This document provides information for assessing the thermal risk of a batch reaction process through a case study. Experimental measurements found the heat of the desired reaction to be 250 kJ/kg and the heat of decomposition to be 500 kJ/kg. These results are to be summarized in risk analysis forms 1 and 2 to allow preliminary evaluation of the severity and probability of risks for the process.
This document provides information for assessing the thermal risk of a batch reaction process through a case study. Experimental measurements found the heat of the desired reaction to be 250 kJ/kg and the heat of decomposition to be 500 kJ/kg. These results are to be summarized in risk analysis forms 1 and 2 to allow preliminary evaluation of the severity and probability of risks for the process.
This document provides information for assessing the thermal risk of a batch reaction process through a case study. Experimental measurements found the heat of the desired reaction to be 250 kJ/kg and the heat of decomposition to be 500 kJ/kg. These results are to be summarized in risk analysis forms 1 and 2 to allow preliminary evaluation of the severity and probability of risks for the process.
This document provides information for assessing the thermal risk of a batch reaction process through a case study. Experimental measurements found the heat of the desired reaction to be 250 kJ/kg and the heat of decomposition to be 500 kJ/kg. These results are to be summarized in risk analysis forms 1 and 2 to allow preliminary evaluation of the severity and probability of risks for the process.
This case study shows through an example of a batch
reaction how to systematically assess the thermal risk related to runaway reactions. It was prepared by R.Perrayon and P.Lerena based on the knowledge of the Swiss Safety Institute (Basel, Switzerland) Lesson 1 is a step by step procedure to allow a preliminary evaluation of both severity and probability using simple experimental techniques (SCREENING). Summary of lessons What is risk? Traditionally the risk is defined as the product of the severity of a possible incident times its probability of occurrence. Hence the risk assessment requires the evaluation of both the severity and probability. The following lessons are a guide to a systematic evaluation of the risks of a chemical process. Lesson 1 is a step by step procedure to allow a preliminary evaluation of both severity and probability using simple experimental techniques (SCREENING). Lesson 2 expands the study through the use of more data if the conclusion of the previous SCREENING is that the thermal risks of the process are high. Lesson 3 summarizes the results obtained in the previous lessons through the construction of a COOLING FAILURE SCENARIO and the assessment of its CRITICALITY. Lesson 4 analyzes the operating conditions required to mantain the process under thermal control as well as the measures that should be taken to prevent an incident from occuring. Case study : Batch reaction Lesson 1 The following is a short description of an actual manufacturing procedure for the substitution of para-chloro-nitrobenzene: A quantity of 1-chloro-4-nitrobenzene is charged in a reactor with ammonia (27% by weight in water). The autoclave is then heated in about 3 hours to 195C and maintained at this temperature for 5 hours. The pressure finally reaches 41-42 atms. After this time, the reaction mass is colled down to room temperature. Cl NO 2 H 2 N 2 NH 3 NH 4 Cl NO 2 Reaction scheme + + Process data Charge Compound Mass kmol Molar ratio (kg) 1-Chloro-4- nitro-benzene 423 2.7 1 Ammonia 27% 2024 32.1 12 (pure NH 3 ) Total 2447 Reactor data Stage Reaction mass Approximate (kg) volume (m 3 ) Initial 2447* 2.6 Final 2447* 2.6 *In a batch process, the initial and final reaction mass are the same. Lesson 1 The results of lesson 1 should be summarized in risk analysis forms 1 and 2. Using these forms fill in the headings and the BATCH SIZE section of form 1 for the process data shown opposite. Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 Product: Batch reaction Ident No: Location: Case study Proc. dated: Author of risk analysis: ( Your name ) Date: ( actual date ) DESCRIPTION OF SYNTHESIS REACTION (USE ONE SHEET PER STEP) BATCH SIZE 2.7 kmol at the start 2.6 m 3 2447 kg at the end 2.6 m 3 2447 kg Case study : Batch reaction Thermal Stability BASIC DATA FOR RISK ANALYSIS FORM 0h Product: Batch reaction Ident No: Location: Case study Proc. dated: Author of risk analysis: ( Your name ) Date: ( actual date ) CHARACTERISTIC DATA OF DECOMPOSITION REACTIONS (USE SEVERAL SHEETS IF NECESSARY) Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 Product: Batch reaction Ident No: Location: Case study Proc. dated: Author of risk analysis: ( Your name ) Date: ( actual date ) DESCRIPTION OF SYNTHESIS REACTION (USE ONE SHEET PER STEP) BATCH SIZE 2.7 kmol at the start 2.6 m 3 2447 kg at the end 2.6 m 3 2447 kg Case study : Batch reaction Thermal Stability BASIC DATA FOR RISK ANALYSIS FORM 0h Product: Batch reaction Ident No: Location: Case study Proc. dated: Author of risk analysis: ( Your name ) Date: ( actual date ) CHARACTERISTIC DATA OF DECOMPOSITION REACTIONS (USE SEVERAL SHEETS IF NECESSARY) Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Case study : Batch reaction Lesson 1 Assessment of severity Lesson 1 In order to obtain a preliminary evaluation (SCREENING) of the severity of the chemical process under study, one should determine the following data: Heat of the desired reaction Heat of the decomposition reaction Specific heat capacity of the reaction mixture Lesson 1 In order to evaluate the heat of the desired reaction and the heat of the decomposition reaction two thermograms were supplied by the thermal safety laboratory. A linear temperature ramp from 23C to 450C was used in both measurements (scan rate 4Cmin -1 ). The overall potential thermogram shows an endothermic signal (fusion of the product) and two overlapping exothermic signals. The first signal equals a potential of +30 kJkg -1 and the second ones a total potential of -750 kJkg -1 . A sample of the reaction mixture after completing the desired reaction (final reaction mixture thermogram) shows, excepted the endotherm, only one peak of -500 kJkg -1 . This energy is in the same temperature range of the second exothermic peak of the overall potential thermogram. Overall potential thermogram: Quantitative differential thermal analysis of a mixture of the starting materials. Final reaction mixture thermogram: Quantitative differential thermal analysis of the final reaction mixture. -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2 0 100 200 300 400 -500 kJkg -1 +30 kJkg -1 Heat release rate (Wg -1 ) scan rate: 4Cmin -1 Temperature (C) Heat release rate ( Wg -1 ) -1 -0.5 0 0.5 1 1.5 2 50 100 150 200 250 300 350 -750 kJkg -1 +30 kJkg -1 Temperature (C) scan rate: 4Cmin -1 Baselines Answer this question: According to the results of experimental measurements, what is the heat of the desired reaction? (Units should be kJkg -1 ) Overall potential thermogram: Quantitative differential thermal analysis of a mixture of the starting materials. Final reaction mixture thermogram: Quantitative differential thermal analysis of the final reaction mixture. -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2 0 100 200 300 400 -500 kJkg -1 +30 kJkg -1 Heat release rate (Wg -1 ) scan rate: 4Cmin -1 Temperature (C) Heat release rate ( Wg -1 ) -1 -0.5 0 0.5 1 1.5 2 50 100 150 200 250 300 350 -750 kJkg -1 +30 kJkg -1 Temperature (C) scan rate: 4Cmin -1 Baselines Answer this question: According to the results of experimental measurements, what is the heat of the desired reaction? (Units should be kJkg -1 ) Right answer: The heat of the desired reaction is 250 kJkg -1 Overall potential thermogram: Quantitative differential thermal analysis of a mixture of the starting materials. Final reaction mixture thermogram: Quantitative differential thermal analysis of the final reaction mixture. -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2 0 100 200 300 400 -500 kJkg -1 +30 kJkg -1 Heat release rate (Wg -1 ) scan rate: 4Cmin -1 Temperature (C) Heat release rate ( Wg -1 ) -1 -0.5 0 0.5 1 1.5 2 50 100 150 200 250 300 350 -750 kJkg -1 +30 kJkg -1 Temperature (C) scan rate: 4Cmin -1 Baselines Answer this question: According to the results of experimental measurements, what is the heat of the decomposition reaction? (Units should be kJkg -1 ) Overall potential thermogram: Quantitative differential thermal analysis of a mixture of the starting materials. Final reaction mixture thermogram: Quantitative differential thermal analysis of the final reaction mixture. -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2 0 100 200 300 400 -500 kJkg -1 +30 kJkg -1 Heat release rate (Wg -1 ) scan rate: 4Cmin -1 Temperature (C) Heat release rate ( Wg -1 ) -1 -0.5 0 0.5 1 1.5 2 50 100 150 200 250 300 350 -750 kJkg -1 +30 kJkg -1 Temperature (C) scan rate: 4Cmin -1 Baselines Answer this question: According to the results of experimental measurements, what is the heat of the decomposition reaction? (Units should be kJkg -1 ) Right answer: The heat of the decomposition reaction is 500 kJkg -1 Overall potential thermogram: Quantitative differential thermal analysis of a mixture of the starting materials. Final reaction mixture thermogram: Quantitative differential thermal analysis of the final reaction mixture. -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2 0 100 200 300 400 -500 kJkg -1 +30 kJkg -1 Heat release rate (Wg -1 ) scan rate: 4Cmin -1 Temperature (C) Heat release rate ( Wg -1 ) -1 -0.5 0 0.5 1 1.5 2 50 100 150 200 250 300 350 -750 kJkg -1 +30 kJkg -1 Temperature (C) scan rate: 4Cmin -1 Baselines Case study : Batch reaction Lesson 1 Assessment of severity Lesson 1 In a preliminary evaluation (SCREENING) of the severity of the chemical process under study the following data are already known: Heat of the desired reaction QR = 250 kJkg -1 Heat of the decomposition reaction QD = 500 kJkg -1 These results are summarized in the risk analysis forms 1 and 2. Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 POTENTIAL Heat of reaction Specific heat capacity Adiabatic Temperature Rise (Ratio Q R / Cp) Q R = 250 kJ/kg Cp = kJ/kg/K Tad = C Highest theoretical attainable temperature in case adiabatic conditions occur: C Total gas evolution: l/kg l/batch Source of data: Consequences of allowing adiabatic reaction (Check appropriate boxes) Harmless temperature rise Boiling (Bp = C) Gas release Critical temperature rise Decomposition Pressure build up Other : Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 POTENTIAL Heat of reaction Specific heat capacity Adiabatic Temperature Rise (Ratio Q R / Cp) Q R = 250 kJ/kg Cp = kJ/kg/K Tad = C Highest theoretical attainable temperature in case adiabatic conditions occur: C Total gas evolution: l/kg l/batch Source of data: Consequences of allowing adiabatic reaction (Check appropriate boxes) Harmless temperature rise Boiling (Bp = C) Gas release Critical temperature rise Decomposition Pressure build up Other : Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Case study : Batch reaction Thermal Stability BASIC DATA FOR RISK ANALYSIS FORM 2 Severity: Energy potential of relevant decomposition reactions: 500 kJ/kg Specific heat capacity of reaction mass: kJ/kg/K Adiabatic temperature rise: C Boiling point of reaction mass (if relevant): C Gas evolution: m 3 /batch Known decomposition products: Source of data: Assessment of severity: Low Medium High Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Case study : Batch reaction Thermal Stability BASIC DATA FOR RISK ANALYSIS FORM 2 Severity: Energy potential of relevant decomposition reactions: 500 kJ/kg Specific heat capacity of reaction mass: kJ/kg/K Adiabatic temperature rise: C Boiling point of reaction mass (if relevant): C Gas evolution: m 3 /batch Known decomposition products: Source of data: Assessment of severity: Low Medium High Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Lesson 1 In a preliminary evaluation (SCREENING) of the severity of the chemical process under study the following data are already known: Heat of the desired reaction QR = 250 kJkg -1 Heat of the decomposition reaction QD = 500 kJkg -1 The next step of lesson 1 is to estimate the specific heat capacity of the reaction mixture. Case study : Batch reaction Lesson 1 Assessment of severity Example Estimate of the specific heat capacity of a mixture of 2000 kg of an organic compound in 2500 kg of ammonia (27% by weight) in aqueous solution. Table of data Compound Cp M MCp (kJkg -1 K -1 ) (kg) (kJK -1 ) Organic compound 1.8 2000 3600 Ammonia 27% by wt. 3.9 2500 9750 Total 4500 13350 Cp Specific heat capacity of the reaction mixture (kJkg -1 K -1 ) Mi Mass of a compound (kg) Cpi Specific heat capacity of a compound (kJkg -1 K -1 ) MR Total mass of the reaction mixture (kg) Cp MiCpi MR = = 13350 4500 = 3.0 kJkg -1 K -1 Specific heat capacity calculation Lesson 1 A rough estimate of the specific heat capacity of the reaction mixture can be obtained by addition of the heat capacities of its components. The table below shows approximate values of specific heat capacities for different compound classes. The example shows how to calculate the specific heat capacity of a mixture of 2000 kg of an organic compound in 2500 kg of ammonia (27% by weight) in aqueous solution. Compound Specific heat capacity (kJkg -1 K -1 ) Organic 1.8 Inorganic 1.0 Ammonia 27% 3.9 Water 4.2 Process data Charge Compound Mass kmol Molar ratio (kg) 1-Chloro-4- nitro-benzene 423 2.7 1 Ammonia 27% 2024 32.1 12 (pure NH 3 ) Total 2447 Remember the following approximate values of specific heat capacities for different compound classes: Compound Specific heat capacity (kJkg -1 K -1 ) Organic compounds 1.8 (fused or in solution) Inorganic 1.0 Ammonia 27% 3.9 Water 4.2 Answer this question: According to process data shown opposite, what is the specific heat capacity of the reaction mixture? (Units should be kJkg -1 K -1 ) Process data Charge Compound Mass kmol Molar ratio (kg) 1-Chloro-4- nitro-benzene 423 2.7 1 Ammonia 27% 2024 32.1 12 (pure NH 3 ) Total 2447 Remember the following approximate values of specific heat capacities for different compound classes: Compound Specific heat capacity (kJkg -1 K -1 ) Organic compounds 1.8 (fused or in solution) Inorganic 1.0 Ammonia 27% 3.9 Water 4.2 Answer this question: According to process data shown opposite, what is the specific heat capacity of the reaction mixture? (Units should be kJkg -1 K -1 ) Right answer: The specific heat capacity of the reaction mixture is 3.5 kJkg -1 K -1 Lesson 1 In a preliminary evaluation (SCREENING) of the severity of the chemical process under study the following data are already known: Heat of the desired reaction QR = 250 kJkg -1 Heat of the decomposition reaction QD = 500 kJkg -1 Specific heat capacity of the reaction mixture Cp = 3.5 kJkg -1 K -1 These results are summarized in risk analysis forms 1 and 2. Remark The following procedure is suggested for estimating the specific heat capacity of the reaction mixture. Table of data Compound Cp M MCp (kJkg -1 K -1 ) (kg) (kJK -1 ) 1-Chloro-4- 1.8 423 761.4 nitro-benzene Ammonia 27% 3.9 2024 7893.6 Total 2447 8655 Cp Specific heat capacity of the reaction mixture (kJkg -1 K -1 ) Mi Mass of a compound (kg) Cpi Specific heat capacity of a compound (kJkg -1 K -1 ) MR Total mass of the reaction mixture (kg) Cp MiCpi MR = = 8655 2447 = 3.5 kJkg -1 K -1 Specific heat capacity calculation Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 POTENTIAL Heat of reaction Specific heat capacity Adiabatic Temperature Rise (Ratio Q R / Cp) Q R = 250 kJ/kg Cp = 3.5 kJ/kg/K Tad = C Highest theoretical attainable temperature in case adiabatic conditions occur: C Total gas evolution: l/kg l/batch Source of data: Consequences of allowing adiabatic reaction (Check appropriate boxes) Harmless temperature rise Boiling (Bp = C) Gas release Critical temperature rise Decomposition Pressure build up Other : Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 POTENTIAL Heat of reaction Specific heat capacity Adiabatic Temperature Rise (Ratio Q R / Cp) Q R = 250 kJ/kg Cp = 3.5 kJ/kg/K Tad = C Highest theoretical attainable temperature in case adiabatic conditions occur: C Total gas evolution: l/kg l/batch Source of data: Consequences of allowing adiabatic reaction (Check appropriate boxes) Harmless temperature rise Boiling (Bp = C) Gas release Critical temperature rise Decomposition Pressure build up Other : Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Lesson 1 In a preliminary evaluation (SCREENING) of the severity of the chemical process under study the following data are already known: Heat of the desired reaction QR = 250 kJkg -1 Heat of the decomposition reaction QD = 500 kJkg -1 Specific heat capacity of the reaction mixture Cp = 3.5 kJkg -1 K -1 The adiabatic temperature rise of the decomposition reaction will be determined in the next step of lesson 1. Lesson 1 The adiabatic temperature rise of a reaction is calculated by dividing the heat of reaction by the specific heat capacity of the reaction mixture. Example The adiabatic temperature rise of a high exothermic decomposition reaction having a heat of reaction of 2000 kJkg -1 in a reaction mixture with 2 kJkg -1 K -1 specific heat capacity is: Tad = QR Cp = 2000 2 = 1000 C Tad adiabatic temperature rise (K or C) QR heat of reaction (kJkg -1 ) Cp specific heat capacity (kJkg -1 K -1 ) Remember For the process under study, the following data are already known: Heat of the desired reaction QR = 250 kJkg -1 Heat of the decomposition reaction QD = 500 kJkg -1 Specific heat capacity of the reaction mixture Cp = 3.5 kJkg -1 K -1 Lesson 1 The adiabatic temperature rise of a reaction is calculated by dividing the heat of reaction by the specific heat capacity of the reaction mixture. Example The adiabatic temperature rise of a high exothermic decomposition reaction having a heat of reaction of 2000 kJkg -1 in a reaction mixture with 2 kJkg -1 K -1 specific heat capacity is: Tad = QR Cp = 2000 2 = 1000 C Tad adiabatic temperature rise (K or C) QR heat of reaction (kJkg -1 ) Cp specific heat capacity (kJkg -1 K -1 ) Remember For the process under study, the following data are already known: Heat of the desired reaction QR = 250 kJkg -1 Heat of the decomposition reaction QD = 500 kJkg -1 Specific heat capacity of the reaction mixture Cp = 3.5 kJkg -1 K -1 Answer this question: What is the adiabatic temperature rise of the decomposition reaction? (Units should be K) Lesson 1 The adiabatic temperature rise of a reaction is calculated by dividing the heat of reaction by the specific heat capacity of the reaction mixture. Example The adiabatic temperature rise of a high exothermic decomposition reaction having a heat of reaction of 2000 kJkg -1 in a reaction mixture with 2 kJkg -1 K -1 specific heat capacity is: Tad = QR Cp = 2000 2 = 1000 C Tad adiabatic temperature rise (K or C) QR heat of reaction (kJkg -1 ) Cp specific heat capacity (kJkg -1 K -1 ) Remember For the process under study, the following data are already known: Heat of the desired reaction QR = 250 kJkg -1 Heat of the decomposition reaction QD = 500 kJkg -1 Specific heat capacity of the reaction mixture Cp = 3.5 kJkg -1 K -1 Answer this question: What is the adiabatic temperature rise of the decomposition reaction? (Units should be K) Right answer: The adiabatic temperature rise of the decomposition reaction is 143 K Lesson 1 The adiabatic temperature rise of the decomposition reaction is a direct measure of the severity of a possible incident. As a guideline, the following values can be used Severity Adiabatic temperature rise HIGH Tad > 200 C MEDIUM 50 C < Tad < 200 C LOW Tad < 50 C (1) (1) where the boiling point is not reached Remember In the previous step of lesson 1 the adiabatic temperature rise due to the decomposition reaction was calculated. Its value is 143 C. Answer this question: What is the severity of a potential incident? (Type HIGH, MEDIUM or LOW) Lesson 1 The adiabatic temperature rise of the decomposition reaction is a direct measure of the severity of a possible incident. As a guideline, the following values can be used Severity Adiabatic temperature rise HIGH Tad > 200 C MEDIUM 50 C < Tad < 200 C LOW Tad < 50 C (1) (1) where the boiling point is not reached Remember In the previous step of lesson 1 the adiabatic temperature rise due to the decomposition reaction was calculated. Its value is 143 C. Answer this question: What is the severity of a potential incident? (Type HIGH, MEDIUM or LOW) Right answer: The severity of a potential incident is MEDIUM Lesson 1 The conclusion of the initial steps of lesson 1 is that the severity of a possible incident in the process is MEDIUM. Lesson 1 The severity of a possible incident in the process is MEDIUM due to the amount of energy which can be released by the decomposition reaction. The adiabatic temperature rise is a direct measure of this energy potential. Data used for the assessment of severity are summarized in risk analysis form 2. Case study : Batch reaction Thermal Stability BASIC DATA FOR RISK ANALYSIS FORM 2 Severity: Energy potential of relevant decomposition reactions: 500 kJ/kg Specific heat capacity of reaction mass: 3.5 kJ/kg/K Adiabatic temperature rise: 143 C Boiling point of reaction mass (if relevant): C Gas evolution: m 3 /batch Known decomposition products: Source of data: Assessment of severity: Low Medium High Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Case study : Batch reaction Thermal Stability BASIC DATA FOR RISK ANALYSIS FORM 2 Severity: Energy potential of relevant decomposition reactions: 500 kJ/kg Specific heat capacity of reaction mass: 3.5 kJ/kg/K Adiabatic temperature rise: 143 C Boiling point of reaction mass (if relevant): C Gas evolution: m 3 /batch Known decomposition products: Source of data: Assessment of severity: Low Medium High Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Case study : Batch reaction Lesson 1 Rough estimate of probability Lesson 1 The conclusion of the initial steps of lesson 1 is that the severity of a possible incident in the process is MEDIUM. The next step of lesson 1 is to make a rough assessment of the probability of triggering the decomposition reaction in the event of loss of control of the desired reaction. Tad, R adiabatic temperature rise of the desired reaction(C). Tmax, R maximum attainable temperature if the desired reaction occurs under adiabatic conditions (C). Lesson 1 To give a rough estimate of the probability of triggering the decomposition reaction in the event of loss of control of the desired reaction, the following data should be determined: Lesson 1 Use the equation below to calculate the adiabatic temperature rise of the desired reaction. The parameters which are already known are given. Tad, R = QR Cp Tad, R adiabatic temperature rise of the desired reaction (K or C) QR heat of the desired reaction ( 250 kJkg -1 ) Cp specific heat capacity of the reaction mixture ( 3.5 kJkg -1 K -1 ) Lesson 1 Use the equation below to calculate the adiabatic temperature rise of the desired reaction. The parameters which are already known are given. Tad, R = QR Cp Tad, R adiabatic temperature rise of the desired reaction (K or C) QR heat of the desired reaction ( 250 kJkg -1 ) Cp specific heat capacity of the reaction mixture ( 3.5 kJkg -1 K -1 ) Answer this question: What is the adiabatic temperature rise of the desired reaction? (Units should be K) Lesson 1 Use the equation below to calculate the adiabatic temperature rise of the desired reaction. The parameters which are already known are given. Tad, R = QR Cp Tad, R adiabatic temperature rise of the desired reaction (K or C) QR heat of the desired reaction ( 250 kJkg -1 ) Cp specific heat capacity of the reaction mixture ( 3.5 kJkg -1 K -1 ) Answer this question: What is the adiabatic temperature rise of the desired reaction? (Units should be K) Right answer: The adiabatic temperature rise of the desired reaction is 71 K Lesson 1 Use the equation below to calculate the maximum attainable temperature if the desired reaction occurs under adiabatic conditions. The parameters which are already known are given. Tmax, R maximum attainable temperature if the desired reaction occurs under adiabatic conditions (C) Tp process temperature (195C) Tad, R adiabatic temperature rise of the desired reaction ( 71C) Tmax, R = Tp + Tad, R Answer this question: What is the maximum attainable temperature if the desired reaction runs under adiabatic conditions? (Units should be C) Lesson 1 Use the equation below to calculate the maximum attainable temperature if the desired reaction occurs under adiabatic conditions. The parameters which are already known are given. Tmax, R maximum attainable temperature if the desired reaction occurs under adiabatic conditions (C) Tp process temperature (195C) Tad, R adiabatic temperature rise of the desired reaction ( 71C) Tmax, R = Tp + Tad, R Answer this question: What is the maximum attainable temperature if the desired reaction runs under adiabatic conditions? (Units should be C) Right answer: The maximum attainable temperature if the desired reaction runs under adiabatic conditions is 266C Tad, R: adiabatic temperature rise of the desired reaction(71C). Tmax, R: maximum attainable temperature if the desired reaction occurs under adiabatic conditions (266C). Lesson 1 To give a rough estimate of the probability of triggering the decomposition reaction in the event of loss of control of the desired reaction, the following data are already known: These results should be summarized in risk analysis form 1. Case study : Batch reaction Lesson 1 Rough estimate of probability Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 POTENTIAL Heat of reaction Specific heat capacity Adiabatic Temperature Rise (Ratio Q R / Cp) Q R = 250 kJ/kg Cp = 3.5 kJ/kg/K Tad = 71 C Highest theoretical attainable temperature in case adiabatic conditions occur: 266C Total gas evolution: l/kg l/batch Source of data: Consequences of allowing adiabatic reaction (Check appropriate boxes) Harmless temperature rise Boiling (Bp = C) Gas release Critical temperature rise Decomposition Pressure build up Other : Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 POTENTIAL Heat of reaction Specific heat capacity Adiabatic Temperature Rise (Ratio Q R / Cp) Q R = 250 kJ/kg Cp = 3.5 kJ/kg/K Tad = 71 C Highest theoretical attainable temperature in case adiabatic conditions occur: 266C Total gas evolution: l/kg l/batch Source of data: Consequences of allowing adiabatic reaction (Check appropriate boxes) Harmless temperature rise Boiling (Bp = C) Gas release Critical temperature rise Decomposition Pressure build up Other : Lesson 1 Use risk analysis forms 1 and 2 to summarize the results Lesson 1 In the event of loss of thermal control of the desired reaction, the temperature will rise until 266C. The next step in making a rough estimate of the probability of triggering the decomposition reaction, is to determine if at this temperature (266C) the decomposition reaction is active enough to produce an incident, in a time too short to take counter-measures. Case study : Batch reaction Lesson 1 Rough estimate of probability Lesson 1 Taking account of experimental conditions, one can assume that if the trace of the decomposition reaction shows an observable signal at 266C, then at this temperature this reaction is active enough to produce an incident in a time too short (minutes) to take counter- measures. Lesson 1 In the final reaction mixture thermogram, the signal corresponding to the decomposition reaction is detected at 235C. Final reaction mixture thermogram: Quantitative differential thermal analysis of final reaction mixture. Remark: This assumption depends on the sensitivity of the measuring instrument (10 Wkg -1 ) and the scan rate (4Cmin -1 ). -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2 0 100 200 300 400 -500 kJkg -1 +30 kJkg -1 Heat release rate (Wg -1 ) scan rate: 4Cmin -1 Temperature (C) 235C Tmax,R=266C Lesson 1 A rough estimate indicates that at the maximum temperature attainable on loss of control of the desired reaction (266C) , the decomposition reaction will give rise to an incident in a very short time (minutes). This means that in a preliminary approximation (SCREENING), the probability of triggering the decomposition reaction is HIGH. Lesson 1 Remark Remark Morever, the overlapping signals of the heat of the desired reaction and the heat of the decomposition reaction in the final reaction mixture thermogram gives a clear evidence that the PROBABILITY of triggering the decomposition reaction is HIGH. Lesson 1 Pressure build up related to the Pressure build up related to the process... process... The pressure build up caused by uncontrolled heat release of the desired and decomposition reactions is an important risk especially in industrial synthesis reactions performed under pressure. To assure a safe design of the process and the plant including the choice of an appropriate pressure relief system, it is indispensible to know the maximum pressure that can be reached in the event of a failure. We will study it later in lesson3. Case study : Batch reaction Lesson 1 Pressure build-up Lesson 1 Maximum Temperature for Maximum Temperature for Technical reasons (MTT)... Technical reasons (MTT)... In order to complete the consequences of loss of thermal control of the desired reaction, we must consider if the Maximum Temperature for Technical reasons (MTT) could be reached in the event of a failure. The Maximum Temperature for Technical reasons is the temperature at which the pressure reaches the maximum permissible value. In the case under study, the reactor is equipped with a safety valve. The safety limit of this valve will be attained if the temperature of the reactor attains 200C. Lesson 1 Potential at the Maximum Potential at the Maximum Temperature for Technical Temperature for Technical reasons (MTT)... reasons (MTT)... As the process temperature is 195C, only 5C of the 71C adiabatic temperature rise of the desired reaction is needed to reach the Maximum Temperature for Technical reasons (MTT = 200C). Consequently, the remaining energy potential of the desired reaction will be still high at this point. Lesson 1 According to the results of a preliminary evaluation of the thermal risks of the process under study (SCREENING), the consequences of a loss of thermal control over the synthesis reaction may lead to a critical situation: - the Maximum Temperature for Technical reasons (MTT) will be reached - at this point, the potential of the desired reaction is still high: there exists a risk of pressure build up - the decomposition reaction will be triggered. The results obtained in lesson 1 should be summarized in risk analysis forms 1 and 2. Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 POTENTIAL Heat of reaction Specific heat capacity Adiabatic Temperature Rise (Ratio Q R / Cp) Q R = 250 kJ/kg Cp = 3.5 kJ/kg/K Tad = 71 C Highest theoretical attainable temperature in case adiabatic conditions occur: 266C Total gas evolution: l/kg l/batch Source of data: Consequences of allowing adiabatic reaction (Check appropriate boxes) Harmless temperature rise Overpressure (MTT = 200C) Gas release Critical temperature rise Decomposition Pressure build up Other : Lesson 1 Conclusions Case study : Batch reaction Thermal Data of Reaction BASIC DATA FOR RISK ANALYSIS FORM 1 POTENTIAL Heat of reaction Specific heat capacity Adiabatic Temperature Rise (Ratio Q R / Cp) Q R = 250 kJ/kg Cp = 3.5 kJ/kg/K Tad = 71 C Highest theoretical attainable temperature in case adiabatic conditions occur: 266C Total gas evolution: l/kg l/batch Source of data: Consequences of allowing adiabatic reaction (Check appropriate boxes) Harmless temperature rise Overpressure (MTT = 200C) Gas release Critical temperature rise Decomposition Pressure build up Other : Lesson 1 Conclusions Case study : Batch reaction Thermal Stability BASIC DATA FOR RISK ANALYSIS FORM 2 Severity: Energy potential of relevant decomposition reactions: 500 kJ/kg Specific heat capacity of reaction mass: 3.5 kJ/kg/K Adiabatic temperature rise: 143 C Maximum Temperature for Technical reasons (MTT): 200 C Gas evolution m 3 /batch Known decomposition products: Source of data: Assessment of severity: Low Medium High Lesson 1 Conclusions Case study : Batch reaction Thermal Stability BASIC DATA FOR RISK ANALYSIS FORM 2 Severity: Energy potential of relevant decomposition reactions: 500 kJ/kg Specific heat capacity of reaction mass: 3.5 kJ/kg/K Adiabatic temperature rise: 143 C Maximum Temperature for Technical reasons (MTT): 200 C Gas evolution m 3 /batch Known decomposition products: Source of data: Assessment of severity: Low Medium High Lesson 1 Conclusions