DETAILED PROJECT PLAN

Transcription

1 Proposal No. EVG SAFEKINEX 1 PROGRAMME ENERGY, ENVIRONMENT AND SUSTAINABLE DEVELOPMENT Call identifier: EESD-ESD-3 (JO 2000/C 324/09) Project No. EVG SAFEKINEX DETAILED PROJECT PLAN TABLE OF CONTENTS 1 INTRODUCTION WORK PACKAGE NR. 2 EXPERIMENTS ON EXPLOSION SAFETY INTRODUCTION TO THE EXPERIMENTS EXPERIMENTAL DETERMINATION OF THE IGNITION DELAY TIME IDT (AIT, CFT) EXPERIMENTAL DETERMINATION OF MINIMUM IGNITION ENERGY MIE EXPERIMENTAL DETERMINATION OF EXPLOSION LIMITS (FL) EXPERIMENTAL DETERMINATION OF P EX, P MAX AND (DP/DT) EX SUMMARY AND SAFETY DATABASE WORK PACKAGE NR. 3 MODELLING / PREDICTION OF EXPLOSION INDICES OBJECTIVE: DEVELOPMENT OF MODELS ENABLING THE PREDICTION OF EXPLOSIONS INDICES INTRODUCTION MODELLING OF LAMINAR BURNING VELOCITY MODELLING OF MAXIMUM EXPLOSION PRESSURE MODELLING OF (DP/DT) MAX MODELLING OF AUTOIGNITION TEMPERATURE MODELLING OF FLAMMABILITY LIMITS MODELLING OF MINIMUM IGNITION ENERGY MODELLING OF EXPLOSION PROPAGATION WORK PACKAGE NR. 4 KINETICS MODEL DEVELOPMENT OBJECTIVES : DESCRIPTION OF THE PROPOSED WORK LITERATURE REVIEW (WP WP 4.2.1, FROM MONTH 0 TO MONTH 4) DEVELOPMENT AND VALIDATION OF DETAILED KINETIC MODELS FOR THE OXIDATION OF C1-C3 HYDROCARBONS (WP WP WP WP 4.2.6, FROM MONTH 2 TO MONTH 26) DEVELOPMENT AND VALIDATION OF DETAILED KINETIC MODELS FOR THE OXIDATION OF C4-C10 HYDROCARBONS (WP WP WP WP WP WP 4.3.2, FROM MONTH 2 TO MONTH 30) DEVELOPMENT AND VALIDATION OF DETAILED KINETIC MODELS FOR THE OXIDATION OF AROMATIC HYDROCARBONS (WP WP 4.3.3, FROM MONTH 10 TO MONTH 34) WORK PACKAGE NR. 5 REDUCTION METHODS AND VALIDATION OBJECTIVES : DESCRIPTION OF THE PROPOSED WORK

2 Proposal No. EVG SAFEKINEX MILESTONES AND CRITERIA WORK PACKAGE NR. 6 TRANSFER OF RESULTS INTO INDUSTRIAL APPLICATION WORK PACKAGE NR. 7 MANAGEMENT DISCUSSION AND CONCLUSION...31

3 Proposal No. EVG SAFEKINEX 3 1 INTRODUCTION In the Description of Work of 23 September 2002 of the SAFEKINEX project the Work Package organisation of the project, the overview of effort of the various partners with respect to Work Package tasks and timing was given. Also the list of deliverables has been presented. In fact this report is the first deliverable of the project. This Detailed Project Plan has been drafted based on the contributions of the Work Package leaders (lead partner) after discussing the work at the kick-off meeting in Delft at February 11, An overview of the Work Packages is given in Table 1. Table 1-1: Work Package list WP No. Work Package title WPL Work Package list Lead Personmonths Start Partner month No. End month Deliverable No. 1 Initialisation TUDelft Experiments on explosion BAM ,3,4,5,6,7,8,9,10, safety 11,12 and 13 3 Modelling / prediction of explosion indices WUT ,15,16, 17,18,19,20,21,22 23, 24, and 25 4 Kinetics model development CNRS ,27,28,29,30,31 32,33,34,35 and 36 5 Reduction methods and UL and 38 validation 6 Transfer of results into TUDelft ,46,47,48 and industrial applications 49 7 Management TUDelft and 51 TOTAL 617 For convenience the list of deliverables is reproduced here as well, see Table 1-2. Work package 1 is not considered here anymore. The product is this report. Since the bulk of the project effort concerns Work packages 2, 3, and 4, this Detailed Work Plan is restricted to these parts. Work package 5 is concise and treated here only briefly. The same is true for WP 6. For a further overview of the Work packages divided in tasks and the time schedule planned, see Table 1-3

4 Proposal No. EVG SAFEKINEX 4 Table 1-2: Deliverable list Deliverable list Delivera Delivery Nature 2 Dissemination level 3 Deliverable title and brief description -ble No. date 1 1 Detailed project plan (including task description of 2 O PU benchmarking problems) 2 Report on experimental factors influencing explosion 6 Re, Da, PU indices determination (further experimental work plan distribution and description), Me 3 Control software (high frequency multi-channel data collection, accurate signal generation) for the explosion tests apparatus 20 O RE 4 Validated data acquisition software, software with 30 O, Me RE incorporated new features for data fitting and numerical analysis 5 Report on experimentally determined self-ignition 8 Re, Da, RE temperature and the ignition delay time (constant volume Me apparatuses) 6 Report on experimentally determined Markstein numbers 10 Re, Da, RE Me 7 Report on experimentally MIE as function of P, fuel type 20 Re, Da, RE and concentration Me 8 Report on experimentally determined flammability limits as 26 Re, Da, RE a function of pressure Me 9 Report on experimentally determined flammability limits as 30 Re, Da, RE a function of temperature Me 10 Report on experimentally determined P max and (dp/dt) max 36 Re, Da, RE as a function of pressure and equivalence ratio Me 11 Report on experimentally determined P max and (dp/dt) max 40 Re, Da, RE as a function of temperature and equivalence ratio Me 12 Data base of explosion indices (software) 38 Da RE 13 Report on determination of non-standardised explosion 46 Re, Da, RE parameters or provided by industrial end-users Me 14 Model and software development for calculation of laminar 14 Si, Th RE burning velocity (software) 15 Validation of laminar burning velocity model 34 Si, Da, RE Me 16 Calculation of the maximum explosion pressure 14 Si, Th RE 17 Tool for calculation of (dp/dt) max and its validation 38 Si, Th RE 18 Model, software for calculation of AIT and its validation 44 Si, Th RE 19 Model, software for calculation of flammability limits and 40 Si, Th RE its validation 20 Model, software for calculation of Markstein numbers and 32 Si, Th RE its validation 21 Model, software for calculation of MIE and its validation 42 Si, Th RE 22 Explosion propagation model, software development. First report on influence of obstacles, turbulence and fuel concentration, spherical vessels. 26 Re, Si, Th RE 23 Explosion propagation model, software development. Second report on influence of obstacles, turbulence and 32 Re, Si, Th RE 1 Month in which the deliverable will be available. Month 0 marking the start of the project and all delivery dates being related to this starting date. 2 Nature of deliverable: Re report, Da data set, Eq equipment, Pr prototype, Si simulation, Th theory, De demonstrator, Me Methodology, O - others 3 Indication of the dissemination level using one of the following codes: PU Public, RE Restricted to a group specified by the consortium (refereed to consortium agreement), CO Confidential, only for some members of the consortium.

5 Proposal No. EVG SAFEKINEX 5 fuel concentration, elongated vessels and (multi-)channels 23 Explosion propagation model, software development. Second report on influence of obstacles, turbulence and fuel concentration, elongated vessels and (multi-)channels 24 Explosion propagation model, software development. Third report; ignition source located in different vessel places and different initial conditions (turbulence, equivalence ratio, fuel type temperature and pressure 25 Model, software developed and validated for calculation of explosion propagation (as function of fuel type, equivalence ratio, turbulence, P, T, obstacles and geometries 26 Report on ongoing progress of C1-C3 detailed kinetic model development 27 Report on ongoing progress of C4-C10 detailed kinetic model development 28 Report on ongoing progress of aromatic hydrocarbon detailed kinetic model development 29 Report on intermediate species concentration during the ignition process 30 Report on experiments needed for kinetic model development (CVB approach) 31 Report on experiments needed for kinetic model development (ST approach) 32 Report on experiments needed for kinetic model development (RCM approach) 33 Report on experiments needed for kinetic model development (high pressure) 32 Re, Si, Th 38 Re, Si, Th 42 Re, Si, Th RE RE RE 16 Re, Si, Th, Da RE 12 Re, Si, RE Th, Da 20 Re, Si, RE Th, Da 16 Re, Si, RE Da 22 Re, Si, RE Da 26 Re RE 28 Re RE 28 Re RE 34 Validated detailed kinetic model for C1-C3 hydrocarbons 26 Si, Th RE 35 Validated detailed kinetic model for C4-C10 hydrocarbons 28 Si, Th RE 36 Validated detailed kinetic model for aromatic 32 Si, Th RE hydrocarbons 37 Kinetic reduction software. Report on reduction 34 Si, Th RE techniques 38 Reduced kinetic models for different classes of problems 36 Si, Th RE 45 4 Workshop materials related to determination methodology 26 De, O RE 46 Teaching materials on P max and laminar burning velocity 24 Re, De, RE O 47 Teaching materials on MIE, AIT and FL 44 Re, De, RE O 49 Workshop materials related to industrial case studies 48 Re, De, RE O 50 Six-monthly brief (management) progress reports 6, 18, Re RE 30, Mid-term progress report 24 Re RE 52 Annual scientific report, edited annual report for 12, 24, Re RE, PU, publication, executive summary and cost statements 36 PU, RE 53 Final report, edited final report for publication, an 48 Re RE, PU, executive summary report, a TIP (Technology PU, RE Implementation Plan) and final cost statements During the kick off meeting the industrial partners expressed their interest in a possible fundamental approach. They preferred this over the determination of some complex nonstandardised explosion parameters. The latter could be too complex to be measured in the limited amount of time. Hence deliverable 13 may not be produced. 4 Numbering interrupted while deliverables of original proposal are not included, see DoW

6 Proposal No. EVG SAFEKINEX 6 No. Table 1-3: Project planning and time table Efforts of all assistant contractors are combined and shown under number 13. WORK PACKAGE / MANPOWER BAR CHART WP description Partner months D1- one day Duration / critical path D - deliverable / M - milestone Partner 1 st year 2 nd year 3 rd year 4 th year For full name of the task see Table TUD CNR S VUB BAM WUT TUW UL UK INER IS BASF Ind Total WP 1 Initialisation State of art inventory - meeting 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 0,5 9,5 1.2 Grouping of end-users into thematic groups D1 D1 D1 D1 D1 D1 D1 D1 D1 D1 D1 0,5 1.3 Detailed project plan description 1 D1 D1 D1 D1 D1 D1 D1 D1 D1 D1 1,5 D WP 2 Experiments on explosion safety Detailed analysis of experimental factors influencing explosion indices determination 4,5 4,0 6,0 5,2 19,7 D Supportive software development 0,5 35,5 36,0 D Software validation 0,5 29,9 30,4 D,M WP 2.1 Experimental Determination of the Ignition Delay time (Self-ignition and CFT) The ignition delay time determination as a function of P The ignition delay time determination as a function of T 2,0 2,0 4,0 2,0 2,0 4,0 D WP 2.2 Experimental determination of Minimum Ignition Energy (MIE) Determination of Markstein numbers 7,3 7,3 D Determination of MIE as function of P, fuel type and concentration 10,3 10,3 D WP 2.3 Experimental Determination of Flammability Limits (FL) FL determination as a function of P 8,0 10,5 2,2 *) 8,1 2,0 30,8 D FL determination as a function of T 10,0 12,5 12,5 *) 8,1 2,5 45,6 D

7 Proposal No. EVG SAFEKINEX 7 WP 2.4 Experimental Determination o Pmax and (dp/dt)max Pmax and (dp/dt)max determination as a function of P Pmax and (dp/dt)max determination as a function of T 5,5 9,0 7,0 *) 8,1 1,0 30,6 D 5,5 9,0 7,0 *) 7,7 1,0 30,2 D WP 2.5 Summary and safety database Data base of explosion indices (software) 5,5 D Summary of safety experimental part Meeting Additional Experiments, (for end-users/o high conditions) D2 D2 D2 D2 D2 D2 D2 D2 D2 0,5 M 3,0 3,0 4,3 *) 4,6 14,9 D,M WP 3 Modelling / Predictions of Explosion Indices Laminar burning velocity 4,0 4,0 8,0 D D 3.2 Maximum explosion pressure 2,0 5,0 7,0 D 3.3 (dp/dt)max 13,0 5,0 18,0 D 3.4 Auto-Ignition Temperature 4,0 4,0 4,0 12,0 D 3.5 Flammability limits 5,0 5,0 10,0 D 3.6 MIE using Markstein numbers 12,4 12,4 D D 3.7 Explosion propagation as function of fuel type, concentration, 0,0 turbulence, obstacles and different 31,5 31,5 D D D D geometries 3.8 Evaluation - Meeting D1 D1 D1 D1 D1 D1 D1 D1 D1 D1 D1 0,5 M WP 4 Kinetics model development Literature review 2,0 2,0 0,5 4, C1-C3 combined with experiments 14,2 2,0 16,2 D C4-C10 EXGAS generation (alkanes and alkenes) C4-C10 EXGAS generation (benzene, toluene, xylene) 10,3 4,3 14,6 D 10,2 2,0 12,2 D WP 4.2 Acquisition of the relevant experimental data

8 Proposal No. EVG SAFEKINEX Definition of the most relevant experimenta data for validation (meeting) D1 2,0 D1 D1 D1 D1 D Sampling and sample analysis (species determination) 9,0 5,0 14,0 D Experiments needed for kinetic mode 6,0 7,0 6,1 19,1 D development (CVB) Experiments needed for kinetic mode 5,0 5,0 D development (ST) Experiments needed for kinetic mode 8,5 8,5 D, M development (RCM) Laminar flame study 8,0 8,0 WP 4.3 Validation of the Detailed Kineti Models Validation of C1-C3 mechanisms 1,0 2,5 10,0 2,0 15,5 D,M Validation of C4-C10 mechanisms 1,0 16,0 0,5 4,2 21,7 D,M Validation of aromatic mechanisms 1,0 13,0 0,5 2,0 16,5 D,M WP 4.4 Additional Experiments Experiments at higher pressure. 1,0 1,1 2, Experiments at higher pressure and temperature. D WP 5 Reduction Methods and their Validation 5.1 Formal reduction and lumping approaches, reaction sensitivity 5.2 Comparisons between reduced and full scheme validation and further development 0,5 1,0 0,5 11,0 13,0 D 0,5 1,0 0,5 4,1 6,1 D, M 16 WP 6 Transfer of results into industrial applications Appraisal of results by industrial end-user 1/use r 0, Workshop on experimental, safety part 0,5 0,5 0,5 0,5 0,5 0,5 0,5 0,5 1,0 5,0 D Workshop on Pmax, Laminar burning velocity 1,0 1,0 1,0 1,0 4,0 D Workshop on MIE, AIT, FL 1,0 1,0 1,0 1,0 0,5 1,0 5,5 D Workshop on explosion propagation and CFD 1,0 1,0 0,5 2,5 D 6.2 Workshop on industrial case studies 1,0 1,0 0,5 1,0 1,0 0,5 0,5 1,0 1,0 1,0 1,0 9,5 D

9 Proposal No. EVG SAFEKINEX Dissemination of results (mini Explo-Risk) 1,0 1,0 D WP 7 Management Overall project co-ordination ,0 7.2 Meetings organisation and co-ordination ,0 7.3 Progress reports 8.5 5,5 Total man-months 110,5 70,0 48,2 67,6 93,0 72,9 53,6 33,5 50,9 8,0 5,5 614 In year 1 31,0 21,5 17,8 18,4 22,5 12,1 9,2 8,2 8,5 2,0 1,6 6 m 12 m 18 m 24 m 30 m 36 m 42 m 48 m In year 2 32,9 21,5 13,8 20,1 28,5 24,2 22,8 10,4 15,8 2,0 1,2 In year 3 25,8 20,3 13,8 20,0 29,5 24,2 17,8 10,4 17,8 2,0 1,1 Mid-term Final In year 4 20,8 6,5 2,8 8,9 12,5 12,4 3,9 4,7 8,8 2,0 1,8 Reporting periods *) Experiment control and data acquisition equipment developed by partner TUW will be used until the end of the project. Partner TUW will be involved in trouble shooting when needed. At the kick-off meeting is for the same kind of reasons as for abandoning deliverable 13 decided to leave out work on industrial cases and in that case task 6.2 will not be executed.

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11 Project No. EVG SAFEKINEX 11 2 WORK PACKAGE NR. 2 EXPERIMENTS ON EXPLOSION SAFETY Table 2-1: Description of Work Package nr. 2 WORK PACKAGE DESCRIPTION Work package Title: Experiments on explosion safety WP nr: 2 Starting data: 1 Duration: 46 months Total Effort (man/month): 267 Partners involved R & D Task / Activity of Effort (man/month) Partner TUD Task 2.0.1, 2.0.2, 2.0.3, 2.1.1, , 2.3.1, 2.3.2, 2.4.1, 2.4.2, 2.5.2, BAM Task 2.0.1, 2.1.1, 2.1.2, 2.3.1, , 2.4.1, 2.4.2, 2.5.2, WUT Task 2.0.1, 2.3.1, 2.3.2, 2.4.1, , 2.5.2, TUW Task 2.0.2, 2.0.3, 2.5.1, 2.5.2, UL Task UK Task 2.2.1, INERIS Task 2.0.1, 2.3.1, 2.3.2, 2.4.1, , 2.5.2, BASF Task 2.3.1, 2.3.2, 2.4.1, 2.4.2, Shell Task Objectives Determination of minimum volume of the explosion test apparatus at which cooling effect of the walls is negligible. Development of supportive software (data acquisition and database software) Experimental determination of explosion indices (IDT, AIT and CFT, Markstein number and MIE, FL, P max, (dp/dt) max ) as a function of P, T, fuel type and equivalence ratio ( ) Creation of explosion indices database Description of explosion indices determination methodology at super-ambient condition Description of work / tasks 2.1 Experimental work plan drafting amongst partners. 2.2 Development of supportive software (data acquisition and database software) 2.3 Experimental determination of the IDT, AIT and CFT as function of P,T, fuel type and 2.4 Experimental determination of the Markstein number and MIE as function of P, fuel type and 2.5 Experimental determination of the FL as function of P,T, fuel type and 2.6 Experimental determination of the P max and (dp/dt) max as function of P,T, fuel type and 2.7 Explosion parameters database (as function of P,T, fuel type and ) 2.8 Description of explosion indices determination methodology at super-ambient conditions TUD, BAM, WUT, INERIS and BASF have explosion test apparatus of different volume ( dm 3 ), operational conditions and different construction. This combination gives a unique opportunity to study factors influencing the determination of explosion indices. After identification of the influence further experimental work will be defined. Experiments will cover wide temperature, pressure, fuel type and equivalence ratio in order to obtain comprehensive data input for explosion models validation. All experiments will be incorporated into database. Special attention will be paid to the heat transfer during self-ignition processes and processes where flame propagation is slow. This is crucial for cool flame, flammability limits, and two-stage phenomena. Thus experiments will be carried out in quiescent and turbulent initial stage, before an explosion. Determination of the proper vessel size will be supported by thermodynamic calculation of the adiabatic flame temperatures. The post explosion mixture will be chemically analysed for comparison of species concentration, especially at fuel rich concentrations.

12 Project No. EVG SAFEKINEX 12 Deliverables 1. Report on experimental factors influencing explosion indices determination 2. Validated control software (high frequency multi-channel data collection, accurate signal generation) for the explosion tests apparatus 3. Reports on experimentally determined explosion sensitivity and severity indices as function of P,T, fuel type and : (1) IDT, AIT (2) CFT (3) Markstein numbers, MIE (4) FL (5) P max and (dp/dt) max 4. Database of explosion indices 5. Description of explosion indices determination methodology at super-ambient conditions 6. Determination of non-standardised explosion parameters or provided by industrial end-users Milestones and criteria 1. Ready to use software controlling operations of the test apparatus / Data acquisition software Criterion: High recording frequency and storage of in-going signal data, High time resolution for out going signals, It meets the design requirements, Approved by users 2. Explosion indices data and database 3. Description of explosion indices determination methodology at super-ambient conditions Criterion: Approval of all partners and end-users Interrelation with other work packages The experimental results of this work package will be used for validation of the explosion models and kinetic models developed in work package 3 and 4, to reduced kinetic models (WP5) 2.1 Introduction to the experiments Detailed analysis of experimental factors influencing explosion indices determination (TUD, BAM, WUT, BASF) 1. Detailed analysis of experimental parameters will be undertaken by literature study and additional experiments. Explosion indices depend on many parameters. In order to get a fundamental database of explosion indices with comparable and also reproducible values which are determined by all participant "internal standard methods" will be worked out by TUD (IDT and AIT) and BAM (FL, p ex, p max,(dp/dt) ex ) after consultation of all involved participants. Within these standard methods fixed parameters will be defined in detail like: explosion vessel geometry and volume. Further parameters to be determined are : 2. ignition source: kind of, position and ignition energy E i 3. initial conditions (temperature, pressure) 4. fuel/oxidiser type and concentration 5. direction of flame propagation 6. turbulence conditions 7. explosion criterion 8. sampling frequencies 9. smoothing techniques of recorded signals 10. residence time of mixture before ignition for experiments at elevated conditions 11. catalytic effect of the vessel walls surface for experiments at elevated conditions Supportive software development (TUD, TUW) Special software for the data acquisition for the determination of explosion indices will be developed. For an accurate data acquisition it is necessary to reach a high recording frequency and the storage of in-going signal data. It is planned to develop software for the data acquisition on at least 14 to 17 different channels, for example 3 channels for pressure, 6 channels for temperature, 2 channels for voltage and current during the ignition process (determination of ignition energy), 3 channels for a signal check and 2-3 channels for free use (reserve). At the end of the acquisition the data should be saved and on basis of the pressure/time-, temperature/time-, current/time- and voltage/time-course the maximum

13 Project No. EVG SAFEKINEX 13 explosion pressure p ex, the maximum pressure rise (dp/dt) ex and the ignition energy will be calculated Software validation (TUD, TUW) Especially for testing of the developed software some additional experiments will be carried out in order to validate the software. If necessary the last modifications have to be done. The end-user have to prove the software in detail. 2.2 Experimental determination of the ignition delay time IDT (AIT, CFT) IDT as function of pressure and temperature (BAM,TUD, INERIS) The ignition delay time (IDT) for self-ignition processes of methane, ethylene and n-butane will be determined in a 0.2-l-autoclave (stainless steel) at initial pressures of p 0 = 1 bar(a), 5 bar(a), 10 bar(a), and 30 bar(a). As criterion of an ignition the pressure rise and temperature rise inside the autoclave is used. The IDT will be determined for at least three different fuel gas/air mixtures. This program is limited to three fuel gas concentration because of the high experimental effort necessary for the determination. Limited number of experiments may be performed in a 100 times larger vessel volume at TUD to determine the scaling up mixture behaviour (heat release rate, surface interactions, etc). Even larger scaling up experiments in 2000 l may be performed by INERIS IDT as a function of temperature (TUD) The ignition delay time (IDT) for auto-ignition processes of methane, ethylene and n-butane in dependence of their concentrations in air will be determined in a 0.1 l, 0.2 l and a 0.5 l- vessel (quartz) at an initial pressure of p 0 = 1 bar(a). In case of the 0.2-l-volume the results in the quartz vessel shall be compared to the results obtained in the stainless steel vessel at an initial pressure of p 0 = 1 bar(a). In this way the wall surface influence on AIT and IDT will be determined. 2.3 Experimental determination of minimum ignition energy MIE Determination of Markstein Numbers (UK) The existing literature will be analysed in order to find or to calculate Markstein numbers for the fuel gases CH 4, C 2 H 6 and C 3 H 8 using the available data of the literature. These Markstein-Numbers will be compared to experimental determined values. For this reason the flame velocity of a stretched flame will be analysed. The flame velocity is determined by using a bomb method (pressure rise analysis). Therefore it is necessary to build a new small vessel in order to produce flames with a large curvature rate Determination of MIE as a function of pressure, combustible and concentration (UK) The minimum ignition energy MIE will be determined for the fuel gases CH 4, C 2 H 6 and C 3 H 8. In the existing literature the minimum ignition energy is only given for fuel gases in an optimal mixture with air (in most cases near the stoichiometric mixture) and only at ambient conditions. The MIE for these gases will be determined for initial pressures of p 0 = 1 bar(a) up to p 0 = 10 bar(a) and initial temperatures up to 300 C. An important point will also be the determination of the MIE for ternary fuel gas/inert gas/air mixtures as a function of the amount of inert gas (N 2, CO 2 ).

14 Project No. EVG SAFEKINEX Experimental determination of explosion limits (FL) FL as a function of pressure at min. 3 initial temperatures (TUD, BAM, BASF) This point will be split into two parts. The first one treats the determination of the pressure dependence close to explosion limits of fuel gas/air mixtures. The explosion limits will be determined at an initial temperature of T 0 = 20 C and initial pressures of p 0 = 1 bar(a), 5 bar(a), 10 bar(a), 30 bar(a) and in a few cases also for p 0 = 100 bar(a). The following fuel gases will be examined: 1. alkane: CH 4, C 2 H 6, C 3 H 8,C 4 H alkene: C 2 H 4, C 3 H 6 3. other: H 2, CO, (During the kick off meeting we turn down nitrogen chemistry, thus will not be able to establish link between flame propagation and detailed reaction kinetics). Because of the high importance of explosion limits at elevated pressures and temperatures the limits of the fuel gas/air mixtures will also be determined at initial temperatures of T 0 = 100 C and 250 C. If necessary i.e. if extraordinary pressure development is noticed, for some mixtures additional experiment(s) at an initial temperature between T 0 = 100 C and 250 C will be conducted. The main goal is to observe interactions between low temperature oxidation chemistry path and flame propagation. In the second part of the inert gas influence on explosion limits of the above mentioned fuel gases will be examined. As inert gas N 2 will be used. For selected gas systems oxygen will be inserted as oxidator. This point depends strongly on the remaining time within the project. At first the safety characteristics with air should be determined, then the limiting oxygen concentrations will be determined at the same initial conditions (elevated pressures and temperatures) mentioned above (see fig. 1). Only for a few gas systems the explosion limits will be determined at fixed amounts of inert gas (for example 20 mol-% N 2 added to the air) FL as a function of temperature (TUD, BAM, BASF) In the past the temperature dependence of explosion limits has been examined in different research projects and PhD-works at an initial pressure of p 0 = 1 bar(a). Thereby the determination method according to German DIN was used. These experimental data were collected and reported in the databank "CHEMSAFE", a database published by DECHEMA, BAM and PTB. In case of a new examination of the temperature dependence using a test method according to pren 1839 (T) great deviations are not to expect. A comparison of both methods was given by a students work, carried out in BAM. It is more reasonable to determine the pressure dependence on explosion limits ( 2.3.1) and to determine explosion limits for higher initial pressures combined with higher initial temperatures (2.5.3). 2.5 Experimental determination of p ex, p max and (dp/dt) ex The experimental determination of p ex, p max and (dp/dt) ex (also LOC) will be done according to an internal standard method which will be worked out (BAM) after consultation of all involved participants (BASF, WUT, TUW, INERIS, TUD) p ex and (dp/dt) ex as a function of pressure and temperature (TUD, BAM, WUT, INERIS, BASF) The maximum explosion indices shall be determined at the same initial conditions as mentioned under point (p 0 = 1 bar(a), 5 bar(a), 10 bar(a), 30 bar(a); T 0 = 20 C, 100 C, 250 C and one temperature between 100 C and 250 C). The number of experiments

15 Project No. EVG SAFEKINEX 15 for each condition will depend on the observed phenomenon. In the flammable range at given conditions of initial pressure and temperature at least ten experiments without repetition should be conducted including the flammability limit concentrations. If an interesting or non-typical behaviour is observed, for example decelerated pressure evolution, plateau in measured values etc. more experimental points should be performed to examine this behaviour in more detail. The main goal is to observe interactions between low temperature oxidation chemistry path and flame propagation. In fig. 1 the working program for one fixed initial pressure and one initial temperature is shown. The first two steps (examination of fuel gas/air mixtures and LOC) will be done for all proposed gas systems. Especially the third step strongly depends on the remaining time within the project Fig. 1: fuel gas [mol-%] LEL UEL 60 air line 0 p ex, (dp/dt) ex oxygen [mol-%] inert gas [mol-%] LOC 100 Overview of the working program for the determination of FL, p ex, (dp/dt) ex for different gas mixtures at different initial conditions The p ex and (dp/dt) ex values depend on the explosion vessel volume. In order to examine this dependence some of the experiments shall be done in different explosion vessel volumes at the same initial conditions (depending on the strength of explosion vessel). For this exist a 6- l-cylindrical autoclave (BAM), a 14-l-spherical autoclave (BAM), two 20-l-spherical autoclaves (TUD, BASF), a 40-l-spherical autoclave (WUT, p 0 = 1 bar(a) and 2 bar(a)), a 1250-lautoclave (WUT, p 0 = 1 bar(a)) and a 2000-l-autoclave (INERIS). The gas systems and their compositions shall be proposed by the industrial partners. 0

16 Project No. EVG SAFEKINEX Summary and safety database Data base of explosion indices (software) (TUW) A database will be built for the explosion indices which shall be determined in WP 2. This database includes all experimental determined safety related properties and those which can be calculated from the existing experimental data. Tools for different interpolation of the pressure or temperature dependence on some explosion indices, for example LEL and UEL, will be included, so that it is possible to estimate the explosion indices in a non-measured region. The database shall be used for the interrelation with other workpackages. Especially the experimental data is useful for the validation of the explosion models and (reduced) kinetic models, which will be developed in WP 3, WP 4 and WP Summary of safety experimental part meeting (all) In an overall meeting it has to be decided how to define a standard method for the determination of safety related properties at non-atmospheric conditions. At this time no standard methods exist. It has to be verified whether the newly acquired knowledge (determination of explosion indices, special behaviour of some fuel gases at elevated conditions etc.) can be applied to other fuels Additional experiments (high conditions/special wish of end-users) (TUD, BAM, WUT, BASF) In some cases it may be desirable to complete the acquired knowledge by carrying out special experiments at super-ambient conditions (combination of an high initial pressure and high initial temperature, extra large volume etc.) or to determine explosion indices of other fuels which will be proposed by the industrial participants. After the experimental determination of p max, (dp/dt) max as well as p ex and (dp/dt) ex for several gas mixtures it also may be desirable to do some experiments with venting. Especially at the UEL it is interesting for the industry to determine the necessary diameter of rupture disks in dependence of initial pressure and/or initial temperature.

17 Project No. EVG SAFEKINEX 17 3 WORK PACKAGE NR. 3 MODELLING / PREDICTION OF EXPLOSION INDICES 3.1 Objective:Development of models enabling the prediction of explosions indices. Table 3-1: Description of work package nr. 3 WORK PACKAGE DESCRIPTION Work Package Title: Modelling / prediction of explosion WP nr: 3 indices Starting data: 10 Duration: 36 months Total Effort (man/month): 101 Partners involved R & D Task / Activity of Partner Effort (man/month) TUD Task 3.1, 3.2, 3.4, 3.5 and CNRS Task 3.4 and VUB Task 3.1 and BAM Task 3.5 and WUT Task 3.2, 3.3, 3.7 and TUW Task UL Task 3.3, 3.4 and UK Task 3.6 and INERIS Task BASF Task Shell Task Objectives Development of models enabling the prediction of explosion indices. Description of work / tasks 3.1 Modelling of laminar burning velocity 3.2 Modelling of maximum explosion pressure (P max ) 3.3 Modelling of (dp/dt) max 3.4 Modelling of Auto ignition Temperature (AIT) 3.5 Modelling of Flammability Limits (FL) 3.6 Modelling of Minimum Ignition Energy (MIE) 3.7 Modelling of explosion propagation 3.8 Evaluation meeting The explosion sensitivity and severity parameters will be modelled by several partners, which have the highest expertise concerning investigated conditions and explosion parameter. Models will be developed and validated against experimental values. Deliverables Tools enabling prediction of : Laminar burning velocity Maximum explosion pressure (P max ) (dp/dt) max Auto-ignition temperature Flammability limits MIE using Markstein numbers Explosion propagation as function of fuel type, concentration, turbulence, obstacles and different geometry's Milestones and criteria 1. Creation and validation of safety predictive models. Ready for use models and software Criterion: Agreement between calculated and measured values accepted by partners and end-users

18 Project No. EVG SAFEKINEX 18 Interrelation with other work packages The experimental results of work package nr.2 will be used to validate the models. The tools developed will be used in work package nrs.5 and 6. The detailed (WP4) and partly reduced kinetic models (WP5) will serve as input for work package nr Introduction One of the major issues in hazard assessment is scaling from laboratory conditions to practical industrial dimensions and how the potential hazard is affected by changes in buoyancy and convection, especially in systems of complex geometry in which recirculation vortices occur. This requires the development of special computer tools. The origin of the difficulty is the unclear relationship between complex chemistry and the rate of heat dissipation augmented by natural convection. Extremely accurate predictions of critical transition points between cool flame and ignition phenomena are required. Convection, driven by buoyancy forces, is caused by density differences within the studying area and by gravitational acceleration acting on the fluid. Reliable simulation of reactive gas dynamics focussed on optimisation and safety of processes is non existent. This is due to the fact that simple kinetics does not reflect reality and present computer capacity do not allow flow and kinetic equations to be too large in number. Turbulent reacting flows have to be tackled using Computational Fluid Dynamics or CFD codes, of which there are many commercially available tools. However, the majority of CFD codes used as the basis for process and equipment design, rely on reaction models that generally introduce the assumption of fast chemical reaction in order to close the modelled equations. This excludes the incorporation of direct chemical kinetic effects which in turn severely limits the accuracy and range of applicability of these models, and hence their overall usefulness. Nevertheless, there has been some progress. More advanced techniques that permit the inclusion of chemical kinetic effects in turbulent flow calculations are becoming available. Multi-dimensional analysis of buoyancy and convection and the CFD of reactive flows both require significant mechanism reduction without loss of relevant information. Thus formal procedures to mechanism reduction are a prerequisite to the simulation and prediction of hazards in large-scale systems. 3.3 Modelling of laminar burning velocity The Task 3.1 includes two parts: development of the model and software for calculation of laminar burning velocity and also validation of the laminar burning velocity model. These two parts will be presented as contractual deliverables No. 14 and 15 to be finalized on months 14 and 34 respectively. Report on the development of the model and software for calculation of laminar burning velocity will demonstrate the ability of the combustion chemical kinetic model and of the existing software package CHEMKIN to predict laminar burning velocities in the mixtures of simple hydrocarbons with oxygen and inert gases. At this stage, a satisfactory qualitative agreement between model predictions and available literature data is expected. After the development and validation of the detailed C1-C3 kinetic model (within Work package 4) the calculated burning velocities will be validated against possibly wide range of the measurements from the literature and those obtained within this Project (Task 4.2.6). Good quantitative agreement must be achieved at this stage. The performance of the model will be assessed at the Evaluation meeting (Task 3.8). The main variables that will be considered will be the kind of mixture, the initial pressure and the temperature. The research team will pay a special attention to the results obtained for specific conditions that are not available in literature. Nevertheless, it will be necessary to begin with simulations for well-known regimes in order to check the models. Therefore the final initial data, which will be included in simulation should match exactly the data used for experiments carried out in the Work Package 2.

19 Project No. EVG SAFEKINEX 19 The task will be performed by partners: TUD and VUB. 3.4 Modelling of maximum explosion pressure A zero th-dimensional model will be used. The main objective is obtaining of maximum explosion pressure. Procedures that are included in CHEMKIN software could be adapted for that task while considering the detailed kinetics of reactions. Since existing standard, guidelines and methodologies do not cover conditions encountered in process industry, there is a need for determination of such indices at super-ambient conditions. It could be done by mathematical modelling. The obtained results are to be validated against the experiments done in Work Package 2.4. Some of the results could be also checked with data from literature, which can serve as an additional tool for investigating the correctness of the models. The task will be performed by partners: TUD and WUT. 3.5 Modelling of (dp/dt) max This part could be performed together with the Work Package 3.2. The parameter (dp/dt) max will be derived using the same procedure and compared with experimental data from Work Package 2.4. The task will be performed by partner WUT in cooperation with partner UL. 3.6 Modelling of autoignition temperature The autoignition temperature is one of the parameters that is of importance from the safety point of view. It is connected with the chemical properties of the mixture, the boundary and the initial conditions. A code will be developed where all the aspects will be included with the usage of CHEMKIN procedures. The autoignition temperature obtained from the modelling will be compared with the experimental results from the Work Package 2.1. The task will be performed by partners: CNRS, TUD and UL. 3.7 Modelling of flammability limits The models mentioned above could be used for determination flammability limits, as well. The mixtures that are going to be measured in the Work Package 2.3 are to be investigated using their chemical kinetics description and flammability limits and ignition delay time could be obtained using the tool of modelling. The task will be performed by partners: TUD and BAM. 3.8 Modelling of minimum ignition energy The simulation model INSFLA will be used to investigate the influence of Markstein number on minimum ignition energy. With this model one dimensional unsteady ignition and subsequent flame front propagation process under quiescent conditions without the influence of spark electrodes can be modelled. The model uses a detailed multi species transport model and a detailed reaction mechanism. In order to model the ignition process of C2 and C3 hydrocarbons well validated reaction mechanisms of the oxidation of C2 and C3 hydrocarbons in the gas phase, which will be delivered from partners of this project, are necessary.

20 Project No. EVG SAFEKINEX 20 The results of the simulation model INSFLA will also provide a detailed picture of the spatial temporal evolution of all species and of the temperature. So, a deeper insight into the physical and chemical process during the ignition period will be possible. This information will be helpful to develop new simplified models in which some physical effects can be neglected because of their different time scales. With these models a phenomenological description of real ignition process such as spark discharge experiments will be possible whereas M Markstein number will be an important parameter. We will use the results of experiments on the determination of minimum ignition energy and Markstein number of our contribution to Work Package 2 and results form the literature to validate the simplified theoretical models. The task will be performed by partner UK. 3.9 Modelling of explosion propagation Preparation of a code for 2D simulation of propagation of gas mixtures in channels with complex geometries a) the choice of a proper numerical scheme The scheme must be well prepared in order to resolve high discontinuities present in phenomena of gas explosions. The research team has experience in using Godunov method for simulations of dust explosions, where strong shock waves have been presented. b) the choice of a proper turbulent model It is planned to adapt RNG k- model that is an improved version of standard k- model. The model should be generally valid for simulations of gas flow in large geometries. It is expected that it can work not too well in the presence of chemical reactions, so it will be of importance to investigate the problems more thoroughly. c) the testing of the models against benchmarks presented in literature The part of the research will require some literature studying. Thanks to that it will be possible to avoid carrying out unnecessary experiments, as well as speed up the research Preparation of a code for 2D simulation of propagation of gas mixtures in channels with complex geometries and in the presence of chemical reactions a) the analysis of models of turbulent combustion There are a few models available for simulations of such processes. The first task will be to check how they will work for our applications. The models that are going to be investigated are as follows: Eddy Break-up Model, probability density function approach, and the flamelet concept. The objective will be to compare the numerical results with experiments carried out for small geometries. Parameters like burning velocity and maximum pressure will be validated. The objective will be also the comparison with zeroth-dimensional simulations performed by other groups during the Work Package 2. The results will be also compared with literature. It must be, however, considered that our research will be devoted to gas explosions in special conditions, like high pressure. It is of importance to extrapolate the data available to those cases. b) the choice of a best model and modification of it As a result a model will be chosen that has the best availability for our applications. Computation will be performed and the results will be validated against the experiments. The model will be further modified to include all the necessary aspects.

21 Project No. EVG SAFEKINEX 21 Some of the data, necessary for conducting the simulations, will be taken from Work Package 2 and Work Package 4. It will be of importance to take into account problems like reactions kinetics and values of laminar burning velocity. The latter will be also compared with the parameters from Work Package 3.1. One of the problems, while carrying out the experiments, will be the choice of proper initial conditions (like pressure, temperature, concentration of the mixture), the kind of reactive gas and the boundary conditions (the geometry of the computational domain). They should correspond to experiments performed by other research teams and it is planned to exchange suitable information between them. It has to be mentioned that the experiments should be also arranged so that they will match the simulation data as closely as possible. It will be addressed during the meeting in Work Package 1. The task will be performed by partner: WUT.

22 Project No. EVG SAFEKINEX 22 4 WORK PACKAGE NR. 4 KINETICS MODEL DEVELOPMENT 4.1 Objectives : Development of detailed kinetic models for (1) C1-C3, (2) C4-C10 and (3) aromatic hydrocarbons in the low and intermediate temperature oxidation regime. Table 4-1: Description of work package nr. 4 WORK PACKAGE DESCRIPTION Work Package Title: Kinetics model development WP nr: 4 Starting data: 1 Duration: 32 months Total Effort (man/month): 158 Partners involved R & D Task / Activity of Partner Effort (man/month) TUD Task 4.2.1, 4.2.2, 4.2.3, 4.3.1, , 4.3.3, CNRS Task 4.1.1, 4.1.3, 4.1.4, 4.2.1, , 4.3.1, 4.3.2, VUB Task 4.1.1, 4.1.2, 4.2.1, 4.2.2, , 4.3.1, 4.3.2, BAM Task 4.2.2, UL Task 4.1.1, 4.1.2, 4.1.3, 4.1.4, , 4.2.5, 4.3.1, 4.3.2, INERIS Task 4.2.1, BASF Task Objectives Development of a detailed kinetics model for (1) C1-C3, (2) C4-C10 and (3) aromatic hydrocarbons in the low and intermediate temperature oxidation regime. C1-C3 detailed kinetic model will also cover the high temperature oxidation regime. Description of work / tasks 4.1 Development of C1-C3 detailed kinetic oxidation models 4.2 Development of C4-C10 detailed kinetic oxidation models 4.3 Development of aromatic (benzene, xylene, toluene) detailed kinetic oxidation models 4.4 Acquisition of the relevant experimental data to evaluate reaction parameters Constant Volume Bombs experiments (CVB) Shock Tube experiments (ST) Rapid Compression Machine experiments (RCM) Laminar flame study 4.5 Validation of the generated detailed kinetic models 4.6 Additional experiments (high pressure and/or temperature) Oxidation detailed kinetic reaction models of small (C1-C3), larger (C4-C10) and aromatic hydrocarbons will be developed and validated against experimental kinetic and some of explosion experiments. The kinetic models will cover the low, intermediate and high temperature oxidation regime as well as low and high pressure limits. For that it is essential to apply wide range of initial conditions (temperature, pressure, concentration) and different type of experimental methods. Different experimental methods will enable to focus on different model behaviour. e.g. short induction time will be measured in shock tube experiments (ST), intermediate in rapid compression machines (RCM) and long induction time in constant volume bombs (CVB). Deliverables Validated detailed C1-C3 kinetic oxidation models Validated detailed C4-C10 kinetic oxidation models Validated detailed aromatic hydrocarbon (b,x,t) kinetic oxidation models Reports on experimental results for kinetic modelling (CVB, ST, RCM, flame study approaches) Report on validation of the generated detailed kinetic models

23 Project No. EVG SAFEKINEX 23 Milestones and criteria 1. Validated detailed C1-C3 kinetic oxidation models 2. Validated detailed C4-C10 kinetic oxidation models 3. Validated detailed aromatic hydrocarbon (b,x,t) kinetic oxidation models Criterion: Agreement between model and measured and literature data Accepted by partners and end-users Interrelation with other work packages The results of this work package will be used in work package nrs.3, 5 and 6 Several experimentally determined explosion indices (WP2) may serve as a validation for this work package 4.2 Description of the proposed work Detailed kinetic models for the oxidation and the auto-ignition of (1) C1-C3, (2) C4-C10 and (3) aromatic hydrocarbons will be developed. These models will be validated by using results existing in the literature from Constant Volume Bombs (CVB), Shock Tube (ST), Rapid Compression Machine (RCM), Jet-Stirred Reactor (JSR), Flow Tube (FT) and Laminar Flame (LF), or data obtained in this project through experiments performed in a CVB, ST, RCM, or FL. The expected range of validity of these models will be : Temperature : from 550 to 1600 K, NB : There are still important uncertainties concerning the low temperature chemistry of hydrocarbons containing from 1 to 3 atoms of carbon and very few data are available for validations. The existing models for C1 C3 hydrocarbons have not been fully developed to take into account reaction at temperatures below about 900 K, so this will be one of the initial tasks. Pressure : from 1 to 50 bar, NB : Some validations at sub-atmospheric pressure could be also performed. Equivalence ratio : from 0.5 to 2. NB : The equivalence ratio is defined as : = (x+y/4) x(%cxhy/%oxygen) by using the total reaction CxHy + (x+y/4) O2 = x CO2 + y/2 H2O. 4.3 Literature review (WP WP 4.2.1, from month 0 to month 4) The existing literature will be analysed in order to define the experimental data the most fitted to be used for validated the developed kinetic models. The literature review (4.1.1) will serve to establish realistic goals of the model development and to define the needs of the experimental data for the model validation (CNRS, VUB, UL). The choice will be analyzed during the meeting (4.2.1) and should be approved by all partners. 4.4 Development and validation of detailed kinetic models for the oxidation of C1-C3 hydrocarbons (WP WP WP WP 4.2.6, from month 2 to month 26) The development (4.1.2) and validation (4.3.1) of the C1-C3 kinetic model will include the following steps: 1. Establishment of the list of C1-C3 species and their intermediates relevant to the project goals and to the interest of industrial partners. In addition to the species commonly present in the combustion mechanisms (alkanes, alkenes, alkynes), oxygenated species such as alcohols, acids, ethylene and propylene oxides will be included (VUB, UL). 2. Establishment of a thermodynamic database for these species. The data will be taken from the literature or will be estimated using THERGAS code developed at the CNRS, Nancy (VUB, UL). 3. Compilation of the list of relevant reactions. The list will include all reactions important in the combustion and oxidation at temperatures higher than 550 K and at pressures of 1-50 atm. Very slow reactions important in atmospheric chemistry and reactions of excited