acombined loss-of-ow and loss-of-heat-sink accident the beamshould be shut off within 4 minutes to avoid exceeding the ASMElevel D of 977 K, and within 8 minutes to avoid fast creep.Assuming the same core inlet temperature, both the reactordesign with heat-exchanger in the risers and the downcomershave similar temperature evolutions after a total-loss-ofpoweraccident. A large accelerator-driven system of 800 MWth with a 17 mtall vessel may eventually become a standard size. For thishigher power ADS, the location of the heat-exchangers hasgreater impact on the natural convection capability. This isdue to that larger heatexchangers have more inuence on thedistance between the thermal centers during a lossof- owaccident. The design with heat-exchangers in the downcomers,the long-term vessel temperature peaks at 996 K during aloss-of-ow accident with the beam on. This does not pose athreat of creep rupture for the vessel. However, the locationof the heat-exchangers in the downcomers will probably requiresecondary coolant other than water, like for example oil (fortemperatures not higher than 673 K) or Pb/Bi coolant.

<p>This thesis is devoted to the investigation of passivesafety and inherent features of subcritical nucleartransmutation systems - accelerator-driven systems. The generalobjective of this research has been to improve the safetyperformance and avoid elevated coolant temperatures inworst-case scenarios like unprotected loss-of-ow accidents,loss-of-heat-sink accidents, and a combination of both theseaccident initiators. The specific topics covered are emergencydecay heat removal by reactor vessel auxiliary cooling systems,beam shut-off by a melt-rupture disc, safety aspects fromlocating heat-exchangers in the riser of a pool-type reactorsystem, and reduction of pressure resistance in the primarycircuit by employing bypass routes.</p><p>The initial part of the research was focused on reactorvessel auxiliary cooling systems. It was shown that an 80 MWthPb/Bi-cooled accelerator-driven system of 8 m height and 6 mdiameter vessel can be well cooled in the case of loss-of-owaccidents in which the accelerator proton beam is not switchedoff. After a loss-of-heat-sink accident the proton beam has tobe interrupted within 40 minutes in order to avoid fast creepof the vessel. If a melt-rupture disc is included in the wallof the beam pipe, which breaks at 150 K above the normal coreoutlet temperature, the grace period until the beam has to beshut off is increased to 6 hours. For the same vessel geometry,but an operating power of 250 MWth the structural materials canstill avoid fast creep in case the proton beam is shut offimmediately. If beam shut-off is delayed, additional coolingmethods are needed to increase the heat removal. Investigationswere made on the filling of the gap between the guard and thereactor vessel with liquid metal coolant and using water spraycooling on the guard vessel surface.</p><p>The second part of the thesis presents examinationsregarding an accelerator-driven system also cooled with Pb/Bibut with heat-exchangers located in the risers of the reactorvessel. For a pool type design, this approach has advantages inthe case of heat-exchanger tube failures, particularly if wateris used as the secondary uid. This is because a leakage ofwater from the secondary circuit into the Pb/Bi-cooled primarycircuit leads to upward sweeping of steam bubbles, which wouldcollect in the gas plenum. In the case of heatexchangers in thedowncomer steam bubbles may be dragged into the ADS core andadd reactivity. Bypass routes are employed to increase the owspeed in loss-of-ow events for this design. It is shown thatthe 200 MWth accelerator-driven system with heat-exchangers inthe riser copes reasonably well with both a loss-of-ow accidentwith the beam on and an unprotected loss-of-heat-sink accident.For a total-loss-of-power (station blackout) and an immediatebeam-stop the core outlet temperature peaks at 680 K. After acombined loss-of-ow and loss-of-heat-sink accident the beamshould be shut off within 4 minutes to avoid exceeding the ASMElevel D of 977 K, and within 8 minutes to avoid fast creep.Assuming the same core inlet temperature, both the reactordesign with heat-exchanger in the risers and the downcomershave similar temperature evolutions after a total-loss-ofpoweraccident.</p><p>A large accelerator-driven system of 800 MWth with a 17 mtall vessel may eventually become a standard size. For thishigher power ADS, the location of the heat-exchangers hasgreater impact on the natural convection capability. This isdue to that larger heatexchangers have more inuence on thedistance between the thermal centers during a lossof- owaccident. The design with heat-exchangers in the downcomers,the long-term vessel temperature peaks at 996 K during aloss-of-ow accident with the beam on. This does not pose athreat of creep rupture for the vessel. However, the locationof the heat-exchangers in the downcomers will probably requiresecondary coolant other than water, like for example oil (fortemperatures not higher than 673 K) or Pb/Bi coolant.</p>