FM Global Property Loss Prevention Data Sheets

7-46 17-11
January 2002 Revised January 2003 Page 1 of 63

CHEMICAL REACTORS AND REACTIONS

Table of Contents
Page 1.0 SCOPE ................................................................................................................................................... 3 1.1 Changes ............................................................................................................................................ 3 2.0 LOSS PREVENTION RECOMMENDATIONS ....................................................................................... 3 2.1 Recommendations for Process Safety ............................................................................................ 3 2.2 Recommendations on Chemical Reactivity ..................................................................................... 5 2.3 Recommendations for General Chemical Processing .................................................................... 6 2.4 Recommendations for Reactor Design and Operation ................................................................... 8 2.5 Recommendations for Chemical Process Risk Assessment ......................................................... 11 2.6 Recommendations for Common Reaction Hazards ...................................................................... 11 2.6.1 Unstable Materials ............................................................................................................... 11 2.6.2 Pyrophoric Materials ............................................................................................................ 12 2.6.3 Water-reactive Materials ...................................................................................................... 12 3.0 SUPPORT FOR RECOMMENDATIONS ............................................................................................. 14 3.1 Physical and Chemical Properties ................................................................................................. 14 3.2 Chemical Functional Groups that Deserve Special Attention due to their Structural Elements ........................................................................................................................................ 20 3.3 Interaction Matrix ........................................................................................................................... 21 3.4 Chemical Hazard Analysis ............................................................................................................. 22 3.5 Chemical Thermodynamics ........................................................................................................... 24 3.6 Chemical Reaction Types .............................................................................................................. 26 3.6.1 Addition ................................................................................................................................ 26 3.6.2 Alkylation ............................................................................................................................. 26 3.6.3 Amination ............................................................................................................................. 27 3.6.4 Aromatization ....................................................................................................................... 28 3.6.5 Biochemistry: Biocatalysis, Bioconversion, Biotechnology and Biotransformation ............. 28 3.6.6 Calcination ........................................................................................................................... 28 3.6.7 Combustion ......................................................................................................................... 29 3.6.8 Condensation ...................................................................................................................... 29 3.6.9 Double Decomposition ........................................................................................................ 30 3.6.10 Electrolysis ........................................................................................................................ 30 3.6.11 Esterification ...................................................................................................................... 31 3.6.12 Fermentation ..................................................................................................................... 31 3.6.13 Fuel Gas Processes .......................................................................................................... 32 3.6.14 Grignard Reactions ........................................................................................................... 32 3.6.15 Halogenation ..................................................................................................................... 32 3.6.16 Hydrogenation ................................................................................................................... 33 3.6.17 Hydration, Hydrolysis and Saponification ......................................................................... 34 3.6.18 Isomerization and Stereoisomers ...................................................................................... 35 3.6.19 Neutralization ..................................................................................................................... 35 3.6.20 Nitration ............................................................................................................................. 36 3.6.21 Organometallic Compounds .............................................................................................. 36 3.6.22 Oxidation ........................................................................................................................... 37 3.6.23 Photochemical ................................................................................................................... 39 3.6.24 Polymerization ................................................................................................................... 39 3.6.25 Pyrolysis & Cracking ......................................................................................................... 41 3.6.26 Reduction .......................................................................................................................... 42

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Page 2

Chemical Reactors and Reactions
FM Global Property Loss Prevention Data Sheets

3.6.27 Reforming .......................................................................................................................... 43 3.6.28 Saponification — See Hydration, Hydrolysis and Saponification ..................................... 43 3.6.29 Silicon, Silane, Silicone, and Siloxane .............................................................................. 43 3.6.30 Sulfonation ......................................................................................................................... 44 3.7 Water-Reactive Materials .............................................................................................................. 44 3.8 Reaction Quenching Methods ....................................................................................................... 45 3.9 Unstable Materials and Explosion Hazards due to Uncontrolled Chemical Reactivity ................. 45 3.10 Experimental Screening and Thermal Hazard Analysis .............................................................. 47 3.11 Scale-up Effects ........................................................................................................................... 48 3.12 Chemical Risk Assessment and Management ............................................................................ 48 3.13 General Chemical Processing ..................................................................................................... 48 3.14 Reactor Selection ........................................................................................................................ 49 3.15 Reactor Aging and Corrosion Resistance ................................................................................... 53 3.16 Illustrative Losses ........................................................................................................................ 54 4.0 REFERENCES ..................................................................................................................................... 56 4.1 FM Global ...................................................................................................................................... 56 4.2 NFPA .............................................................................................................................................. 57 4.3 Other .............................................................................................................................................. 57 APPENDIX A GLOSSARY OF TERMS ..................................................................................................... 58 A.1 Acronyms and Abbreviations ........................................................................................................ 58 A.2 Definitions ...................................................................................................................................... 59 A.3 Chemical Functional Groups ......................................................................................................... 61 APPENDIX B BIBLIOGRAPHY ................................................................................................................. 62

List of Figures
Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. Fig. 1. Reactive chemical and chemical reaction hazard evaluation. ........................................................ 15 2. Vapor pressure-temperature properties of a pure material (ethylene oxide). ................................. 16 3. Pressure-temperature properties of a typical pure material. ........................................................... 17 4. Effects of pressure on the flammability of natural gas ..................................................................... 17 5. Effects of temperature and pressure on flammability and autoignition temperature. ..................... 18 6. Effects of temperature on common salt solubility. .......................................................................... 19 7. Example of an in-progress interaction matrix for a generic chemical process. .............................. 22 8. Enthalpy diagram of an exothermic reaction. .................................................................................. 26 9. Types of polymerization reactions. .................................................................................................. 39 10. Types of Explosions. ..................................................................................................................... 45 11. Thermal Explosion Heat-Temperature Graph. ................................................................................ 46 12. Deflagration versus Detonation Pressure-Time Graph. ................................................................ 47 13. Pfaudler CSTR. .............................................................................................................................. 50 14. Braun bioreactor. ........................................................................................................................... 51 15. Plug Flow Reactor. ........................................................................................................................ 52 16. Membrane Reactor. ....................................................................................................................... 52 17. Applicability of Materials in Oxidizing and Reducing Acids. .......................................................... 55

List of Tables
Common Types of Reactions ......................................................................................................... 13 Estimated Energy of a Confined Gas ............................................................................................ 20 Unstable Structure Decomposition Energies ................................................................................ 21 Enthalpy of Decomposition, CART values, and relative hazard rankings for selected compounds ..................................................................................................................... 24 Table 5. Advantages and Disadvantages of Various Reactor Types .......................................................... 51 Table Table Table Table 1. 2. 3. 4.

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Chemical Reactors and Reactions
FM Global Property Loss Prevention Data Sheets

7-46 17-11
Page 3

1.0 SCOPE This data sheet describes the general hazards and concepts associated with chemical reactions and chemical processing. The chemical reaction section emphasizes hazard evaluation throughout product development. The chemical reactor section includes process safety management concepts and new technology. This data sheet does not apply to boilers, chemical coating processes, chemical dipping, chemical mixing, cryogenic extractions and separations, high energy material (explosive and rocket motor) manufacturing processes, radioactive material processing, solvent extraction, solvent recovery, vulcanization, and waste treatment. 1.1 Changes January 2003. Editorial changes were done for this revision. Section 3.16 was revised. Data Sheet 7-46 has been completely rewritten. Major revisions are as follows: 1. The recommendation section has been expanded and segmented to highlight recommendations dealing with an inherently safer design philosophy, chemical hazard analysis, process hazard analysis, and reactor selection. Reference is made to other data sheets rather than repeating information contained elsewhere. 2. The chemical reaction section has been streamlined and includes the information previously located in Data Sheet 7-43/17-2, Loss Prevention in Chemical Plants (February 1974 edition). 3. A section on photochemical reactions has been added. 4. A section on chemical properties and thermodynamics has been added under Support for Recommendations. 2.0 LOSS PREVENTION RECOMMENDATIONS 2.1 Recommendations for Process Safety 2.1.1 Conduct chemical process safety evaluations, analysis, and assessments from discovery, throughout development, and into production. 2.1.2 Consider the potential energy of the chemicals involved, the reaction rates, the process equipment and the equipment configuration in all chemical process safety evaluations. 2.1.3 Use the inherently safer design concepts of intensification, substitution, attenuation, and limitation throughout new product and process development to avoid hazards, thereby reducing the need for mitigation. The greatest opportunity to develop an inherently safer chemical process occurs early in the research and development process, generally prior to selecting the final synthesis route. See Data Sheet 7-43/17-2, for details on these techniques. 2.1.4 Provide protection/mitigation measures when hazards cannot be eliminated by inherent safety concepts. Passive measures should be used wherever possible. Active protection measures should be used where passive protection is not adequate. Procedural measures alone should be avoided and are generally not acceptable protection. 2.1.5 Use a formal management of change (MOC) procedure to evaluate and control all proposed chemical process procedural and equipment changes that are not in like kind. 2.1.6 Update as-built process piping and instrumentation drawings (P&IDs) as part of the MOC procedure. Have these drawings readily available for use by operation, maintenance, and emergency response personnel, and Process Hazard Analysis (PHA) revalidation teams. 2.1.7 Have standard operating procedures (SOPs) for all processes readily available. 2.1.7.1 To be effective, be sure that SOPs are clear and concise to read, and comprehensive. 2.1.7.2 In addition to normal operating procedures, SOPs should address the following situations:

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compatibility. initiate dumping.1. c) Actions to be taken in the event of an identified upset condition.11 Implement a preventive or predictive maintenance program for all instrumentation systems. ©2003 Factory Mutual Insurance Company.12 Implement inventory management systems where hazardous materials are present. concentration.3 Control the distribution of official copies of SOPs by a management system that includes approval and distribution data. including unstable intermediates. liquid levels. etc. d) Verification of process equipment configuration. use the management of change system to request and receive approval for a deviation.1. Instrumentation and Control in Safety Applications.1. Data Sheet 5-20.1. ground fault indication systems. and quantity. c) A pre-operational verification that all critical utilities are available to meet process requirements. or add inhibitor. f) A summary of the safe limits of temperature. such as the agitator or heat transfer system. 2. and flow rates as listed in the current SOPs. as a minimum.7. electrical equipment.10 Use reliability engineering to maintain a preventive or predictive maintenance program.4 Circulate only the latest revision of the SOPs. 2. ensure that process instruction sheets include the following: a) A pre-operational check of the reactor and associated equipment confirming that it is clean and empty. Protective Grounding for Electrical Power Systems and Equipment.13 Specifically address hazardous chemical reactivity potential in all emergency response plans and keep them readily available for reference. Include guidance on when to stop scheduled additions. All rights reserved. Document the removal and destruction of superseded SOPs. pressure. covering the process safety management (PSM) mechanical and equipment integrity element. Data Sheet 5-10. Data Sheet 5-8. 2. Emergency and Stand-By Power Systems. Advise operators of all new and revised SOPs. 2. d) The addition of rework materials. Electrical Testing and Data Sheet 5-23.8 Ensure that operators use process instruction sheets. 2. behavior-based safety (why people behave the way they do) may be valuable. Since chemical process accidents continue to occur despite routine chemical safety and process hazards training. .7-46 17-11 Page 4 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets a) The margin of safety between normal operating conditions (temperature. Rework may have a significant concentration of undesired materials. Static Electricity. b) Potential consequences of operating outside the normal boundaries. Unused feed lines and equipment should be blanked or physically disconnected. and lightning protection systems in accordance with Data Sheet 7-45. chemical concentration. Data Sheet 5-11.) and those that might initiate a runaway reaction. As a minimum. Providing abnormal situation management systems (intelligent control systems that are used to assist operators in determining what may be going wrong and what may be done) may also be valuable.1.1. or batch sheets.7.1.7. 2. initiate quenching. 2.1. e) Verification that reactants have been analyzed for chemical identity and purity and are within specifications. 2. as appropriate. b) Instructions to conduct an integrity check of internal components. 2. Include information on composition. Review completed sheets and then maintain them on file.9 Train process operators on relevant chemical and process safety issues on a periodic basis. location of storage/processing vessel. grounding and bonding systems.5 If the SOPs cannot be followed. This is especially important where different products are campaigned in the same equipment. The goal should be a design with minimum inventories.1. Lightning and Surge Protection for Electrical Systems. pressure.

or dumping the contents into another vessel that contains a quench liquid.8 Avoid use of unstable raw materials or intermediates if at all possible. rust.2.7 Evaluate measures to inhibit uncontrolled chemical reactions. quenching with water or another diluent.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 5 2. decomposition products. whether onset temperature and overall kinetic information is needed.3 Calculate theoretical reaction energies and computed adiabatic reaction temperature (CART) and compare them with the values for known hazardous compounds. The choice of test equipment for a detailed thermal stability study will depend on the size of sample available.5 Conduct the following reactivity screening tests.2 Recommendations on Chemical Reactivity 2.2.2. for details on ARC and RSST techniques. All rights reserved. and temperature ramp screening using accelerating rate calorimetry (ARC). 2. adiabatic calorimetry. Oxygen balance calculations may be used for organic nitrates and nitro compounds. Give special attention to the handling of rework material. isothermal storage tests. and whether special materials of construction are needed.g. and cleaning products: a) Pyrophoric properties b) Water reactivity c) Oxidizing properties d) Solid (dust). intermediates.2 Obtain preliminary estimates of the hazardous chemical reactivity potential using theoretical screening methods.2. See Data Sheet 7-49/12-65. Carefully select the inhibitor or quench material and thoroughly understand the inhibition reaction. runaway reaction. 2. and/or vapor flammability properties e) Common contaminant reactivity (e. Common measures include adding an inhibitor.6 The results of the hazardous chemical reactivity screening tests determine to what extent detailed thermal stability. by-products. Do not allow unstable intermediates to accumulate or be isolated.2. In addition. prepare an interaction matrix and conduct a Chemical Hazard Analysis. and gas evolution testing is needed. reactive system screening tool (RSST).1 Conduct chemical hazard assessments for all new processes and whenever significant changes are made to existing processes so that inherent safety and inherently safer design concepts may be included in the design of new chemical processing plants. Preliminary estimates can be obtained by using kinetic rate equations. Where unavoidable. unintended products. quenchers. mixing needs. inhibitors. on raw materials.2. . conduct chemical hazard assessments for existing processes whenever process knowledge and documentation is lacking. liquid. 2. neutralization.9 Evaluate use of the proposed chemicals and synthesis route to optimize safety before proceeding with process and equipment design. ©2003 Factory Mutual Insurance Company. heat transfer fluid. solvents. as appropriate. the required temperature range. as applicable..4 Determine chemical reaction rates and kinetics. Ensure that a reliable means of material addition or dumping is provided. 2. isoperibolic calorimetry.2.2. 2. products. 2. catalysts.2. Emergency Venting of Vessels. carefully control unstable raw material feed so that concentrations are kept low and the material is consumed as rapidly as it is added. Some information may need to be determined experimentally. 2. scrubber solutions) f) Mechanical sensitivity (mechanical impact and friction) g) Thermal sensitivity h) Self-reactivity 2. As a minimum. and adiabatic storage tests (AST). Include the appropriate concentration and rate of addition of the inhibitors in the SOPs. Screening tests may include reaction calorimetry.

side reaction.. scrubbers.. • Equipment failures (e. All rights reserved. heat exchanger and condenser.4 Consider the potential loss of site and process utilities during the process safety evaluation including the following: • Electrical power • Steam • Compressed air • Instrument air • Raw water • Process water. chilled water.3. • Loss of Agitation: electric or hydraulic. stuck pressure relief devices. • Loss of Inerting Media. rust. etc. plugged lines. • Contamination of raw materials or equipment: water. deionized water (DI).1 Consider the results of the Chemical Hazard Analysis in the chemical process and equipment design. • Backflow of materials. foaming. heat and air conditioning • Area containment and drainage • Waste treatment/land fills • Environmental systems (e. consider all single events as well as a single event that occurs while an independent component is not available (e. settling of solids. awaiting repair) as credible. brine) and any associated equipment including cooling towers • Heating media • Natural gas • Inerting gas • Vacuum • Area humidity. • Abnormal Temperatures: reaction rate. or cleaning products.3 During the chemical process safety evaluations consider credible upset conditions that are listed below.g. chemical residue. 2.3. Analyze each step not only for its own safety. determine the worst case scenario. side reactions. undercharge of limiting reagent. non-uniform distribution of gas. As a minimum. and/or other special water treatment systems • Cooling media (e. wrong catalyst. 2.2 For all chemical processes.g. etc.g. controls. ventilation. the worst case scenario should be the worst possible combination of events that could realistically occur. or use of re-work. • Mischarge of Reactants: overcharge of monomer. 2. phase separation. wrong sequence of addition or inadvertent addition. • Mass Load Upset/Composition & Concentration: accumulation of unreacted materials.7-46 17-11 Page 6 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 2.. • Abnormal Pressures: reaction rate.3. failed valves. out-of-service. • Inadequate and/or Loss of Cooling: jacket. . leaking heat transfer fluid.. In general. but also for its effect on the safety of other steps.g.3 Recommendations for General Chemical Processing 2. fume incinerators) • Instruments.3. inaccurate instrumentation readings) caused by highly viscous materials or high freezing point materials. and information/data systems • Fire protection water ©2003 Factory Mutual Insurance Company. excess catalyst.

provide separate excess temperature interlocks and pressure relief devices as a minimum. instrument air compressors.3.11 Arrange compressed air systems reliably. For water-based heat transfer systems (e. 2. steam). transfer pumps. • Raw material specifications: Bulk material quality may differ from lab material quality. • Waste handling.5 Consider less hazardous chemical processing alternatives. Failure Mode and Effect Analysis (FEMA). All rights reserved. Arrange air system automatic valves to fail-safe.3. Heat Transfer by Organic and Synthetic Fluids. 2.g. FM Global Data Sheet 7-43/17-2.1 Keep the Chemical Hazard Analysis and Process Hazard Analysis current as scale-up progresses. Ignitability of flammable materials will change with flow rates.3. Vapor space composition may vary and also is a concern. cooling systems including cooling tower fans.3.12 Arrange heat transfer systems safely and reliably: a) Provide alarms and interlocks for organic and synthetic heat transfer systems in accordance with Data Sheet 7-99. 2.8 Supply critical process utilities from completely redundant systems. 2.3. Provide a sufficient number of accessible isolation and shutoff valves. provides information on these techniques.3.2 Consider the following variables as the scale is increased. • Vessel shape effects on agitation and flow patterns: Excessive agitation and stagnation zones are both concerns. and is linked to the rate of heat loss from the system.3. 2.6. heat transfer fluid systems. Critical process utilities are those utilities identified during a process hazard analysis as those whose loss would either result in an unacceptable process condition or a significant interruption to production. which may include the following: agitators.9 Do not locate critical site and process utility lines in an area where they may be exposed by a process upset. Impurities are a concern. reliably arranged.3. and What-if. • Vessel size effects on mixing capacity and flow stability: Pockets of reactive and/or flammable mixtures may result and are a concern. 2. • Surface-to-volume ratio effects on concentration and temperature gradients: Heat removal is a concern since the minimum temperature for a runaway reaction is not absolute. Preliminary PHA methodologies may include Hazard and Operability (HAZOP) studies.3. • Mode of operation changes: Different residence time distributions are a concern.10 Provide emergency power to permit the safe shutdown of chemical processes in the event of an electrical power failure. • Use of recycled materials. • Vapor space composition variations and potential side reactions in the vapor space. • Isolation and storage of intermediates. 2. ©2003 Factory Mutual Insurance Company. Checklist. Evaluate these alternatives for process safety using recognized Process Hazard Analysis (PHA) methodologies and best industry practices. Size the emergency power generator to handle critical equipment loads. Loss Prevention in Chemical Plants.7 Provide critical site utilities from two separate sources wherever possible. Use the results of these evaluations in the manufacturing process development.3. • Materials of construction changes: Different contamination levels are a concern. .Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 7 2. 2. • Viscosity changes affecting adequate emergency relief venting (plugging vents). Design compressed air systems intended for multiple services to prevent contaminants from entering the instrument air system. Fault Tree Analysis (FTA). 2. a completely redundant in-line spare should be provided (n+1 design basis).. Where more than two systems are provided. but will depend on process conditions and scale.6. Arrange supply and distribution reliably. and fire protection systems. instrumentation and control equipment. vacuum pumps and associated equipment.6 Address scale-up effects systematically during process development and optimization.

2.3. Arrange vacuum pump seal systems using flammable or combustible liquids in accordance with Data Sheet 7-32.14 Arrange vacuum systems reliably with automatic valves that fail safe. standards. heat tracing may be installed around the device and associated piping.. c) Use a compatible heat transfer fluid in place of water whenever water-reactive materials are present or are generated by a chemical process. and corrosion allowances on the most severe combination of conditions anticipated.7-46 17-11 Page 8 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets b) Arrange automatic valves to fail-safe. 2. b) If potential blockage of pressure relief devices is a concern.4. rupture disks may be used alone or installed below a pressure relief valve. Emergency Venting of Vessels. 2. See Data Sheet 7-59. Provide vacuum pump seal water systems with a back-up water supply. where appropriate. liners. multiple. shutdown and emergency venting. Flammable Liquid Operations. Provide suitable instrumentation to facilitate proper inerting. Monolithic construction is preferred due to the serious mechanical integrity issues associated with the use of materials with different coefficients of expansion (e. location. when selecting reactor vessel materials of construction: a) Compatibility with all process materials.4 Provide adequate emergency pressure relief for all chemical reactors as follows: a) Determine the size.4. The test procedure should indicate normal performance specifications/ranges and the point at which action should be taken to address performance problems. Pressure Vessels. 2. generally closed. This may be done by inerting on startup and shutdown if the equipment passes from an air atmosphere to a flammable atmosphere and back.1 Design and construct reactors in accordance with applicable codes.4 Recommendations for Reactor Design and Operation 2.13 Maintain an inert gas purge where the vapor space above a liquid phase can contain an explosive mixture. Section VIII and Data Sheet 12-2. simultaneous release and may result in incompatible materials being discharged at the same time. ©2003 Factory Mutual Insurance Company. temperatures. . In some cases explosion suppression systems may be applicable and advisable. with the frequency based on the properties of the materials.4.3. 2. d) Route the discharge of emergency pressure relief vents to a point where ignition of escaping vapors or liquids will not seriously expose the equipment or structure. c) The effects of pressure and temperature cycling. and implement a scheduled replacement program. d) Install strainers in cooling water systems to collect any debris that could block flow. Process Vessels and Equipment. This can be achieved with proper alloy selection.4. vessels with sacrificial linings consumed in use and/or special or exotic materials).15 Conduct performance maintenance tests on critical process utilities under load conditions as applicable. or an inert gas sweep may be provided near the inlet to the relief device. d) The effect of operating outside the normal operating range including startup.3. For pressure vessels the minimum standard of construction should be the most recent version of the American Society of Mechanical Engineers (ASME) Boiler and Pressure Vessel Code. and state and local laws and regulations. All rights reserved. Shared vent system designs should be based on the worst case. c) If solid accumulation is a concern. e) Use antifouling agents and corrosion inhibitors appropriate for the system.3 Select reactor size and type to minimize hazardous material inventories. Base design pressures. materials of construction and arrangement of emergency pressure relief devices for each process in accordance with Data Sheet 7-49/12-65. Inerting and Purging of Tanks.g. 2.2 Review and evaluate the following factors. and by continuous inerting if an explosive mixture may be generated during operation. at a minimum. 2. conduct periodic visual inspections. b) Adequate corrosion resistance. double walled vessels or corrosion inhibitors.

strongly exothermic reactions where the reaction can generate pressure at a rate beyond the practical capacity of relief devices. Alternatively. and associated distillation columns. 2. Where overcharging a raw material could create a hazard. g) Provide adequate emergency pressure relief for reactor jackets. and chemical processes using large volume equipment. b) Design the agitator to function under all foreseeable viscosity conditions. Provide low level alarms on seal fluid reservoirs. as this arrangement is prone to operator error. or diluents to control viscosity increases. All rights reserved. c) Preferably. f) Brace emergency pressure relief lines to withstand the thrust encountered with full relieving flow. Do not use the same weigh or feed tank for charging more than one reactive raw material. g) Consider using process additives to improve agitation. the agitator should be of variable speed design with shaft speed limited. Size vacuum breakers for the greater of the fill or discharge flow rates. 2. particularly hydrogen. Hot bearings and seals are potential ignition sources. size the feed tank to hold only the required amount. Do not use a weigh or feed tank that requires multiple fills to charge the full amount of a reactant.8 Arrange raw material charging systems to minimize potential mistakes and problems.4.4.1 Do not premix reactive raw materials. For reactor/reflux condenser configurations. chemical reactions where significant quantities of unstable chemicals are used or produced. consider one or more of the following: a) Inert gas pressure control may be used to minimize vacuum effects. Examples include high pressure chemical reactions.4. Where a runaway reaction may occur due to high temperature at an unwetted internal heating surface. e) Provide adequate cooling for shaft seals and bearings. c) Equip cold liquid feed lines with temperature and heater alarms and interlocks if the reactor is not designed for full vacuum or if an adequately sized vacuum breaker is not provided. d) Securely attach agitator components according to manufacturer’s guidelines.7 Select reactor heat transfer equipment taking material properties into consideration as well as process requirements. . These could include emulsifying or de-emulsifying agents to control phase separation.4. limit the temperature of the heat transfer fluid. d) Limit the liquid/gas discharge rate from the reactor by orifice size or pump rate interlocks if the reactor is not designed for full vacuum or if an adequately sized vacuum breaker is not provided. h) Where adequate pressure relief is impractical. heat exchangers. an external heating system with process recirculation or a sparging system. Sudden discharge of cold liquid into the vessel can cause condensation and an unexpected vacuum condition. Provide vibration or temperature sensors where this is a concern. Methods to limit temperature could include split heating/cooling systems. 2. Any flexible couplings should meet the same design criteria as the fixed relief lines. Shaft speed and load should be monitored. 2.5 Design reactors to withstand full vacuum or provide vacuum breakers.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 9 e) The diameter of the emergency pressure relief discharge piping should be no smaller than the diameter of the pressure relief device to ensure that the full relieving capacity is unrestricted. for details. Spacing of Facilities in Outdoor Chemical Plants. Charge lines should have no cross connections to other reactive raw materials. b) Provide insulation for equipment in geographical areas where rapid ambient temperature changes may cause vacuum conditions. provide substantial isolation (by distance and barricades).4. Pump power supplies should be interlocked to reactor pressure. ©2003 Factory Mutual Insurance Company. See Data Sheet 7-44/17-3.8. 2. f) Use double or tandem mechanical seals with inert seal fluid when seal failure could release flammable or other hazardous materials. separate emergency pressure relief should be provided for each piece of equipment. Elevate feed vessels above reactors to minimize the potential for back-feed into the charge tank.6 Design agitation equipment for reliable service with consideration of the following factors: a) Design the agitator to withstand maximum process temperatures and pressures.

Check for cuts. Provide continuous continuity testing devices on vessels where needed. b) Inspect welds that are prone to physical stress (e. couplings. fittings.. near agitator or bottom). at head nozzles and agitator mounts) and chemical corrosion (e.. dents. All rights reserved. valves. or as determined by a process hazard analysis. and preferably a predictive maintenance program.3 Valves should not trap materials. and chemical reactivity areas (e. liquid/vapor interface) visually and using a non-destructive examination technique (e. liquid/vapor interfaces) into consideration.4.7-46 17-11 Page 10 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 2. arrange piping so that one chemical cannot back up into the supply piping for another incompatible chemical.g.g. Static Electricity.12 Do not allow utility connections to exceed the pressure rating of the reactor and/or jacket.9.4 Add flammable liquids using non-splash methods (e. 2.8.4.9. Check riveted vessels for rivet shank corrosion. flanged cap and remove all permanently idled piping.. 2. 2. Use independent pump timers where raw materials are fed by metering pumps. including sample lines.4.8. Take similar readings one to two years later. 2.4 Locate emergency block valves on or as close as possible to the reactor containing hazardous materials.4. gaskets. Select test points after taking erosive forces (e. Level monitoring devices and independent high level interlocks are advisable.8. high flow areas (e.g. 2. 2.9. 2. and design the piping system to the greatest extent possible to make incorrect assembly impossible.4. where corrosion is suspected. use a nondestructive examination technique (e.4. In no case should an open manhole be used to ‘‘shake’’ powdered materials into the reactor.4. 2.9.g. ©2003 Factory Mutual Insurance Company. where corrosion is a concern. Provide pressure regulators and pressure relief devices with pressure alarms and interlocks arranged to isolate the utility system whenever utility pressure could create a hazard.11 Size vapor lines and condensers for the worst credible case scenario as determined by a process hazard analysis..4. Provide all dead end piping with a screwed or bolted. sight glasses. for chemical reaction system vessels and piping that includes the following activities as appropriate: a) Take initial (ultrasonic) thickness readings on all important reaction system vessels and piping during commissioning to serve as a baseline for the mechanical integrity (MI) program. and other components in accordance with Data Sheet 7-32. 2. Verify structural attachments and vessel connections are in good condition. Automatic valves in solvent charge lines should fail-safe. or other evidence of deterioration.5 Do not permit open ended piping on operating equipment.3 Arrange automatic valves in reactive raw material charge lines to fail closed. 2. flanges.13 Implement a preventive maintenance program. or as determined by a process hazard analysis.. Install blanks close to the source of temporary idled piping to minimize fluid filled piping. spot radiography). 2..4. Conduct reactor thickness tests at least annually. liquid penetrant or magnetic particle) during the first scheduled process shutdown to determine if there is any previously undetected manufacturing defect.. As a minimum. 2. Flammable Liquid Operations. . Arrange these valves to fail closed.9 Design pipe.g. as determined by process hazard analysis and product value.8. 2.4. and one to two years after that to establish a corrosion/erosion rate for use in calculating vessel half-life.2 Be sure that valve and valve seat materials are compatible with process materials.5 Add combustible solids using closed charging systems under an inert atmosphere. Check for evidence of leakage. c) Conduct continuity tests on glass-lined and Teflon-lined vessels regularly. d) Conduct external visual inspections of reactors at least annually.1 Keep reactor pipe connections to a minimum. charge nonflammables first then add flammables via a sub-surface inlet).4..g. Check the condition of external insulation and corrosion resistant coverings if provided.g.4. as this invites static charge buildup and loss of inert atmosphere in the reactor head space.4.10 Provide permanent grounding and bonding in accordance with Data Sheet 5-8.9.2 Provide overfill protection.g. distortion. near nozzles).4.

as a minimum. use certified personnel. The most common types of reactions. 2. inspect vacuum breakers and pressure relief devices frequently to determine that the operating mechanisms have not become stuck together. 2. according to the National Board Inspection Code (RB-3237) and API 510 Section 6. Additional information on specific reaction types may be found in the Support for Recommendations section.1 Prior to installation of a process with chemical reactions in an existing or new building or area. it is impossible to provide specific guidance for every possible scenario. d) Maintain an excess of inert solvent or inhibitor so that the concentration of the highly reactive or unstable chemical is at a safe level. . f) Conduct external visual inspections of reactor agitators at least annually.6. and update equipment maintenance records. conduct a complete review of the process and site risk levels (consequence and probability). etc.4. as the minimum. where applicable. conduct the reaction so that it is removed as quickly as it is produced. but must be converted to an air atmosphere for maintenance. b) Operate the reactor under conditions such that the highly reactive or unstable chemical is used up in the process as quickly as it is introduced.5 Recommendations for Chemical Process Risk Assessment 2. j) Inspect points of potential flammable gas leakage from equipment on a regular basis with the frequency based on the gas pressure and previous operating history. temperature sensors. Use more restrictive jurisdictional inspection requirements. pressure sensors. However. Conduct the inspections at least monthly until sufficient information is available to establish a predictive maintenance program. if programmable logic devices are part of the safety interlock system. inspect the vacuum breakers monthly. See Data Sheet 7-43/17-2. for additional guidance on risk assessment and management. and other instrumentation at least annually. Check to see that agitator blades are securely attached and the shaft is in good condition as part of every internal inspection. Instrumentation and Control in Safety Applications. c) If the highly reactive or unstable chemical is produced in the reaction. most chemical reactions can be classified into a limited number of categories. Chemical reactions and processes may present very little hazard or be extremely hazardous. change in process chemistry. g) Calibrate and functionally test flow meters. 2. design and operate the reactor so that these chemicals will be present in the smallest quantity possible: a) Use low-volume equipment to limit the quantity of highly reactive or unstable material present.6 Recommendations for Common Reaction Hazards Chemical reactions and processes may be simple or complex. A less desirable alternative would be to design the equipment to withstand the pressures developed by an internal vapor-air explosion. ©2003 Factory Mutual Insurance Company.1 Unstable Materials Where highly reactive or unstable materials are present in a reaction. 2. operational service history. h) When high viscosity (sticky) materials are being handled. and common critical processing parameters are summarized in Table 1. Use more restrictive inspection requirements where warranted by unique or unusual conditions due to the possibility of non-uniform degradation (non-continuous service. Because of the large number of possible chemical reactions and processes.3. k) Where equipment operates with flammable gases or vapors above their upper flammable limit (UFL). severe environment. take mitigation steps or relocate the process elsewhere.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 11 e) Conduct internal inspections of reactors. Follow the installation criteria in Data Sheet 7-45. Correct leaks promptly and properly.). relative energies.5. Perform all repairs to pressure vessels in accordance with applicable codes. All rights reserved. use inerting or another approved procedure to avoid passing through the explosive range.14 Arrange all process safety interlocks to be independent of the basic process control system. Loss Prevention in Chemical Plants. Where risk levels of the process do not meet predetermined acceptability criteria. i) When reactors are steam-cleaned.

h) Install automatic sprinkler protection in areas where significant quantities of flammable liquids will be present.6. d) Use low-volume equipment to limit the quantity of pyrophoric material present. b) Design process equipment to withstand deflagration pressures. g) Arrange scrubbers. b) Transport water-reactive materials in watertight containers.6.7-46 17-11 Page 12 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 2. 2. c) Use closed feed systems. design and operate the reactor so that these chemicals will be present in the smallest quantity possible: a) Design process equipment to prevent the accumulation of pyrophoric materials inside the equipment. g) Provide oxygen detection interlocked to an emergency purge and isolation system. f) Provide equipment isolation valves. if provided. f) Check raw materials to be sure that they are dry. Where some accumulation is unavoidable. e) Provide interlocks to prevent opening of the equipment during processing. e) Dry compressed air and inerting gas streams prior to use.3 Water-reactive Materials Evaluate the storage. ©2003 Factory Mutual Insurance Company. equipment cleaning or as barrier fluid in mechanical seals. All rights reserved. and processing of water-reactive materials during Chemical and Process Hazard Analyses: a) Store water-reactive materials in a small. provide explosion suppression systems. . d) Do not use water or steam for heating or cooling. handling. Where this is not practical.2 Pyrophoric Materials Where pyrophoric materials are present in a reaction. design equipment so that the pyrophors may be safely and easily removed on a periodic basis. c) Limit quantities of water-reactive materials in manufacturing areas to one shift usage. to prevent backflow to equipment processing water-reactive materials. detached building of noncombustible construction.

2. 7. 2 1-6. 12 1-5. 5. 5. 10. 7. 3. 2. 2 1. 5 10. 5 2 2. Detonation potential Viscosity issues ©2003 Factory Mutual Insurance Company. 6. 2 1. Liquid Level Notes Excess reagent may be needed Dumping/Suppressant may be needed NH3 decomposition potential pH. Agitation Energy Moderately to Highly Exothermic Endothermic to Highly Exothermic Endothermic to Moderately Exothermic Endothermic Moderately Exothermic Endothermic to Mildly Exothermic Endothermic Mildly Exothermic Mildly Exothermic Endothermic to Highly Exothermic Mildly Exothermic Moderately Exothermic Mildly Exothermic Mildly Exothermic Mildly Exothermic Highly Exothermic Highly Exothermic Endothermic to Moderately Exothermic Mildly to Moderately Exothermic Endothermic Endothermic to Mildly Exothermic Endothermic to Moderately Exothermic Endothermic to Mildly Exothermic Mildly Exothermic 4. 7 1. 12 1. Concentration 7. 1. 8 1. . 8 5. Flammable gases (LEL detection) 8. 1. 5 1 5. 6 1-5 12 (diazo) 1-4 1. Addition Rate 6.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 13 Table 1. 12 (some) 1. 8. 1. 2. 3. Reactive metals 12. 6 (offgas) 1-5 6. 10 (some) 3. 8. 9 1. 6. 2. Cooling/Heating 5. Temperature 2. Critical that adequate and reliable process control be provided Type Alkylation Amination Aromatization Calcination Condensation Double Decomposition Electrolysis Esterification (organic acids) Fermentation Halogenation Hydration Hydrogenation Hydrolysis Isomerization Neutralization Nitration Organometallic Oxidation Polymerization Pyrolysis and Cracking Reduction Reforming Substitution Sulfonation Processing Parameters: 1. 11 (some) 1-7. 8. 2. Common Types of Reactions Potentially Critical Processing Parameters 1. 2. 11 (some). Water reactive 11. electrical variables Moisture. Pressure 3. 3 1. 4. Dumping may be needed. 12 (some) 1. All rights reserved. Inerting 9. contaminants Excluding acetylene production Includes enzymes Contamination. 4.

toxicity.. ∆Hsol is positive.7-46 17-11 Page 14 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 3. decrease the minimum autoignition temperature. however. However. is shown in Figure 2. This heat of solution should not be confused with the heat of formation associated with a chemical reaction. water reactivity and oxidizing potential).) = C1/LFL1 + C2/LFL2 + … + Cn/LFLn where Cn is the concentration fraction. The flammable limits of a mixture may be different from the flammable limits of the individual components. Physical properties may also change significantly as a solute is put into solution. This is particularly true of inorganic compounds in water. increase the UFL. . An increase in pressure will decrease the minimum autoignition temperature and the minimum oxygen concentration for combustion (MOC). solubility. mixing with a chemical oxidant generally decreases the energy requirement for ignition. Figure 5 shows this for two pressures P1 and P2.g. and reactivity characteristics (e. solubility decreases as temperature increases. fire point. 3. An increase in temperature will similarly decrease the LFL. and corrosion. The LFLs and MOCs at one atmosphere decrease by about 8% of their values at room temperature for each 100°C increase. This is a multi-step process as shown in Figure 1.1 Physical and Chemical Properties All the pertinent physical and chemical properties of chemical materials should be evaluated in relation to the hazards of fire. Mixing with other flammables may widen the flammable limits. Likewise.0 SUPPORT FOR RECOMMENDATIONS Identifying reactive chemical hazards and chemical reaction hazards requires 1) knowledge of the physical and chemical properties of the reactants. vapor pressure. since physical property data is frequently listed at ambient conditions. where the pure material is in neither the gas nor the liquid phase. there is no change in enthalpy. nonideal solutions are formed. Since the equilibrium vapor pressure of a flammable liquid at its closed-cup flash point is about equal to its LFL in percent by volume. For example. flammability range. the LFL of the mixture can be estimated (by using Le Chatelier’s principle): 100 Composite LFL (% by vol. ©2003 Factory Mutual Insurance Company. explosion. flash point. If the enthalpy change that accompanies the mixing. A generalized pressure-temperature curve of a pure material is shown in Figure 3. It is important to understand the physical and chemical properties of the chemicals at actual reaction conditions. Lower & Upper explosive limit are often used interchangeably with LFL & UFL. accompanied by a change in enthalpy. Conversely. and products at process conditions and 2) an understanding of the reaction rate and the reaction mechanism. An increase in pressure raises the flash point. It should be noted that temperature changes designed to increase solubility might result in solute decomposition. When ideal solutions are formed.) A decrease in pressure to about one-half atmosphere has minimal effect. a mixture may be flammable even though each component is below its LFL. The temperature-solubility properties of three salts in water are shown in Figure 6. The solubility of a chemical is a function of the liquid composition and temperature. and decrease the MOC. Vapor pressure and temperature have a direct relationship. if ∆Ssol is negative. this data could be misleading. A vapor pressure-temperature curve for ethylene oxide with the atmospheric boiling point and critical point indicated. a decrease in pressure lowers the flash point. where P1<P2. If the energy change that accompanies the dissolution of a solute is known. The energy requirement for ignition of a mixture may be different from the energy requirements for ignition of the individual components. ignition temperature. Information can be found in available references or determined by testing. Beyond the critical point is the fluid region. intermediates. The UFLs at one atmosphere increase by about 8% of their values at room temperature for each 100°C increase. boiling point. Further decreases in pressure narrow the flammable range and it may essentially disappear. All rights reserved. shock sensitivity. These properties should include thermal stability. More commonly. it is possible (by using Le Chatelier’s principle) to predict the effect of a change in temperature on the solubility. (Note: LEL & UEL. the lower flammability limit (LFL) decreases and the upper flammability limit (UFL) increases (Fig. 4). An increase in pressure also will widen the flammability limits. solubility increases as temperature increases.

All rights reserved. 1.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 15 Fig. Reactive chemical and chemical reaction hazard evaluation. ©2003 Factory Mutual Insurance Company. .

Van Nostrand Reinhold. 1990. . ©2003 Factory Mutual Insurance Company. Compressed Gas Association.7-46 17-11 Page 16 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Fig. 2. All rights reserved. Vapor pressure-temperature properties of a pure material (ethylene oxide) Note: From the Handbook of Compressed Gasses.

M. Effects of pressure on the flammability of natural gas Note: Zabetakis. McGraw-Hill 1975. H.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 17 Fig. J. Pressure-temperature properties of a typical pure material Note: Smith. Fig. Michael Fire and Explosion Hazards at Temperature and Pressure Extremes. 4. and Van Ness. from the AIChE Fundamentals of Fire & Explosion Hazards Course Workbook. . 3. All rights reserved. Introduction to Chemical Engineering Thermodynamics.C. ©2003 Factory Mutual Insurance Company.

Michael Fire and Explosion Hazards at Temperature and Pressure Extremes. All rights reserved. Effects of temperature and pressure on flammability and autoignition temperature Note: Zabetakis. from the AIChE Fundamentals of Fire & Explosion Hazards Course Workbook ©2003 Factory Mutual Insurance Company.7-46 17-11 Page 18 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Fig. . 5.

All rights reserved. . 6. Effects of temperature on common salt solubility ©2003 Factory Mutual Insurance Company.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 19 Fig.

7-46 17-11 Page 20 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets An increase in temperature and/or pressure may significantly increase the potential energy of chemical materials. 2. | | -C-C\ / O These include ethylene oxide and propylene oxide. Hazards include uncontrolled polymerization and formation of unstable peroxides. Causes and Effects of Fires and Explosions) to the energy of TNT as shown in Table 2. As an example. classification systems have been developed. Hazards include explosive decomposition. Note: aldehydes (RCHO) and ketones (R1R2CO) are both included in the carbonyl compound group. Hazards include self-accelerating decomposition initiated at low temperatures. dinitrotoluene.(two or more double bonds) These include acrylonitrile and 1. | | | | 3.000 10. Haloacetylene derivatives: -C≡C-X These include acetylene and propargyl alcohol. Estimated Energy of a Confined Gas Gas Pressure (psig) 10 100 1. Aldehydes are easily oxidized. Peroxides: R-O-O-R. 6. Conjugated unsaturated compounds: . uncontrolled polymerization.42 6. All rights reserved.001 0. . Hazards include explosive decomposition and contaminant catalyzed uncontrolled polymerization. Organic chemicals are further classified by functional group into subclasses and families. Hazards include highly exothermic reaction with inorganic acids and instability. than do ketones. Table 2. Compounds within the following families deserve special attention due to their structural elements. Hazards include rapid oxidation or reduction. and formation of unstable peroxides.53 3. ©2003 Factory Mutual Insurance Company. Hazards include uncontrolled polymerization and formation of unstable peroxides. and vinyl chloride. Aldehydes more readily undergo nucleophilic addition. Alkylperoxides: C-O-O-H. and Metal peroxides: -O-O-M These include benzoyl peroxide and >60% hydrogen peroxide. Hazards include explosive decomposition. whereas ketones are oxidized only with difficulty. Chemicals are classified as either organic (carbon based) or inorganic (non-carbon based).000 TNT Equivalent (lb) Per cubic foot of gas 0.C = C . the potential energy of a confined gas can be estimated by using the isothermal expansion equation (see Data Sheet 7-0.C = C . The hydrogen atom versus organic group attached to the carbonyl group makes a significant difference in their reactivity. and trinitrotoluene (TNT).02 0. Nitrated organic compounds: Nitro-Alkanes: R-NO2 These include nitromethane. vinyl benzene (styrene).3 butadiene. Alkynes (triple-bonded hydrocarbons): R1-C≡C-R2. 4. Fortunately. Epoxides (oxirane ring): 5. Alkenes (double-bonded hydrocarbon): R-CH = CH-R These include vinyl acetate. Carbonyl compounds: -C = O These include acetaldehyde and butyraldehyde. the characteristic reaction of carbonyl compounds. 1. 7. Azo compounds: R-N = N-R These include p-hydroxyazobenzene.2 Chemical Functional Groups that Deserve Special Attention due to their Structural Elements There are a tremendous number of chemicals that have been identified to date.

2. Reactive Chemical Hazards: An Overview. Process utilities are generally listed on only one axis. Hazards include explosive decomposition/detonation. materials of construction. International Symposium on Preventing Major Chemical Accidents. 7). Azides: -N3 These include sodium azide. All rights reserved. isopropyl compounds. These structures include acetals. ethers.6. catalysts. and vinyl compounds. 1987 ©2003 Factory Mutual Insurance Company. a human factor. as utility interactions are outside the scope of process development (these 1 Bretherick. N-Nitroso. Some other families of compounds that have been known to undergo violent or explosive decompositions are as follows (Note: this is not an all-inclusive list). fulminates and N-metal derivatives Nitroso. L. .3 Interaction Matrix The interaction matrix is a tool for understanding potential reactions between materials. A typical matrix will list all the chemical raw materials. and N-Nitro compounds Perchloryl compounds Perchloric acid Polynitro alkyl and aryl compounds Tetrazoles Teiazenes A qualitative analysis of unstable structures can be made by comparing the molar energy of decomposition (U) of some well-known unstable compounds (Table 3). Aci-nitro salts Acyl or alkyl nitrates and nitrites Aminachromium peroxo complexes Alkyl and ammonium perchlorates Aminemetal and nitrogenous base oxosalts Chlorite salts Diazeno Diazirines Difluoroamino compounds Halogen azides and oxides Hydrazinium salts Hydroxylammonium salts Hypohalites Metal acetylides. 3.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 21 Diazo compounds: R = N = N These include o-toluenediazonium chloride (salt). Table 3. allyl compounds. Hazards include explosive decomposition.2. and any other pertinent factors on the axis (Fig. Oxidation). styrene. potential contaminants. Unstable Structure Decomposition Energies1 Compounds (# tested) Aromatic nitro (30) Aromatic nitroso (4) Oxime (5) Isocyanate (4) Aromatic azo (5) Hydrazo Aromatic diazonium (5) Peroxide (20) Epoxide (4) Alkene (6) Molecular Structure C-NO2 C-N = O C = N-OH C-N = C = O C-N = N-C C-NH-NH-C C-N2+ C-O-OCH-CH-O (ring) C=C -U (kJ/mol) range 220-410 90-290 110-170 50-55 100-180 65-80 130-165 200-340 65-100 40-90 Bretherick has identified several structures as susceptible to autoxidation (see section 3. solvents. dienes. process utilities. cumene.

All rights reserved. more. and previous incidents. and other. part of. The ©2003 Factory Mutual Insurance Company. modification. Example of an in-progress interaction matrix for a generic chemical process. less. and review. There may be interactions with unknown consequences that require further research and/or experimentation. Documentation should include notes on the anticipated interactions.7-46 17-11 Page 22 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets are usually addressed later on during process HAZOPs). Each interaction is then considered and the answer documented. as well as. 3. 7. An interaction matrix is best prepared by a chemist or chemical engineer. . Interaction of three or more components is generally handled by listing combinations as separate entries. They are similar in that the seven basic HAZOP guidewords are used: no. reverse. Fig. They are different in that the CHA assumes the proposed chemical reaction is basically safe when conducted as specified (should be confirmed) and focuses on the consequence of operating outside of the specifications.4 Chemical Hazard Analysis Chemical Hazard Analysis (CHA) is derived from Hazard and Operability Study (HAZOP) methodologies and can be considered a precursor to a Process Hazard Analysis (PHA). specific references. then circulated to others to fill in open blocks.

Selected values are also listed in Table 4. Note that this range is highly dependent on the process conditions and does not pertain to substances that produce significant quantities of gas. A substance should be considered as having a detonation potential if the experimental enthalpy of decomposition in the absence of oxygen is greater than 700 cal/g (2. The dehydration activation energy is nearly the same as the reaction enthalpy. The ASTM Computer Program for Chemical Thermodynamics and Energy Release Evaluation (CHETAH) is an analytic tool used to determine the maximum enthalpy of decomposition. Can Solvent Choices Enhance Both Process Safety and Efficiency. and carbonate decompositions. hydroxide. Known explosive compounds have CART values higher than 1500 K. . Evon. No.2 and different solvents may have different effects on the decomposition temperature and rate. All rights reserved..000 J/g)4. The CHA is used for reference during future PHAs.. nitramines. A. Oxygen balance is an analytic tool based on the difference between the oxygen content of the chemical compound and that required to fully oxidize the elements of the compound. Endothermic decompositions are usually reversible and are typified by hydrate. Oxygen balance calculations may be used for organic nitrates and nitro compounds. Values of 170 to 300 cal/g can be found in the literature 4 ∆Hd of 700 cal/g is the value adopted by the CCPS. diazo compounds. S. Several exceptions are known. Essentially all materials are unstable above certain temperatures and will thermally decompose. J. oxygen-containing salts and metal styphnates. The calculated adiabatic reaction temperature (CART) also provides some indication of a compound’s potential hazard. However. Solids that decompose without melting usually generate gaseous products.1) 3 ∆Hd of 250 cal/g is the value adoptedby the Center for Chemical Process Safety (CCPS). S. Age may result in crystallization of the solid surface. A substance should be considered energetic and potentially hazardous if any of the theoretical methods indicate hazardous thermal properties or if the experimental enthalpy of decomposition in the absence of oxygen is over 50-70 cal/g (∼200-300 J/g). Chervin. G. It is based on molecular structure-reactivity relationships. there is no correlation between oxygen balance and general self-reactivity. a substance may have several hydrates depending on the partial pressure of water vapor. Its major limitation is that it can predict the reactivity of organic compounds only. A substance should be considered as having a deflagration potential if the experimental enthalpy of decomposition in the absence of oxygen is greater than 250 cal/g (∼1. and organic peroxides have ∆Hd of less than 475 cal/g 2 ©2003 Factory Mutual Insurance Company. E.900-3. Process Safety Progress (Vol. not inorganic compounds.18. For example. 7. 5.. Decomposition characteristics of energetic materials can be significantly different from those of the same chemical when combined with a solvent. Particle size and aging affect the decomposition rate. or 12 molecules of water. FeCl2 combines with 4.000 J/g)3. Improper application of the oxygen balance criterion can result in incorrect hazard classifications. Ferric chloride. azides. Exothermic decompositions are usually irreversible and frequently explosive. and Torres. Ammonium nitrate. Selected enthalpy of decomposition (∆Hr) values are listed in Table 4. Bodman.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 23 consequences are then considered and potential hazards documented for reference. There may be unknown consequences that require further research and/or experimentation..T. Materials and processes approaching zero oxygen balance have the greatest heat release potential and are the most energetic. Organic compounds that are known to decompose before melting include azides. Thermal decompositions may be exothermic or endothermic.

and Melham.27 -0. or reversibly. The heat or enthalpy of formation provides information on the thermochemical stability of the elements that are involved in the subject reaction.73 -2. and relative hazard rankings for selected compounds 5.S. 1995 ©2003 Factory Mutual Insurance Company. concurrently. but is in the high hazard category based on its enthalpy of decomposition value. For complex reactions.05 -5.78 -2. but is in the moderate hazard category based on its enthalpy of decomposition value. Mononitrotoluene has no vigorous self-reactivity hazard. This is obvious if the maximum enthalpy of decomposition and the CART data in Table 4 are compared. They vary in complexity relative to the chemical reaction complexity.13 -1.92 -3.92 -1. The rate at which that energy is released is not a constant.A. Toluene has no known selfreactivity hazard. Enthalpy of Decomposition.70 -5.80 -6. but the rate of energy release is more important than the amount of energy released. . It is the rate of the reaction that differentiates normal chemical reactions from uncontrollable chemical reactions.38 -4. 5 Shanley. On the Estimation of Hazard Potential for Chemical Substances.23 -1. For simple reactions. The enthalpy of reaction provides some guidance as to the potential hazard.77 -1.5 Chemical Thermodynamics All chemical reactions involve energy changes in order to transform reactants into the products. A positive enthalpy of formation value provides a warning of a potential hazard.09 0.00 -4.72 -10.18 -2. the rate expression can be derived from the stoichiometric equation. Compound Acetone Acetylene Acrylic acid Ammonia Benzoyl peroxide Dinitrotoluene Di-t-butyl peroxide Ethyl ether Ethyl hydroperoxide Ethylene Ethylene oxide Furan Maleic anhydride Mercury fulminate Methane Mononitrotoluene Nitrogen trichloride Nitroguanidine Octane Phthalic anhydride RDX Silver azide Trinitrotoluene Toluene Formula C3H6O C2H2 C3H4O2 NH3 C14H10O4 C7H6N2O4 C8H18O2 C4H10O C2H5O2 C2H4 C2H4O C4H4O C4H2O3 Hg(ONC)2 CH4 C7H7NO2 NCl3 CH4N4O2 C8H18 C8H4O3 C3H6N6O6 AgN3 C7H5N3O6 C7H8 ∆Hr (kJ/g) -1. All rights reserved.13 -2. 3.72 -0.18 CART (K) 706 2824 789 972 1511 847 723 1058 1253 1009 995 901 5300 298 104 1930 1840 552 933 2935 >4000 2066 810 Hazard Index N E N N E E E N E N N N N E N N E E N N E E E N N-no known unconfined explosion hazard E-unconfined explosion hazard No single tool should be depended upon in a chemical hazard analysis.18 2.60 -2. Reaction rate studies can be conducted to determine reaction rates. G.7-46 17-11 Page 24 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Table 4. For complex reactions. the rate expression is usually based on the rate expression for a similar chemical reaction and compared to the experimental data to determine its validity. International Symposium on RunawayReactions and Pressure Relief Design. E. the total amount of energy released or required is a constant. Neither the enthalpy of decomposition nor CART values adequately predicts the hazards presented by organic peroxides. For a given chemical reaction. A negative enthalpy of formation value is of no potential use from a hazard evaluation perspective. CART values.43 -2. there may be several reaction steps proceeding consecutively. The heat or enthalpy of reaction provides information on the amount of stored chemical energy.65 -1.59 -3.

This is why temperature control of exothermic reactions is important. In an exothermic reaction. the reaction rate may also be affected by chemical and physical interactions. In a homogeneous catalytic reaction. and interfacial surface area. Catalyzed reactions have lower activation energy and/or activation entropy than the uncatalyzed reactions. Exothermic reactions generally proceed readily at ambient temperatures. Activation entropy is affected by the presence of a catalyst. the faster the reaction rates. They may have an inherent tendency to spontaneously decompose. However. Usually the catalyst is a solid. the faster the reaction rates. All rights reserved. flow pattern. Endothermic reactions generally proceed with difficulty and are slow except at elevated temperatures. The minimum energy of activation is an important reaction rate characteristic that must be overcome. the catalyst is present in a different phase from the reaction mixture. Common examples are enzymes. the reaction occurs in one phase and the reaction rate depends on the catalyst concentration. Practically.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 25 Basic factors affecting chemical reaction rates are the frequency of the molecular collisions. Intuitively. exothermic decompositions and side reactions may occur. Since the rate of reaction increases exponentially with temperature. The less specific the orientation required for the reaction to proceed. and the reaction rate depends on the surface area. It is dependent on pressure and is affected by the presence of a catalyst. Phase changes involving pure substances will exhibit latent heat effects even though no chemical reaction takes place. the rate of a reaction increases exponentially with temperature. concentration and material purity. the overall energy change is negative. 8). a heat of mixing is associated with the process even though no chemical reaction takes places. It is usually necessary to add heat to overcome the energy of activation of both exothermic and endothermic reactions (Fig. Comparison of the positive energy of activation for the decomposition reaction to the negative energy of the decomposition reaction will indicate if a self-sustained decomposition reaction is likely. while vessel heat losses to the surroundings only increases linearly with temperature. ©2003 Factory Mutual Insurance Company. pressure. this means temperature. The lower the activation energy. . the reaction activation energy and the reaction activation entropy. Activation energy generally is not affected by temperature (within moderate ranges). Reaction rate studies need to take all these factors into consideration. Practically. The rate that energy is released depends on several factors. A negative catalyst or inhibitor may be used to stop a reaction. proteins that catalyze biochemical reactions. And the catalyzed reaction may favor one reaction mechanism over others. In Arrhenius’ Rate Law equation. When two or more substances are mixed to form a solution. The intermediate complex then reacts with the other reactants to form the desired product and regenerate the catalyst. The products of the endothermic reactions are typically highly unsaturated. the greater the frequency of collisions. there is a temperature above which an exothermic reaction cannot be controlled simply by cooling. In many cases. reaction rates will double or triple for every 10°C increase in temperature. contain high concentrations of nitrogen. the reaction occurs at the solid surface. if an endothermic reaction temperature is raised too high. the overall energy change is positive (more heat is added than given off). the rate of reaction can be limited by the addition rate of the reactants or by an inhibitor to prevent excessive reaction rates. The assumption that heat given off by a process indicates an exothermic reaction may also be false. this means fluid dynamic properties. Catalysts can be thought of as forming intermediate complexes with some of the reactants. with temperature being the most significant. Catalytic reactions are classified as homogeneous or heterogeneous. In an endothermic reaction. The assumption that heat addition to a reactor indicates endothermic reactions is frequently not correct. Practically. In a complex reaction. or nitrogen-halogen bonds. In a heterogeneous catalytic reaction. the faster the reaction rates.

aluminum chloride or similar -RX catalysts in the presence of a Lewis acid. halogenation. and carbon-oxygen reactions. In some processes. Grignard reactions and many other organometallic reactions are also alkylation reactions.7-46 17-11 Page 26 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Fig. hydration. Quaternization is an example of carbon-nitrogen alkylation.6 Chemical Reaction Types Common types of reactions are described and examples are provided. organometallic compounds. high pressure is applied to promote completion of the reaction.6. 8. In other cases. . Temperatures in this class of alkylation reaction vary widely.6. 3. sulfonation. Pressures also vary considerably. 3. Alkylation reactions are diverse in nature and include carbon-carbon. 3. Williamson reactions are carbon-oxygen alkylations. see organometallic compounds.2 Alkylation Alkylation is the addition or insertion of an alkyl group (CnH2n+1) into a molecule. polymerization. ©2003 Factory Mutual Insurance Company. are primarily carboncarbon alkylations. These reactions are best described by the functional group of the reagent. oxidation.1 Addition Addition reactions are reactions in which two molecules combine to form a single molecule of product. etc. universal method of conducting alkylations. All rights reserved. There is no inclusive. Friedel-Crafts reactions. ranging from ambient to 750°F (400°C) for processes conducted in the vapor phase. Enthalpy diagram of an exothermic reaction. carbon-nitrogen. pressure is applied to keep the volatile reactants liquid. hydrogenation. see alkylation. but are better considered separately. amination. Pressures can be in excess of 1000 psi (7 MPa). Carbon-oxygen alkylations can use acids or bases as catalysts.

diethanolamine. but also can involve reaction with liquid or gaseous anhydrous ammonia. Special attention should be given to moving parts and instruments to protect them from corrosion. a corrosion-resistant lining must be used. but pressures are usually high. -OH. but most range from 0° to 150°F (. -SO3H. Amination by reduction is the preparation of amines by the reduction of an -NO2 or a similar oxidized nitrogen component of a compound to an -NH2 group. Ammonolysis using gaseous anhydrous ammonia is usually performed in the presence of a catalyst. see hydrogenation. The process usually involves reaction of a material with ammonia in water solution. It can also involve the addition of ammonia to an unsaturated compound. and triethanolamine: (CH2)2O + NH3 (aq) → NH2(CH2)OH + NH((CH2)2 OH)2 + N((CH2)2 OH)3 ethylene ammonia monoethanolamine diethanolamine triethanolamine H2O water ©2003 Factory Mutual Insurance Company.3 Amination Amination is the replacement of another functional group with –NH2 or –NH3 in an unsaturated compound or by the reduction of –NO2 to –NH2 with hydrogen. and phosphoric acids are also used.5 MPa). Temperatures and pressures vary. and -O. Alkylation products include ethyl benzene. . cooling. glycols. cumene. For example. and synthetic lubricants.18° to 65°C). detergents. the chlorobenzene process below operates at 355-430°F (180220°C) and 950 psi (6.4-trimethylpentane (iso-octane) b) Addition of an alkyl group onto a benzene ring to produce a larger aromatic hydrocarbon: C6H6 + CH3CHCH2 → C6H5CH2(CH3)2 benzene propylene cumene c) Substitution of the hydrogen attached to a nitrogen atom: + 2CH3OH → C6H5N(CH3)2 + C2H5NH2 aniline methanol dimethylaniline d) Substitution of the hydrogen attached to an oxygen atom: C2H5OH + (CH2)O → C2H5OC2H4OH ethanol ethylene oxide Cellosolve Equipment Alkylation reactors are normally constructed of steel. sulfuric.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 27 Alkylation of saturated hydrocarbons is done catalytically. All rights reserved. hydrofluoric.2. dyes. Where a highly corrosive catalyst or reagent is used. pressure relief and instrumentation. Process Chemistry a) Ammonolysis of ethylene oxide produces a mixture of monoethanolamine. Smaller-scale alkylations may be performed in batch reactors. For reduction processes using hydrogen. temperatures of alkylation reactions vary considerably depending upon the reactants and the catalyst used. ethers. Large-scale alkylations are generally continuous processes. With catalysts. and instruments are often made from special alloys such as Monel. Aqueous ammonolysis are usually performed without catalysts. Process Chemistry a) Substitution of hydrogen attached to a carbon atom with an acid catalyst: + CH(CH3)3 acid (CH3)2CHCH2C(CH3)3 CH(CH2)(CH3)2 isobutylene isobutane → 2. Process pressures of 3000 psi (21 MPa) are not unusual. Ammonolysis using liquid anhydrous ammonia is less common than aqueous solutions since higher pressures must be used to maintain the liquid state.6.with -NH2 to form an amine. The autoclave may have agitation and may need heating. -NO2. 3. Because of pressure requirements. valves. an autoclave is usually used. In addition to –RX catalysts. Pumps. Pressures are normally only high enough to maintain the reactants in the liquid state. Amination by ammonolysis is the replacement of constituents in a compound such as -CI.

6 MPa). hydroxylation. chemical and pharmaceutical industries. Small diameter tubes are commonly employed where the reaction is rapid or the heat of reaction must be removed rapidly. 3. Biotechnology increasingly refers to processes using recombinant DNA technology. Conversion is primarily by catalytic reforming. See fermentation for process equipment and hazard descriptions. Bioconversion.6 MPa) are usually carried out in tubular reactors. lime. and biotransformation are all names for the use of biological substances in a biochemical reaction. amination. which must be dehydrated to produce urea. epoxidation. .6. 3. continuous reactors are used.7-46 17-11 Page 28 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets b) Ammonolysis of chlorobenzene produces aniline: C6HCl + 2NH3 (aq) → C6H5NH2 chlorobenzene ammonia aniline + NH4Cl ammonium chloride c) Ammonolysis of carbon dioxide produces ammonium carbonate as an intermediate. Vessels may be solid-walled or built up of successive layers. hydrolysis. In small-scale processes. bioconversion. or reduction.6 Calcination Calcination is the heating of a material to a high temperature to cause it to lose moisture or another volatile component. batch reactors are used. Reactions at pressures above 800 psi (5. Operations are typically conducted at elevated temperatures and pressures in the presence of a catalyst. gypsum. These reactions involve the rearrangement of the atoms in an organic molecule without changing the number of carbon atoms. This is true despite the fact that the actual reaction mechanism may be an addition. autoclaves are normally used as both batch and continuous reactors. which is commonly used in the agricultural.4 Aromatization Aromatization is the conversion of aliphatic compounds to aromatic compounds (benzene ring derivatives). For pressures up to 800 psi (5.6. It is most common in the cement. polymerization. All rights reserved. Process Chemistry a) Calcination of lime at 2200 to 2370°F (1200 to 1300°C): CaCO3 → CaO + CO2 calcium carbonate calcium oxide carbon dioxide b) Calcination of gypsum at 250 to 375°F (120 to 190°C): → CaSO4 + 2H2O CaSO4z2H2O gypsum anhydrite gypsum water catalyst → C6H5CH3 toluene + 4H2 hydrogen ©2003 Factory Mutual Insurance Company. Biochemical reactions are classified as fermentation reactions because of their use of biological substances. dehalogenation. esterification. Process Chemistry CH3CH2CH2CH2CH2CH3 n-heptane Equipment In large-scale processes. 3. biotechnology. Some gas-phase reactions are carried out continuously in reactors that are essentially shell-and-tube heat exchangers. The overall reaction is: CO2 + 2NH3 (l) → (NH2)2CO + H2O carbon dioxide ammonia urea water d) Ammonolysis of methanol with an aluminum oxide catalyst to produce methylamines: CH3OH + NH3 (g) → NH2CH3 + NH(CH3)2 + N(CH3)3 + H2O methanol ammonia methylamine dimethylamine trimethylamine water Equipment Aminations by ammonolysis are usually carried out most economically at elevated temperatures and pressures.6. Biotechnology and Biotransformation Biocatalysis.5 Biochemistry: Biocatalysis. and soda ash manufacturing. see reforming.

Waste Solvent Recovery. or electricity. 3. Doebner. Condensation reactions are diverse in nature. and thiazoles. or conducted at elevated temperatures. water. Equipment may be constructed of stainless steel or special alloys (Hastelloy.7 Combustion Combustion is the reaction of a solid. then the reactions are better considered separately. All rights reserved. see Data Sheet 6-9. waste fuels/gases. Combustion reactions are also used to generate gas for use as an inerting agent. Process Furnaces. and heat. Aldol condensations are an example of an aldehyde or ketone condensation.6. but they are usually conducted at moderately elevated temperatures and near atmospheric pressures. Knoevenagel. see the appropriate reactions for additional information. Industrial Ovens and Dryers and Data Sheet 6-10.) to improve corrosion resistance. dyes.6. Fume Incinerators and Data Sheet 7-2. with or without catalysts. Equipment Large steel kilns are used for calcining. They may be catalyzed by bases or acids. and Perkin condensations are closely related to the Aldol condensation. Horizontally rotating kilns are most common. H2O water H2S hydrogen sulfide ©2003 Factory Mutual Insurance Company. Elements of Industrial Heating Equipment and the appropriate data sheet on heating equipment. Process Chemistry a) Aldol condensation using sodium hydroxide or sodium ethoxide as the catalyst: C6H5CHO + CH3CHO → C6H5CH = CHCHO + H2O benzaldehyde acetaldehyde cinnamaldehyde water b) Condensation using sulfuric acid as the catalyst at 250°F (120°C): C6H4(CO)2O + 2C6H5OH → C6H4C(C6H4OH)2COO + phthalic anhydride phenol phenolphthalein c) Condensation at a higher temperature. Some condensation reactions are also alkylation or polymerization reactions. oil. If the combustion is intentionally incomplete (producing carbon monoxide or other unburned combustion products) or if other elements such as sulfur are burned. Monel. etc. Vertical kilns are often used for lumpy material. and at the same time splitting off a small molecule such as water or hydrochloric acid (HCl). The principal objective normally is to produce heat. 560°F (293°C): CH3CH2CH2CH3 + S → C4H4S + n-butane sulfur thiophene Equipment Most condensation reactions take place in stirred batch reactors. quinalines. pulverized coal. Condensation reactions are frequently used to produce the active ingredients in flavorings. Inconel. pyrazoles. and pharmaceuticals. see oxidation. Claisen.8 Condensation Condensation is the joining together of two or more molecules by two carbon atoms. Condensation reaction conditions vary. see Data Sheet 6-0/12-1. Rotary Kilns and Dryers. perfumes. Dieckmann. Additional information on off-gas treatment is provided in Data Sheet 6-11. Alloy C. liquid. Alloy B. They are also used to produce heterocyclic compounds such as imidazoles. 3. with corrosion resistant linings when necessary. Additional information on kilns is provided in Data Sheet 6-17/13-20.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 29 c) Sodium bicarbonate is converted to sodium carbonate (soda ash) at 350 to 440°F (175 to 225°C): 2NaHCO3 → Na2CO3 + CO2 + H2O sodium bicarbonate sodium carbonate carbon dioxide water d) Calciners are also used in heating petroleum coke to 2550°F (1400°C) to drive off flammable volatile materials before converting the coke to graphite. Kilns may be heated by gas. or gaseous hydrocarbon with air to produce carbon dioxide. .

see the appropriate reactions for additional information. Process Chemistry a) Electrolysis of water. Electrolytic Chlorine Processes. or condensation reactions. An inorganic salt generally exchanges a constituent with an acid. The reactor may also be used for separation. usually in water. Some double decomposition reactions are also halogenation. 3. or another salt.9 Double Decomposition Double decomposition reactions involve an exchange of one or more constituents. and magnesium salts. in the form of a molten salt. Non-metals and/or oxygen are discharged at the anode (+). calcium. in diaphragm cells to produce hydrogen and oxygen: H2O → H2 + O2 water hydrogen oxygen b) Electrolysis of anhydrous hydrofluoric acid in potassium bifluoride.6. HF → KF . Fluorine is also produced commercially using an electrolytic process. and pigments. HF + KF . Highly reactive products or by-products can be generated. between two reacting molecules. Electrolysis is frequently used to extract or purify metals. and sodium reacts with the water to generate hydrogen at the cathode. at medium temperature and operating currents >6000A to produce fluorine. base. All rights reserved. As a general rule. Special linings or materials may be used for corrosion resistance. The most common electrolytic process in a water solution is the electrolysis of sodium chloride in diaphragm cells. Process Chemistry a) Double decomposition of two inorganic salts: + KCl → NaCl + NaNO3 sodium nitrate potassium chloride sodium chloride b) Double decomposition of an inorganic salt and an acid: → Na2O4 + 2NaCl + H2SO4 sodium chloride sulfuric acid sodium sulfate c) Double decomposition of an inorganic salt and a (NH4)2S2O8 + 2NaOH → 2NH4OH + ammonium sodium ammonium persulfate hydroxide hydroxide Equipment These reactions are conducted in steel reactors or ordinary tanks.10 Electrolysis Electrolysis is the separation of ions by means of electric current. 2HF → F2 Hydrofluoric acid potassium biflouride electrolyte fluorine c) Electrolysis of ammonium sulfate or sulfuric acid produces ammonium persulfate or persulfuric acid.6. The oxygen reacts with the carbon anode to form carbon dioxide: 2Al2O3 + 3C → 4Al + 3CO2 Alumina carbon aluminum carbon dioxide KNO3 potassium nitrate 2HCl hydrochloric acid H2O water base: Na2S2O8 + NH3 + sodium ammonia persulfate ©2003 Factory Mutual Insurance Company. or as a crystallizer. using a dilute sodium hydroxide solution to improve conductivity. . potassium. respectively: 2H2SO4 → H2S2O8 + H2 sulfuric acid persulfuric acid hydrogen d) Aluminum is produced by electrolysis of alumina dissolved in molten cryolite (Na3AlF6). inorganic acids. or present as the anode. as a still.7-46 17-11 Page 30 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 3. Chlorine is evolved at the anode. esterification. These reactions are common in water softening and the manufacture of sodium. metals and/or hydrogen are discharged at the cathode (-). This process is described in more detail in Data Sheet 7-34. The ionic compound may be in a water solution.

Operational temperatures are typically a little above ambient. Fermentation processes are classified based on whether they are catalyzed by microorganisms (microbial) or by enzymes (enzymatic). or hydrochloric acid. the catalytic agent does not reproduce. or other metals. This reversibility is a disadvantage. Esterification via the acid chloride route is essentially irreversible. of being a single step route. In enzymatic fermentation. and protozoa) or their enzymes. 3. Esterification of an organic acid and an alcohol is an equilibrium reaction. Many esters are used in fragrances. Thionyl chloride (SOCl2) is the catalyst for the first step. proteins. monoclonal antibodies.12 Fermentation Fermentation was originally defined as the anaerobic (without oxygen) metabolism of organic compounds by microorganisms (yeast. the desired product could be a cell waste product or a cell component. sulfuric. or rubber. Electrodes may be copper. see nitration. particularly in lacquers.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 31 Equipment Electrolytic cells are normally of steel. All rights reserved. . Equipment Esterification reactions between an alcohol and an organic acid are usually conducted in stirred batch reactors with a distillation column attached to the reactor. the reaction may also be classified as a nitration. They are also used widely as solvents. Esterifications involving strong inorganic acids are better considered separately. ©2003 Factory Mutual Insurance Company. carbon. bacteria. Acids can also be converted into their esters using acid chlorides. algae. as appropriate. This definition has been expanded over time to also include aerobic (with oxygen) microbial processes. or food additives because of their pleasant odor. fire brick.11 Esterification Esters are organic compounds corresponding in structure to salts in inorganic chemistry. in order to make the reaction go to completion.6. but has multiple steps. the catalytic agent reproduces itself as part of the microbe’s metabolism. Fermentations are typically aqueous and in some aerobic fermentation reactions supplemental oxygen may be added. Operations are conducted at moderate temperatures and pressures. It has the advantage. catalyzed using either an acid or base (transesterification). or halogenation. This section covers only esters of organic acids. Ethanol is used as the solvent for the second step: (CH3)3CCOOH + (CH3)3CCOCl → (CH3)3CCOOC2H5 trimethylacetic acid acid chloride ethyl trimethylacetate c) A mixture of methyl esters and glycerol is prepared by reacting a glyceride (fat) with methanol. Fermentation is used to produce active pharmaceutical ingredients (antibiotics. sulfonation or halogenation reactions. Where the acid is a strong inorganic acid such as nitric. This difference is significant because it influences the addition of reactants and equipment selection. Operational pressures obviously vary depending on whether it is an anaerobic or aerobic fermentation. the equilibrium must be shifted by either removing one of the products or by using an excess of one of the reactants. They may also be constructed partly of concrete or plastic. sulfonation. 3.6. molds. They may be lined with carbon. Esters are most often prepared by reacting an acid and an alcohol. Transesterification is the replacement of one alcohol with another alcohol in an ester. platinum. Ammonia may be used to regulate pH and as a nitrogen source for the microbe. flavors. The key distinction between these two types of fermentations is that in microbial fermentation. and vitamins) and in the fine chemical and chemical intermediate industries to replace chemical synthesis steps and/or as an alternative to petrochemical routes. though. Process Chemistry a) Esterification of an alcohol with an organic acid to form an acetate: + CH3COOH → C6H5CH2OCOCH3 + C6H5CH2OH benzyl alcohol acetic acid benzyl acetate H2O water b) Esterification via the acid chloride route.

This may be done by addition to an unsaturated bond or by replacement of an -H. yogurt. and proceed at relatively slow rates. Iodinations can be difficult to initiate. 3.15 Halogenation Halogenation is the process of introducing halogen atoms (fluorine. Halogenation reactions are conducted at moderate temperatures and pressures. Mechanical anti-foaming devices may be provided. chilled water. Flammable Liquid Operations. or -SO3 H group. by the mold Aspergillus niger. -OH.000 gal (187. chlorine. Utility reliability is critical throughout the fermentation process. Mechanical Refrigeration and Data Sheet 7-50. Tower fermenters may be used to retain heavily coagulated cells. Fermenters operate in batch or semi-batch mode and are as large as 50.6. sauerkraut. 3. Reactions are often initiated by a light source within the reactor as an alternative to operating at higher temperatures.7-46 17-11 Page 32 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Fermentation is most commonly used to produce alcoholic beverages by the enzymatic breakdown of carbohydrates to simple sugars with subsequent yeast metabolism to produce ethanol. C6H12O6/water + Ca (OH)2 + glucose solution calcium hydroxide Equipment Most fermenters are stirred tank reactors constructed of stainless steel. All rights reserved. Fermentation processes are also used to produce foodstuffs (tea. lactic acid. reactions must be carefully controlled. Most fermenters are equipped with sparger systems with large openings to avoid clogging by microbial growth. Compressed Gases in Cylinders and Data Sheet 7-52/17-13. and compressed air are needed to achieve optimum yield from a batch.6. Downstream processing equipment is usually sized to operate continuously. The reactivity of the halogen atoms varies a great deal. A batch may take a few days or up to three weeks to complete. and are usually accompanied by surface active antifoam agent delivery systems. citric acid. Additional information on fermentation processes is provided in Data Sheet 7-32. Toroidal fermenters (ring-shaped) may be used where air mixing is part of the process. by yeast.6. Additional information on oxygen use is provided in Data Sheet 7-50. Compressed Gases in Cylinders. See the appropriate data sheets for additional utility equipment information and safeguards. supplied from multiple fermenters. Large quantities of electric power. Chlorinations and brominations proceed at relatively reasonable rates. and to purify organic wastes (sewage). . or iodine) into an organic molecule. Data Sheet 7-47. to produce ethanol and fusel oil (mixture of primary alcohols): C6H12O6 → CH3COCOOH + CO2 N → NCH3CHO → 2C2H5OH + fusel oil + CO2 glucose pyruvic acetaldehyde ethanol carbon dioxide b) Aerobic fermentation of molasses. Process Chemistry a) Anaerobic fermentation of sugar cane or starch. 3.000 liters).13 Fuel Gas Processes See Oxidation.14 Grignard Reactions See Organometallic Compounds. to citric acid: H2SO4 + O2 → C6H8O7 + Ca SO4 sulfuric oxygen citric gypsum acid acid + CO2 carbon dioxide ©2003 Factory Mutual Insurance Company. Fluorinations usually proceed so vigorously that even in the dark and at room temperature. and pickles). Additional information on ammonia use is provided in Data Sheet 7-13. Oxygen. Distilleries. Physical Operations in Chemical Plants and Data Sheet 7-74. bromine.

The reaction of an unsaturated carbonyl compound with ammonia and hydrogen. and in the preparation of amines. in the production of synthetic natural gas. Hydrogenation reactions can be conducted at low to very high pressure. . even at high temperatures. or aluminum. 3. (C17H31COOO)3C3H5 + 3H2 → (C17H33COO)3C3H5 linolein hydrogen olein b) Hydrogenation of carbon monoxide to form methanol. fluorination is often conducted by first chlorinating the compound and then substituting the fluorine for chlorine: CCl4 + 2HF → CCl2F2 + 2HCl carbon hydrofluoric dichlorohydrochloric tetrachloride acid difluoromethane acid Equipment Halogenations are normally carried out in reactors designed for the corrosive characteristics of the chemicals present. Hydrogenations are also is used in many petrochemical processes. The products are recycled to get the degree of chlorination desired: CH4 + Cl2 → CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl methane chlorine methyl methylene chloroform carbon hydrochloric chloride chloride tetrachloride acid c) Halogen replacement: Because fluorine is violently reactive with many compounds. In the absence of a catalyst. and localized high temperatures will exist on the catalyst surface. C6H5NO2 + 3H2 → nitrobenzene hydrogen C6H5NH2 + 2H2O aniline water ©2003 Factory Mutual Insurance Company. CO + 2H2 → CH3OH carbon monoxide hydrogen methanol c) Amination and hydrogenation. The reaction takes place on the surface of the catalyst. steel may be used. Continuous tubular reactors. They may be glass or ceramic lined. CH2 = CHCHO + NH3 + 2H2 → CH3CH2CH2NH2 + H2O acrolein ammonia hydrogen n-propylamine water d) Amination by reduction. The most common use of hydrogenation is the conversion of unsaturated animal and vegetable fats and oils into more highly or completely saturated oils. chromium.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 33 Process Chemistry a) Halogen addition to a double bond: phosgene (highly poisonous gas): → COCl2 CO + Cl2 carbon monixide chlorine phosgene b) Halogen replacement of hydrogen: chlorination of methane to produce any of the four degrees of chlorinated methanes. unsaturated compounds may undergo isomerization as well as hydrogenation. The reaction is usually carried out in the vapor phase with an excess of hydrocarbon at a temperature of 650 to 700°F (345 to 370°C).16 Hydrogenation Hydrogenation is the addition of hydrogen atoms to both sides of a double or triple bond. Because of the presence of the catalysts. This process is conducted at 570°F (300°C) and 4500 psi (31 MPa). If the gases involved are dry. such as C = C. Process Chemistry a) Oil hydrogenation at 250 to 300°F (120 to 150°C) and 50 to 250 psi (350 to 1750 kPa) with a nickel catalyst. but also the chemical properties. with thin tubes for good heat transfer. Hydrogenation not only changes the physical properties of fats. manganese. or C = N. C = O. All rights reserved. hydrogenations usually proceed at a very slow rate. with oxides of zinc.6. The catalyst is silver or copper. usually through the use of hydrogen gas and a catalyst. are preferred for the exothermic reactions.

Alkaline materials can usually be handled in steel vessels. The general formula is XY + H2O → HY + XOH. Process Chemistry a) Hydration of ethylene to ethanol. arranged to sound an alarm at a minimum detectable concentration (not more than 2%). or enzymes. and acetaldehyde. it has a tendency to leak through packings. special corrosion resistant materials or linings usually must be used. Since water is not soluble in fats. In many hydration and hydrolysis reactions. catalysts or high temperatures and pressures must be used for the reaction to proceed at a reasonable speed. Since the hydrogen molecule is small. and sucrose derivatives. (CH2)2O + H2O → (CH2OH)2 ethylene oxide water ethylene glycol c) Hydration of calcium carbide to acetylene (See Data Sheet 7-51. Hydrolysis and Saponification Hydration is the addition of water to a compound. Hydrolysis is the reaction of a compound with water. e) Saponification of glyceryl tristearate to stearic acid and glycerine. ©2003 Factory Mutual Insurance Company. → 3C17H35COOH + C3H5(OH)3 C3H5(C18H35O2)3 + 3H2O glyceryl tristearate water stearic acid glycerine Equipment Materials of construction vary depending on whether the process is carried out in acid or alkaline solution. Leaks should be promptly corrected. The water effects a double decomposition. high purity carboxylic acids.7-46 17-11 Page 34 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Equipment Hydrogenations are usually conducted under pressure in steel reactors.6. C2H4 + H2O → C2H5OH ethylene water ethanol b) Hydration of ethylene oxide to ethylene glycol. Approved hydrogen gas analyzers should be provided in indoor hydrogenation process areas. With acids. the vessel is normally of an alloy resistant to hydrogen or has a corrosion resistant lining. glycols from oxides. . Hydrogen.17 Hydration. A sulfoaromatic-emulsifying compound is usually added to increase the interface area to promote the reaction. Hydrolysis is used to manufacture soaps. alkaline solutions. particularly when operating at high pressures and when conducted indoors. the reaction takes place on the interface between the liquids. Additional information on hydrogen use is provided in Data Sheet 7-91. Possible points of hydrogen leakage from equipment should be regularly checked. CaC2 + H2O → C2H2 + Ca(OH)2 carbide water acetylene lime d) Hydrolysis of a glyceride in a caustic solution to glycerol and soap. All rights reserved. with the hydrogen ion (H+) going to one component and the hydroxyl ion (OH-) going to the other. Care should be taken to see that these are tight. using a phosphoric acid catalyst at 570°F (300°C) and 1000 psi (7 MPa). Since hydrogen gas attacks carbon steels. Hydration is used in the manufacturing of alcohols from alkenes. Saponification is the hydrolysis of fat to form a fatty acid and glycerine. Acetylene for additional information). valves and fittings more than other gases. Inorganic hydrolysis generally involves water alone. Organic hydrolysis involves acidic solutions. 3.

inorganic salt processes. Some optically active compounds are obtained from natural sources. Enantiomers are mirror-image stereoisomers. + NH3 → NH4NO3 HNO3 nitric acid ammonia ammonium nitrate b) Acid reacts with a metal to form a salt and hydrogen + 2HCl + Mg → MgCl2 hydrochloric acid magnesium magnesium chloride c) Metal carbonate reacts with acid to form a salt and water + 2HNO3 → 2NaNO3 + Na2CO3 sodium carbonate nitric acid sodium nitrate Equipment Neutralization is often done in ordinary tanks or in closed reactors or absorbers. Isomerization can be a simple rearrangement. except for the direction of rotation of the plane of polarized light. They have identical physical properties. Materials should be able to resist the corrosive acids or bases present.18 Isomerization and Stereoisomers Isomerization reactions involve the rearrangement of the atoms in an organic molecule without changing the molecular formula. Isomerization reactions are initiated either by heat or light. except toward optically active reagents.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 35 3. H2 hydrogen H2O water CO2 + carbon dioxide ©2003 Factory Mutual Insurance Company. and identical chemical properties. Isomerization can also result in a very small change that produces only subtle differences in spatial orientation. From the naturally occurring compounds. but not identical chemical properties. Stereoisomers are isomers that are different from each other only in their three dimensional orientation. and in soap manufacturing. All rights reserved. 3. (-)-glucose. Neutralization is used widely in fertilizer manufacturing. Special linings or materials may be needed for corrosion resistance. . see Data Sheet 7-89. Diastereomers have different physical properties and similar. Equipment Process equipment should be specified depending on the properties of the materials involved. (+)-mannose. other optically active compounds can be made. water treating.19 Neutralization Neutralization is a reaction between an acid and a base to produce a salt. Reactions normally take place in aqueous solutions at or near ambient conditions. Isomerization reactions are used in petroleum refining and in the preparation of many biopharmaceutical active ingredients. such as a change from a straight chain to a branched molecule or a relocation of a double bond within the molecule that produces a significant change in physical and chemical properties. Diastereomers are stereoisomers that are not mirror-image isomers. For example. Stereoisomers can also be further classified by how they are formed.6. Process Chemistry a) Isomerization and chlorination of n-butane CH3CH2CH2CH3 + Cl2 → CH3CH2CHClCH3 + CH3CH2CH2CH2Cl n-butane chlorine sec-butyl chloride n-butyl chloride b) Aldohexose stereoisomers (C6H12O6): Sixteen stereoisomers including (+)-glucose. They are classified by appearance. Ammonium Nitrate for additional information.6. ethyl alcohol and methyl ether are isomers (C2 H6 O). Process Chemistry a) Acid reacts with a base to form a salt. and (+)-galactose.

RLi. the nitrating agent may not react as it is introduced and may accumulate. Nitration is common in the manufacture of high-energy materials. or reduction reactions. making sure that it reacts as it is added. but usually are prepared as part of the process.6. often in the presence of sulfuric acid. C3H5(OH)3 + 3HNO3 → C3H5(ONO2)3 + 3H2O glycerine nitric acid nitroglycerine water c) Nitration of propane produces a variety of nitrated products (alkane nitration). resemble Grignard reagents in their preparation and reactions. pharmaceutical intermediates.7-46 17-11 Page 36 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 3. The reaction is highly exothermic and the temperature must be controlled by limiting the rate of addition of the organic halide. Organosodium compounds are so reactive that their use is limited to the synthesis of symmetrical alkanes (Wurtz reaction). herbicides. and fungicides. All rights reserved. perfumes. Organolithium compounds. Process Chemistry a) Grignard reagent preparation: Grignard reagents can be purchased for laboratory or small-scale commercial use. C6H6 + HNO3 → C6H5NO2 + H2O benzene nitric acid nitrobenzene water b) Nitration of glycerine to produce nitroglycerine (alcohol nitration). lithium dialkylcopper reagents (Corey-House synthesis). Typically. normally by replacement of a hydrogen atom. Nitrations of aromatic and alcohol compounds are typically performed by using nitric acid.6. the reaction is also an esterification. Process Chemistry a) Nitration of benzene to produce nitrobenzene (aromatic nitration). CH3NO2 + nitromethane CO2 carbon dioxide + H2O water 3. . Pressures range from atmospheric to about 100 psi (700 kPa). Others include organocadmium reagents.20 Nitration Nitration is the introduction of one or more nitro groups (-NO2) into a compound. Grignard reagents. This forms an alkymagnesium halide of the general formula RMgX. –RMgX. are probably the best known of these compounds.21 Organometallic Compounds Organometallic compounds are simply a combination of an organic molecule and a metal. Reactions involving these compounds can also be classified as alkylation. If the temperature is too low. and by providing cooling to the reactor jacket. When the temperature later rises. condensation. except that they are even more reactive. magnesium chips or turnings (Mg) are charged into a vessel after it has been purged with nitrogen. If the hydrogen in the -OH group of an alcohol is replaced. Ethyl ether or tetrahydrofuran (THF) is pumped in and an organic halide (RX) is added. but they are covered separately because of the unique hazards they present. CH3CH2CH3 + HNO3 → CH3CH2CH2NO2 (25%) + CH3CHNO2CH3 (40%) + propane nitric acid 1-nitropropane 2-nitropropane CH3CH2NO2 (10%) + nitroethane Equipment Nitration of alkanes is normally performed as a vapor phase reaction in a high-pressure continuous reactor (NO2+ ions do not react readily with alkanes). If the temperature is too high. The acid and the material to be nitrated are usually not soluble in one another and form two non-miscible layers. the nitrating agent may react all at once. and organozinc compounds (Simmons-Smith reaction and Reformatsky reaction). dyes. Reaction temperatures range from 30°F (0°C) to 750°F (400°C). side reactions such as oxidation or decomposition may result and become violent. ©2003 Factory Mutual Insurance Company. Vigorous agitation or tubular flow is needed to bring the reactants in contact and promote the reaction. Nitration reactions are very sensitive to temperature.

are also used to oxidize aldoses and ketoses. hydrogen peroxide (H2O2).22 Oxidation Oxidation is any process that increases the proportion of oxygen or acid forming elements in a compound. sodium chlorite (NaClO2). an excess of the material to be oxidized is vaporized and mixed with air or oxygen. . Oxidation of alkylbenzenes is used to produce carboxylic acids.6. Upon treatment with periodic acid (HIO4). compounds containing two or more –OH or = O groups attached to adjacent carbons undergo oxidation with cleavage of the carbon-carbon bond. Oxidation of secondary alcohols is used to produce ketones. containing a complexed cupric ion. In liquid phase oxidation. such as purification of natural gas and the production of fuel gases from coal. Phenylmagnesium bromide reacts with ethylene oxide. This is usually followed by hydrolysis of the ozonide to yield the cleavage products. oxidation differs from combustion only in that the reaction is stopped enroute to carbon dioxide and water. but simply open up into a six carbon molecule containing two aldehyde groups. Tollens’ reagent contains a silver ammonia ion. sodium chlorate (NaClO3). CH3CH2CH2CH2MgCl + H2O → CH3CH2CH2CH3 + MgOHCl n-butylmagnesium chloride water n-butane (mixture of magnesium hydroxide and chloride) Equipment Agitated. The chlorine derivatives include potassium perchlorate (KClO4). There are also many biological processes involving oxidation reactions. chromic (VI) acid (CrO3). Fehling’s solution and Benedict’s solution. chlorus acid (HClO2). and metals. ©2003 Factory Mutual Insurance Company. such as sulfur. A common application of this is the oxidative cleavage of carbohydrates into sugar derivatives. phosphorus. Liquid phase oxidations are performed when a higher temperature may cause the molecule to break up. and chlorine dioxide (ClO2). The reaction is prevented from going to completion by using a low oxygen concentration and controlling the temperature. potassium dichromate (K2Cr2O7). 3. Ag(NH3)2+. perchloric acid (HClO4). It is the addition of ozone (O3) to a double bond to form an ozonide. A catalyst is used to promote the reaction at the low temperature. Formaldehyde can be produced from isoprene via ozonolysis. Oxygen is usually added to an organic molecule. Organic oxidation processes can take place either in the liquid or vapor phase. air or oxygen in bubbled through the liquid solution with a catalyst. C6H5MgBr + (CH2)2O → C6H4CH2CH2OMgBr ethylene oxide intermediate C6H5CH2CH2OMgBr + HCl → hydrochloric acid C6H5CH2CH2OH phenylethanol + MgClBr magnesium chlorobromide c) Grignard reactions: Grignard reagent reaction with an organic or inorganic halide. Cycloalkenes and cycloalkynes do not cleave.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 37 C6H5Br bromobenzene + Mg magnesium → C6H5MgBr phenyl-magnesium bromide b) Grignard reactions: Grignard reagents react with a wide variety of compounds. Ozonolysis is another form of oxidation. consisting of aldehydes and ketones. and is used to oxidize aldehydes and aldoses in an alkaline solution. but electrons may be lost or hydrogen removed. dilute nitric acid (HNO3) and numerous chlorine derivatives. In this data sheet. In vapor phase oxidation. Oxidation is common in fuel gas processes. Oxidation of primary alcohols is used to produce aldehydes and carboxylic acids. All rights reserved. CH3CH2MgCl + C6H5Cl → C6H5CH2CH3 + MgCl2 ethyl magnesium chlorobenzene ethyl benzene magnesium chloride chloride d) Grignard reactions: Grignard reagents react violently with water to produce a flammable liquid or gas. potassium permanganate (KMnO4). followed by treatment with an acid to produce phenylethanol (a compound with a rose-like odor widely used in perfumes). Nitrogen blanketing is provided both for safety reasons and to prevent depletion of the reagent by reaction with oxygen and moisture. Common oxidizing agents are oxygen. semi-batch type reactors constructed of carbon steel are frequently used. Oxidation also includes the combination of oxygen with inorganic chemicals.

This may be done pyrometallurgically in smelters or roasters in the presence of high concentration oxygen to produce gaseous sulfur dioxide. . Process Chemistry a) Oxidation of coal: fuel gases are produced by the reaction between carbon and steam or oxygen. Step one is performed in an ordinary furnace. catalyst. iron and other metals to free up the desired valuable metals. using a platinum or vanadium catalyst.7-46 17-11 Page 38 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Inorganic oxidation is most common in the metallurgical refining (mining) industry. and at 850°F (454°C) with a nickel catalyst. autoclaves operate at high temperatures and pressures. nickel and zinc. typically gold. Materials should be able to resist the corrosive materials present. the temperature is usually low. Oxygen is obtained from air in the production of producer gas or low BTU gas. or hydrometallurgically in autoclaves to produce liquid sulfates. Step two is performed in a converter at a lower temperature. S + O2 → SO2 sulfur oxygen sulfur dioxide 2SO2 sulfur dioxide + SO3 sulfur trioxide Equipment The greatest problem in the design of organic oxidation reactors is the removal of heat in vapor-phase reactors. CH4 + 2O2 → CO2 + 2H2O + heat (complete combustion) methane oxygen carbon dioxide water + O2 6CH4 methane oxygen CH4 + methane H 2O water → → 2C2H2 acetylene + 2CO + carbon monoxide 3H2 hydrogen + CH3COOH acetic acid 2H2 hydrogen CO + carbon monoxide c) Oxidation of an alkene using permanganate + KMnO4 → (CH3)2CO CH3CHC(CH3)2 2-methyl-2-butene potassium acetone permanganate d) Oxidation of sulfur to form sulfuric acid. Additional information on oxygen use is provided in Data Sheet 7-52/17-13. Maintenance of temperature at the proper level is necessary to ensure the correct rate of degree of oxidation. All rights reserved. Good mixing of reactants is important. the oxide is hydrated with water to produce the acid. In the third step. sulfur is oxidized. In liquid-phase reactors. Removal of heat is essential to prevent destruction of apparatus. It is used to produce pure metals from metal minerals. but low (atmospheric) pressure. the liquid may flash resulting in overpressurization. While smelters and roasters operate at high temperature. 1065°F (575°C). C + H2O → H2 + CO or CO2 carbon water hydrogen carbon carbon monoxide dioxide C + O2 → CO or CO2 carbon oxygen carbon carbon monoxide dioxide b) Oxidation of methane at flame temperature (1500°F [815°C]). Pure oxygen produces medium BTU gas. and the rate of heat generation can be readily controlled by the rate of introduction of air or other oxidizing agent. copper. or raw material. Oxygen. Autoclaves used in metallurgical refining often constructed of special corrosion resistant alloys such as titanium. Another problem in the design of oxidation reactors is the possible introduction of liquid into vapor-phase reactors. + O2 → SO3 oxygen sulfur trioxide → H2SO4 sulfuric acid H2O water ©2003 Factory Mutual Insurance Company. In the first and second steps. Oxygen selectively reacts with undesired metallic sulfides (pyrite).

9). Fig. as the polymerization progresses and the mix increases in viscosity.3-butadiene cyclobutene 3. the monomer. themselves.23 Photochemical This type of reaction is outside the common classification systems. are otherwise classified.3-butadiene to cyclobutene CH2 = CHCH = CH2 → CH2CH = CHCH2 (cyclic compound) 1. an inorganic peroxide. the reaction is completed by molding or extruding the resin. . particularly.24 Polymerization Polymerization is the joining together of small molecules. or an organometallic compound. In bulk polymerization. There are many ways to form polymers as shown (Fig. Storage of Liquid and Solid Oxidizing Materials. and catalyst are the only materials in the reactor. a base. a) Halogenation using UV light → CH3CH2Cl CH3CH3 + Cl2 ethane chlorine chloroethane b) Isomerization of 1. an acid. polymer.6. 3.6. The catalyst used in addition polymerization may be an organic peroxide. Addition polymerization can be conducted via a homogeneous system (need only one phase for the reaction to proceed) or a heterogeneous system (need at least two phases for the reaction to proceed).Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 39 Additional information on liquid and solid oxidizing materials is provided in Data Sheet 7-82N. Photochemical reactions proceed in the presence of light. Types of polymerization reactions. All rights reserved. to form a much larger molecule. the rate is dependent on the intensity of incident radiation. Bulk polymerization is often done in two stages. known as monomers. In the second stage. Because of the high concentration of reactants. it is the most difficult polymerization to control. This may be by molding into ©2003 Factory Mutual Insurance Company. the monomer is only partly polymerized into a resin. 9. In the first stage. known as a macromolecule or polymer. The reactions. The heat given off is difficult to remove.

However. Condensation polymerization can be carried out in an aqueous or a solvent medium. or another strong oxidizer as the catalyst. absorption of heat by the water or solvent readily controls the reaction. if agitation is lost or the emulsifying agent is inadequate. Elastomers have the elasticity characteristics of rubber. if agitation can be maintained. However. The disadvantage of this process is that the addition of emulsifying or stabilizing agents makes it difficult to prepare a pure or clear polymer.7-46 17-11 Page 40 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets sheets. polyethylene. Plastics are classified as thermoplastics or thermosetting. Note that at very high pressures ethylene can be decomposed by shock. polyurethanes (Spandex. and the solvent must be separated from the polymer after the reaction is completed. and polyvinyl chloride. forming latex. washed. butyl. A curing process completes the polymerization to the final product. In both emulsion and suspension polymerization. Copolymerization processes are similar to polymerization processes. Vycron). The reaction is usually interrupted while the polymers are still soluble or fusible. Thermosetting polymers are highly cross-linked and form rigid. Process Chemistry 1. In suspension or pearl polymerization. and isotatic polypropylene. reliable agitation is vital as well as relief venting equal to that provided for bulk polymerization processes. . butadiene/styrene/vinyl pyridine. but irregular three-dimensional structures. On heating. the reaction is easier to control and the viscosity is reduced. except that the relative concentrations and reactivities of the monomers become important process parameters. The water absorbs the heat of reaction and keeps the reaction mass fluid to simplify agitation. polyacrylonitriles (Orlon. Plastic characteristics depend on the molecular structure. Vycra). fibers. these polymers soften. and plastics. Copolymers are polymers that contain two or more different monomers. Condensation polymerization is commonly used to produce thermosetting resins including alkaline-catalyzed phenyl-formaldehyde and melamine. In emulsion polymerization.910-0. Thermoplastic or thermosoftening polymers are linear and branched polymers that are basically crystalline.000 psi (420 MPa) at up to 660°F (350°C). The droplets are larger (0. The ethylene gas is compressed up to 60. the monomer droplets are usually suspended in water without an emulsifying agent. Elastomeric Materials. or extruding into sheets or films. the monomer is dissolved in a solvent. Therefore. ©2003 Factory Mutual Insurance Company. Polymers usually form as small beads that are easily filtered out. Because of the dilution of the monomer. On heating. Synthetic polymers include elastomers. polyesters (Dacron. butadiene. and by an excess of catalyst. monomer particles are suspended in a water emulsion using soap or another emulsifying agent. Synthetic fibers include polyamides (Nylon 66). published by the International Plastics Selector. This facilitates heat removal and temperature control. Terylene. The monomers are converted to a colloidal suspension of polymer particles. an organic peroxide. the process is normally easier to control than addition polymerization. Since water or a similar condensation product is produced and must be removed. the monomer will concentrate and uncontrolled bulk polymerization would ensue. However.940 g/cm3) at highpressure using small quantities of oxygen. ethylene-propylene. solvents can be used (hexane is used in an older polypropylene process). styrene-butadiene and urethane rubbers. Addition polymerization of ethylene to polyethylene. Addition polymerization is commonly used to produce thermoplastics including acid-catalyzed phenyl-formaldehyde. halogenated.1 to 1 mm) than in the emulsion process. nitrile. Bulk polymerization has the advantage of being free of solvents and impurities. This process is common in the polymerization of vinyl chloride. spraying onto forms and curing (fiberglass reinforced polyester polymers). In solution polymerization. All rights reserved. Acrilon). or tubes (acrylic polymers). 0. or the reactants may be liquids. the product is usually of a lower molecular weight. The catalyst is dissolved in the water. rods. Copolymerization is used to produce materials with varying properties. a) Bulk polymerization of ethylene to produce low density polyethylene (LDPE. Fibers are thread-like. identifies over 20 different generic types of synthetic rubber including acrylic. these polymers may actually become harder due to the formation of additional cross-links. The catalyst used in condensation polymerization is usually an acid or base. polystyrene. and dried to form molding powders.

Cracking of natural gas is conducted at temperatures up to 3000°F (1650°C). isoprene. reducing its concentration and automatically slowing the reaction. Cracking is the pyrolysis of alkanes. CH2 = CH2 → (-CH2 CH2-)n ethylene polyethylene 2. continuous or stepwise addition. Novolaks are thermoplastic and react with cross-linking substances to give the resin desired properties. and light and heavy oils. Acid catalyzed phenol-formaldehyde reactions are historically easier to control than caustic catalyzed reactions. Hydrocracking is conducted in the presence of hydrogen at high pressure and lower temperatures.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 41 b) Solution polymerization of ethylene to produce high density polyethylene (HDPE. the ratio of the reactants.6. (11. Novolaks are produced in both continuous and batch processes.0 to 3. If the temperature rises. The ethylene is dissolved in an inert hydrocarbon. Additional information on organic peroxides is provided in Data Sheet 7-80.0 are used with a caustic catalyst to produce resoles. briefly heated to 700-900°F (370-480°C). Coal may be pyrolized to form coke. ammonia.5 to 0. particularly petroleum. and hydrogen.4 cm) thick walls. In thermal cracking.+ H2O H2N(CH2)6NH2 hexamethylenediamine adipic acid nylon water 3. (22.5 inches (6. Formaldehyde–to-phenol ratios of 0. This method produces alkanes with the highly branched structures desired in fuels.e. In steam cracking. Most resoles are produced in a multi-step batch process. 3. Molten phenol is usually charged into the reactor. C6H5OH + HCHO → C6H4OH(CH2OH) + C6H5OH → C6H5OH-CH2-C6H5OH → polymer phenol formaldehyde o-hydroxymethyl phenol intermediate Equipment Batch. Polystyrene is prepared in batch and semi-batch reactors. propylene. semi-batch or continuous reactors are used depending on the type of polymerization. the ethylene is driven out of solution. i. Resoles are generally of lower molecular weight and may be liquid or solid. alkanes are diluted with steam. including ethylene. they are generally solids.. Organic Peroxides. alkenes. at low-pressure using an organic or an inorganic peroxide as a catalyst. Condensation copolymerization of adipic acid and hexamethylenediamine to Nylon 66: + HOOC(CH2)4 COOH → -NH(CH2)6NHCO(CH2)4CO. The type of catalyst used (caustic or acid). higher boiling petroleum fractions are contacted with a catalyst at moderate temperatures and pressures. Condensation copolymerization of phenol or substituted phenol and an aldehyde to prepare phenolic resins.5 in. Polyvinylchloride is prepared in large batch reactors. The solvent helps to absorb the heat of reaction.1 m) high by 9 in. Large alkanes are converted to smaller alkanes. these reactors may be 1-1⁄4 miles (2 km) long by 2.941-0. butadiene. 0. .e. Polyethylene is typically prepared in tubular flow reactors. and cyclopentadiene. such as phenol-formaldehyde. followed by a precise amount of acid catalyst.25 Pyrolysis & Cracking Pyrolysis is the decomposition of large molecules into smaller ones by heat. 900°F (480°C) and 8-20 psi (50-140 kPa). 250-450°F (120-230°C). In catalytic cracking.4 cm) ID or 20 ft (6.8 are used with an acid catalyst to produce nolovaks.. The formaldehyde solution is then introduced in a slow. ©2003 Factory Mutual Insurance Company. Formaldehyde–to-phenol ratios of 1. i.970 g/cm3). then rapidly cooled. This method is used to produce many hydrocarbon chemicals. alkanes are simply heated to a high temperature. and the reaction conditions (time and temperature) determine the properties of the resin and the reaction hazards. All rights reserved.9 cm) ID with 4.

a) Coke is oxidized to form carbon dioxide C (s) + O2 (g) → CO2 (g) carbon oxygen carbon dioxide b) Carbon dioxide is reduced to carbon monoxide CO2 (g) + C (s) → 2CO (g) carbon dioxide carbon carbon monoxide c) Iron oxide is reduced to iron (with impurities) by carbon monoxide. Note: the oxidation state of hydrogen is +1 in all its compounds except for those with metals. such as the reduction of metal oxides to pure metals such as metallic sodium. sulfur or ammonia as well as the addition of hydrogen to a metal or the generation of hydrogen. However. In addition to removal of oxygen. depending whether organic or inorganic materials are involved. Pyrolysis of natural gas (methane) in a continuous furnace to produce industrial carbon and hydrogen.3-butadiene (used in synthetic rubber).3-butadiene Equipment Pyrolysis and cracking equipment is very large and is designed for the specific application.26 Reduction Historically. using an acid ferrous chloride catalyst. By rapid quenching. sodium hydride. + 2H2 CH4 → C methane carbon hydrogen If the gas is heated in an electric arc. its decomposition can be prevented: 2CH4 → C2H2 + 3H2 methane acetylene hydrogen 2. CH3CH2CH2CH3 → CH3CH = CHCH3 + CH3CH2CH = CH2 → CH2 = CHCH = CH2 n-butane 2-butene 1-butene 1. Among the most common organic reduction processes are the manufacture of amines from nitro compounds. Reduction of nitrobenzene to aniline by iron. Reduction of calcium phosphate to prepare phosphorus with carbon monoxide as a by-product.6. reduction reactions also include removal of halogens. aluminum or magnesium. . a reduction reaction occurred when oxygen was removed from a molecule. or hydrogen may be used in organic reduction reactions. Process conditions vary widely. diborane. Process Chemistry 1. Catalytic cracking of butane to form 1. ©2003 Factory Mutual Insurance Company. acetylene may be formed. 4C6H5NO2 + 9Fe + 4H2O → 4C6H5NH2 + 3FE3O4 nitrobenzene iron water aniline iron oxide 2. These generally involve the generation of hydrogen and subsequent addition of hydrogen to the compound. Reduction reactions are frequently thought of as the reverse of oxidation reactions. Iron extraction from haematite in a blast furnace. Redox reactions occur when reduction and oxidation reactions occur simultaneously. 2P + 5CO Ca(PO4)2 + 3SiO2 + 5C → 3CaSiO3 + calcium sand coke calcium phosphorus carbon phosphate silicate monoxide 3. 3. where it is commonly –1.7-46 17-11 Page 42 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Process Chemistry 1. Fe2O3 (s) + 3CO (g) → 2Fe (s) + 3CO2 (g) iron oxide carbon monoxide iron carbon dioxide Equipment Inorganic reduction is often done in furnaces. Standard redox or electrode potentials can be used to determine simple reduction potentials. Hydrazine. The most common inorganic reduction processes are the removal of oxygen from inorganic chemicals. All rights reserved. reduction is really any process where the number of electrons in the chemical substance increases.

cyclization.g. Reforming of methylcyclohexane to produce toluene. Chlorination of silicon using methyl chloride in the presence of a copper catalyst and at elevated temperatures to produce methylchlorosilanes. 3. Organosilanes also undergo a variety of chemical reactions including additions. and varnishes. Hydrolysis and Saponification 3. and sealants. All rights reserved. fabric coatings. → intermediate → (CH2)3 CH2Cl CH2CH2Cl 1. Silicone. e. and then the intermediate is rearranged. a resin. or an elastomer. Heat-cured elastomers are used in belts.6. Silane (SiH4) is the simplest hydride.3-dichloropropane cyclopropane Equipment Ammonia synthesis and catalytic steam hydrocarbon reformers are detailed in Data Sheet 7-94/12-22. hoses. and photolysis. lubricants. It should not be confused with inert silica (SiO2) or silicates (M2O • mSiO2 • nH2O where M is an alkali metal and m and n are the number of moles of SiO2 and H2O. room-temperature-vulcanizing (RTV) or heat-cured. hydrolysis. The addition of organosilanes to olefins is called hydrosilylation.27 Reforming Catalytic reforming may result in dehydrogenation. 300 psi (2. 3. and penetration seals. Silicones have several unusual properties that make them commercially important. RnSiO(4-n)/2m. CH3Cl + Si → CH3SiCl3 + (CH3)2SiCl2 + (CH3)3SiCl methyl silicon methyltrichlorosilane dimethyldichlorosilane trimethylchlorosilane chloride complex ©2003 Factory Mutual Insurance Company. have good dielectric strength. Process Chemistry 1.is a synthetic polymer where n = 1-3 and m≤2. and have a low surface tension. Silane.6. using a catalyst at 560°F (293°C). and Siloxane Silicon (Si) is an element that is a component of many different minerals. Thousands of inorganic silane and organosilane compounds exist. Silicone.. polymerized or copolymerized.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 43 Organic reductions are normally carried out in ordinary steel reactors. surfactants. paint. RTV elastomers are used in adhesives. The most common commercial application of these reactions is in ammonia synthesis and petroleum refining. gaskets. Catalytic Steam-Hydrocarbon Reformers. Silicone fluids are used as hydraulic fluids. and for waterproofing.28 Saponification — See Hydration. Preparation of silicone involves a number of steps. Inorganic silanes undergo many different types of reactions including oxidations and halogenations.29 Silicon. Silicones are relatively stable and inert. per mole of M2O) from which it is derived. suitably designed for the corrosive conditions that may be present. the siloxane is hydrolyzed to an intermediate. Process Chemistry 1. aminations. Silicon is used extensively in the semiconductor and nonferrous metal industries. a silane monomer is hydrolyzed to siloxane. laminates. . They are resistant to weathering.6.1 MPa) (dehydrogenation). using a catalyst and a salt (cyclization). oxidations. calendering rollers. Silicone elastomers are further categorized by their cure-system chemistry. Ammonia Synthesis Units and Data Sheet 7-72/12-10. reduced. A silane is a compound containing a hydrogen-silicon bond and is also known as a silicon hydride. The final product could be a fluid. electrical insulations. electrical insulations. and isomerization of alkanes into cycloalkanes and aromatic hydrocarbons. respectively. Reforming of 1. → C6H5CH3 + 3H2 C6H11CH3 methylcyclohexane toluene hydrogen 2. A silicone has a repeating silicon-oxygen backbone and has organic groups attached to a significant number of the silicon atoms by silicon-carbon bonds.3-dichloropropane to produce cyclopropane. Silicone resins are used in adhesives. Simply. glazings.

All rights reserved. undergo redox reactions. Normally. . the sulfonating agent used is generally no stronger than necessary. They may also be conducted in continuous tube reactors with tube-bundle reactors (about 100 one inch (2. Reduction of hydrochloric acid and silane to produce chlorosilane. such as glass-lined steel. + NaOH → sodium hydroxide C11H23CH2OSO3-Na+ sodium lauryl sulfate ©2003 Factory Mutual Insurance Company. (72. silicone. Process Chemistry 1. The rapid reaction rate results in significant heat generation and frequently gaseous products that are flammable and/or toxic.7 Water-Reactive Materials Water-reactive materials are labeled as such because they may undergo hazardous hydrolysis or reduction-oxidation (redox) reactions with water. For example. or calcium silicide in the presence of a copper catalyst to produce trichlorosilane. H2SO4 . Again. Examples include aluminum carbide and water reacting to form methane and calcium carbide and water reacting to form acetylene (see Hydrolysis reactions). Certain elements. ferrosilicon.6. It is not the type of reaction.7-46 17-11 Page 44 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 2. equipment must be designed for the specific application taking into consideration material characteristics and process conditions. HSO3. SO3 is the most vigorous sulfonating agent. Sulfonation is one of the reactions used in dissolving lignin in the processing of sulfite pulp in paper mills. Most sulfonation reactions are readily reversible. this is done by reacting a compound with SO3. Sulfonation of an alcohol to a sulfate.5 cm) diameter tubes inside a water-cooled vessel) and falling film reactors (single 30 in. the rapid reaction rate results in significant heat generation and frequently the generation of gaseous reaction products that are flammable and/or toxic. n-C11H23CH2OH + H2SO4 → n-C11H23CH2OSO3H lauryl alcohol sulfuric acid lauryl hydrogen sulfate Equipment Sulfonations may be conducted in ordinary batch reactors equipped with agitators. using an aluminum chloride catalyst. Chlorination of silicon.2 cm) ID tube) being common. It is also used in the manufacture of detergents. but the rate of the reaction and the characteristics of the reaction products that cause concern. Equipment should be constructed of materials able to withstand concentrated sulfuric acid. the reducing agent. is added to a carbon in an organic compound. sodium metal in water produces hydrogen gas that is ignited by the heat of the reaction. and siloxane processes. such as phosphorus and sodium. C6H5OH + H2SO4 → C6H4(OH)(SO3H) phenol sulfuric acid phenolsulfonic acid 2. HCl + Si → HSiCl3 hydrogen chloride silicon complex trichlorosilane 3. Most water-reactive materials undergo exothermic hydrolysis reactions. HCl (g) + SiH4 (g) → SiH3Cl (g) + H2 hydrochloric acid silane chlorosilane hydrogen Equipment Because of the wide range of silicon. or oleum (SO3 dissolved in H2SO4). 3. Sulfonation of phenol to o-phenolsulfonic acid at 15 to 20°F (-9 to -7°C) and p-phenolsulfonic acid at 100°F (38°C). Therefore. Hydrogen is generated.30 Sulfonation Sulfonation is the process by which the sulfonic acid group. The element is oxidized by water. silane. heat transfer systems and condensers. but it has a tendency to initiate side reactions with materials that are easily sulfonated. 3.

For example. 3. The thermal stress caused by quickly adding cold liquid to the equipment should be considered. 10. The potential for boil-over should also be considered. . and the nature of the confinement (Fig. The reactor must be large enough to contain the combined volume or provided with overflow to a safe location. for additional information). the mode of ignition. quenching the reaction is usually the next action taken. Causes and Effects of Fires and Explosions. hydroquinone (an antioxidant) is used to inhibit some vinyl monomer polymerizations.8 Reaction Quenching Methods When application of emergency cooling won’t stop a runaway reaction. and may also cause ensuing fires while disabling protective equipment (see Data Sheet 7-0.9 Unstable Materials and Explosion Hazards due to Uncontrolled Chemical Reactivity Uncontrolled chemical reactivity has resulted in numerous explosions and has caused some of the most severe losses in the chemical processing industries. The cold liquid must be compatible with the reactor contents and introduced at a sufficient pressure and flow rate to be effective (need to overcome runaway reaction pressure and not flash away). Inhibitors work by counteracting the catalyst or by complexing with the free radicals.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 45 3. Dumping acts by rapidly discharging the reactor contents into another vessel. This can be done by adding an inhibitor. It is critical that the dumping be completed before the runaway reaction compromises the reactor. Cold liquids act by decreasing the temperature of the reactor contents. its reaction kinetics. The type of explosion depends on the energy of the material. Types of Explosions. All rights reserved. 10). Examples include gravity addition of a diluent and high-pressure waterspray inside the reactor. and/or dumping the reactor contents. rapidly adding a cold liquid. Fig. Explosions cause direct damage. ©2003 Factory Mutual Insurance Company. Bottom outlet discharge may be via gravity or pressurization of the reactor. The receiving vessel may be precharged with an inhibitor or a cold liquid and should be provided with a vent line.

Note: O’Brien. A deflagration may accelerate to a detonation. Chemical Engineering Progress. This is known as a deflagration to detonation transition (DDT). In a thermal explosion. et al. Thermal explosions may occur when: 1) two chemicals accumulate in the absence of a catalyst that is later added to initiate the reaction.. 11. All rights reserved. Deflagrations can be successfully vented. Physical explosions are those that result from physical failure of a container. Thermal explosions are a result of an exothermic reaction occurring under conditions of confinement with inadequate means of removing the heat of reaction (Fig. via a shock wave.J.280 to 19. velocities may range from 3.000 m/sec). . G. at supersonic velocities. it is therefore called a homogeneous explosion.000 m/sec). at subsonic velocities. January 1982 Deflagrations are chemical explosions that propagate.700 ft/sec (1. the container ruptures.000 to 6. This is usually due to overpressurization. and an explosion ensues. causing it to fail under normal pressures. by heat conduction. Fig. velocities may vary from slow (1 mm/min) to fast (1. or 3) two chemicals that react on contact are layered. no reaction front is present. Detonation pressures can reach 30 times the initial absolute pressure with reflected pressure even higher. Detonations are chemical explosions that propagate. then mixed rapidly. Chemical explosions manifest themselves as flammable vapor-air explosions and as dust explosions. It may also result from a defect or weakened spot in the container. Such reactions can accelerate to the point where high-pressure gases are generated. Thermal Explosion Heat-Temperature Graph. Deflagration pressures in closed equipment can reach eight to ten times the initial absolute pressure. Even higher pressures may occur in compartmented or interconnected equipment due to pressure piling effects. Thermal Stability Hazards Analysis. Detonations proceed so quickly that they cannot be successfully vented. 11). ©2003 Factory Mutual Insurance Company. Figure 12 is a schematic representation of the differences in pressure-time history of deflagrations and detonations.7-46 17-11 Page 46 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Chemical explosions are those that involve a chemical reaction. 2) cooling is interrupted during a chemical reaction.

Methods include the ABL. mixing cell calorimetry (MCC). All rights reserved. See Data Sheet 7-49/12-65. Sensitivity to friction tests may be conducted on solids and semi-solids by placing a sample between two rough surfaces. Adiabatic calorimetry techniques include accelerating rate calorimetry (ARC). BAM. Emergency Venting of Vessels for instrument details. Reaction calorimetry techniques include differential scanning calorimetry (DSC). and PHI-TEC I™. they are therefore called heterogeneous explosions. Materials that do not exhibit an exotherm during thermal stability testing are presumed not to be shock sensitive. The adiabatic temperature rise is a good measure of the thermal hazard of a chemical system since it is the maximum possible temperature increase.10 Experimental Screening and Thermal Hazard Analysis Mechanical sensitivity is divided into sensitivity to impact (shock) and sensitivity to friction. The adiabatic compression test is conducted by rapidly applying high pressure to a liquid in a U-shaped metal tube. Deflagration versus Detonation Pressure-Time Graph. Fig. The weight and height can be varied to provide a qualitative measure of the sample’s susceptibility to decompose upon impact. then forcing hot compressed gas into the liquid. . ©2003 Factory Mutual Insurance Company. and rotary friction test. This test should be applied to any material known or suspected to contain unstable chemical functional groups. card gap. the DIERS vent-sizing package (VSP) and PHI-TEC II™. Shock sensitive materials react exothermically when subjected to a pressure pulse and condensed-phase detonations may occur. The confinement cap test is conducted using a blasting cap to determine sensitivity. confinement cap. then rubbing the surfaces together. 3. This test was designed to simulate water hammer and sloshing effects during transportation. The card gap test uses a shock wave generated by an explosive charge to determine whether a propagating reaction occurs. The drop weight test is conducted by dropping a weight on a sample in a metal cup. and adiabatic compression tests. Thermal stability is determined using reaction and adiabatic calorimetry. Methods include the drop weight.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 47 Both deflagrations and detonations have a reaction front that separates reacted and unreacted material. 12.

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DSC scans are generally the first screening tests performed. These tests determine the temperature and enthalpy of exothermic reactions. A total heat release of as little as 200-300 J/g could present a runaway reaction potential, depending on the process environment. ARC scans help determine the reaction kinetics. ARC scans will also measure the rate of pressure increase, providing information on the generation of volatile materials. The Mettler RCl™ adiabatic reaction calorimeter permits measurement of the heat generation rate as a function of time and the heat of reaction. Heat transport data, between a reaction mixture and the heating or cooling media, is also measured. VSP tests are frequently used to determine the worst credible case scenario. The Reactive System Screening Tool (RSST) and the Advanced Reactive System Screening Tool (ARSST) are calorimeters that can be used to determine the potential for runaway reactions, and measure the rate of temperature and pressure rise for gassy reactions. The temperature and pressure rises are used to determine the energy and gas release rates. The ARSST has increased temperature ramps to simulate fire exposure, a heat-wait-search operation mode with increased onset detection sensitivity, and an isothermal operation at elevated temperature mode. 3.11 Scale-up Effects Chemical reactions frequently behave very differently when conducted in large-scale commercial equipment rather than in small-scale laboratory equipment. Problems observed on a commercial scale, but not necessarily on a lab scale, include non-uniform distribution of gas, settling of solids, phase separation, foaming and localized heating. In many cases, the effect of these variables can be calculated or modeled. In other cases, only carefully designed pilot plant studies can reliably provide needed chemical kinetic, self-heating, mass transfer and heat transfer information. Specially designed reactors may be used for this work (autoclaves, high-heat-flux reactors, microreactors, etc.). Optimizing product yields involves changing process procedures (addition sequences, addition times, hold times, etc.), process conditions (concentrations, temperature profiles, pressure profiles, etc.), and/or process equipment. Obviously, this will affect the reaction and its rate; it should be carefully studied before implementing in large-scale equipment. 3.12 Chemical Risk Assessment and Management Consequence screening usually consists of a blast or explosion evaluation and a structural assessment of the process structure or building and the surrounding structures or buildings. The blast evaluation should analyze all potential explosion sources for magnitude and duration. These sources should including vapor cloud explosions (VCEs), condensed phase reactions, uncontrolled chemical reactions, boiling liquid expanding vapor explosions (BLEVEs), pressure vessel ruptures, and other physical explosions as applicable. The structural assessment should determine the overpressure resistance of the process structures and/or buildings within the significant blast or explosion overpressure ring area. Consequence screening results can then be used in risk management. 3.13 General Chemical Processing The chemical processing industry can be broken down into two manufacturing categories: commodity and fine chemicals. Commodity chemicals are those produced and delivered in bulk and frequently used in the manufacture of other products. The most widely produced chemicals vary from year to year, but usually include the following: sulfuric acid, nitrogen, oxygen, ethylene, lime, ammonia, phosphoric acid, sodium hydroxide, propylene and chlorine. Fine chemicals production is on a much smaller scale and includes active pharmaceutical ingredients. Regardless of the type of process and production levels, the inherently safer design concepts of intensification, substitution, attenuation, and limitation should be applied. See Data Sheet 7-43/17-2, Loss Prevention in Chemical Plants for details.

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3.14 Reactor Selection The selection of the type of reactor for a chemical process is based on many factors including mode of operation, material phases, chemical hazards, reaction kinetics, desired production rate, economics and process safety. Reactors are designed for batch, semi-batch or continuous operation. Batch processes are primarily associated with small production rates, long reaction times, and selective chemistry requirements. Continuous processes are associated with high production rates and short reaction times. In batch reactors, material composition and heat generation rates change over time. In continuous reactors, material composition and heat generation remains constant unless process conditions are changed. A batch reactor is an agitated vessel in which the reactants are all added at the start of the reaction and the reaction products are removed after a fixed time. Agitation is usually provided by internal impellers, gas bubbles, or pumped recirculation. Temperature control is usually provided by jackets, reflux condensers, and/or pumped recirculation through an exchanger. A semi-batch reactor is similar to a batch reactor, except that some of the reactants are fed intermittently or continuously into the vessel. This arrangement is commonly used when feed rates need to be controlled. Exothermic reactions can be slowed down and endothermic rates maintained by limiting the concentrations of some of the reactants. This arrangement is also used to increase product through-put in cases where the product volume is less than the reactant volume in the vessel. A continuous reactor is a vessel in which the reactants are being continuously added at one point and the products are being continuously removed at another point. Reactor selection also depends on the phase of the materials being processed. There are vapor phase reactors, liquid phase reactors, solid phase reactors, gas/liquid reactors, and gas/liquid/solid reactors. Catalysts may be retained in the vessel or separated out downstream. Beds may be fixed, moving, or fluidized. Gas/liquid reactors include tray tower, packed tower, falling liquid film, spray tower, bubble tower, venturi mixer, static in-line mixer, tubular flow, looped, and stirred tank. Liquid/liquid reactors include tray tower, packed tower, spray tower, rotating disk contactor, and stirred tank. Gas/liquid/solid reactors include trickle bed, flooded fixed bed, fluidized bed, bubble columns, slurry, and stirred tank. Solid reactors include horizontal rotary kilns, vertical kilns, multiple hearth, fluidized bed, and vertical moving bed (blast furnace). The bottoms of these reactors may be cone, slope, or dish shaped. The two most common reactor types are continuous-flow stirred tank reactors (CSTR) and tubular flow reactors (TFR). Continuous Stirred Tank Reactors (CSTR) are continuously stirred to maintain uniform concentrations within the reactor. They are adaptable to either batch or continuous operation and may be used in series. They are best suited for small or medium production rates. They can be used for a wide range of pressures and temperatures. Agitation is furnished by stirrer blades, or by forced circulation using external pumps. Jacketed walls, internal coils, external heat exchangers, direct fire, or electric resistance heaters can be used to provide heat transfer. If the reaction occurs with evolution of vapors, reflux condensers can be used for cooling. CSTRs are generally cylindrical vessels, installed vertically (Fig. 13). Horizontal reactors are used for processing of slurries where greater liquid surface is desired, where the boiling point rise due to hydrostatic heat is a concern, where headroom is limited, or if the material is very viscous. Bioreactors are CSTRs used in biochemical and biotechnology applications (Fig.14). High heat flux process reactors are a relatively new application for CSTRs that employ a cryogenic heat transfer system. Tubular flow reactors (TFRs) have continuous concentration gradients in the direction of flow as the reactants are continuously fed in one end and the products are continuously removed from the other end. They are used in continuous operations with medium to high production rates. TFRs may have several pipes or tubes in parallel. Individual tubes are jacketed or shell-and-tube construction is used when auxiliary heat transfer is needed; with shell-and-tube construction, the reactants may be on either the shell or the tube side. The reactant side may be filled with solid particles, either catalytic or inert, to improve heat transfer by increased turbulence or to improve interphase contact. Both horizontal and vertical orientations are common. Tubular reactors are also known as plug flow, slug flow, and piston flow reactors. Plug flow reactors (PFRs) are large-diameter tubular flow reactors with packing or trays that approach plug flow behavior (Fig. 15).

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Chemical Reactors and Reactions
FM Global Property Loss Prevention Data Sheets

Membrane reactors are plug-flow reactors that contain an internal cylinder of porous material, the membrane (Fig. 16). The membrane is a barrier that allows only certain components to pass through; selectivity is based on pore diameter. Catalytic membrane reactors combine reaction with separation to increase conversion and are used for catalyzed reactions such as dehydrogenations. Two types of catalytic membrane reactors are commercially available: the inert membrane reactor with catalyst on the feed side (IMRCF) and the catalytic membrane reactor (CMR). The IMRCF has an inert membrane that contains the catalyst. The CMR membrane is either coated with or made out of a material containing the catalyst. Tube furnaces are a type of tubular flow reactor. They consist of a combustion chamber lined with refractory with tubes mounted on the walls and ceiling and sometimes on the floor. In the radiant section, the tubes are in direct view of the flames. In the convection section, tubes serve to preheat the charge, to maintain the reaction temperature attained in the radiant section, and/or to recover heat by preheating combustion air or generating steam. Microreactors are also a type of tubular flow reactor. Micrometer-scale channels and chambers are used to conduct reactions. Because of the very high surface to volume ratio, good control of extremely exothermic reactions is possible. Custom microreactors are being developed for continuous processes and may be used in parallel to feed downstream equipment. Microreactors, at this time, are best suited for conducting gasphase reactions with very small production rates (lb/day). They can be used over a wide range of pressures and temperatures. The hazard is minimal due to the small quantities of material present.

Fig. 13. Pfaudler CSTR.

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Braun bioreactor. All rights reserved. Table 5. 14.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 51 Fig. . Advantages and Disadvantages of Various Reactor Types Reactor Type Batch Advantages Agitation Disadvantages Large inventory Low throughput rate Heat transfer problems Cycling effects Potential accumulation of reactants Precipitation problems Large inventory Low throughput rate Heat transfer problems Precipitation problems Potential for hot spots Agitation only if in-line mixers are available Inflexible Semi-batch CSTR Agitation Addition rates controllable Agitation Addition rates controllable Stationary conditions TFR Low inventory High throughput rate Stationary Conditions ©2003 Factory Mutual Insurance Company.

Fig. . All rights reserved. ©2003 Factory Mutual Insurance Company.7-46 17-11 Page 52 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Fig. Membrane Reactor. 16. 15. Plug Flow Reactor.

one volume of steel yields twenty volumes of corrosion. All rights reserved. Pitting is a form of very localized corrosion. It is important to understand the factors that influence corrosion. and the effect corrosion may have on the reliability of the process equipment.15 Reactor Aging and Corrosion Resistance Accelerated aging and corrosion can result in unexpected equipment failure. Chlorides may be present in either process materials or utilities. Frequent start-ups and shutdowns accelerate aging and may cause corrosion fatigue. Erosion is a form of corrosion associated with material flow. . Dealloying corrosion occurs when only one alloy is attacked by corrosion. may significantly change corrosion resistance. Crevice corrosion occurs within or adjacent to a crevice. The presence of water may increase the corrosiveness of non-aqueous compounds. Inhibitors can be used to prevent pitting. Inspections alone may not be an adequate predictor of reliability. The absence of water may increase the corrosiveness of some organic halides. This accounts for what is known as rust-jacking. Fretting corrosion occurs when metal pieces slide over one another. Cavitation corrosion occurs when bubbles collapse on a surface. microbiologically induced corrosion (MIC) is one type of biological corrosion that occurs when the microorganism attaches to a metal. Pitting of aluminum and stainless steel in aqueous solutions containing chlorides is an example. this is unusual in that the loss of strength and ductility is not proportional to the amount of metal lost due to the corrosion. the most common type is dezincification of brass. Galvanic corrosion occurs when dissimilar metals are used in contact with each other and are exposed to an electrically conducting solution. pH effects the stability of the oxide films on metal alloys. Liquid-metal corrosion occurs when liquid metal attacks metal grain boundaries. Corrosion may be localized. even relatively minor ones. Intergranular corrosion occurs when there is selective corrosion in the grain boundaries of a metal or alloy without a significant attack on the grains. Stress corrosion occurs from either internal stress or externally applied stress and can result in cracking.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 53 3. Changes in process chemistry. Oxygen-Concentration corrosion frequently occurs under gaskets. Hydrogen embrittlement occurs when a significant amount of hydrogen is present at elevated temperatures. the effect corrosion may have on the chemical process. or carbon steel heated above 455°F (235°C) for prolonged periods and occurs when the metal is converted into corrosion products. potentially resulting in catastrophic failure. Graphite corrosion usually involves gray cast iron. the National Association of Corrosion Engineers has published charts detailing recommended operating limits for various hydrogen partial pressures. Corrosion may also be structural. ©2003 Factory Mutual Insurance Company. Water sometimes contributes to corrosion. particularly the halides. Significant changes in pH may change the corrosivity of some chemicals. a process whereby rust forces surfaces apart. temperatures and steel alloys. Biological corrosion occurs due to metabolic activity of microorganism. As a rule-of-thumb. The following conditions may increase corrosion: • Chlorides • Water: presence or absence • pH • High Temperature • High Flow Rates • Low Oxygen Concentration • Oxidizing Agents • Environmental Conditions: internal and external • Equipment Stress • Equipment Arrangement The presence of chlorides increases localized corrosion problems.

Using harder materials. or if the materials of construction are exotic or special (long lead times). Reference Data Sheet 12-2. Subsequent investigations of these incidents confirmed that damage could have been prevented or at least significantly minimized had inherently safer design concepts been used. High flow rates. The resistance of materials to similar environments and process conditions is a good screening tool. nitric. and <70% sulfuric are common reducing acids. The general applicability of materials in oxidizing and reducing acids is shown in Figure 17. Environmental conditions. phosphoric. and shifting of reaction mechanisms. this is physiochemical deterioration rather than corrosion. Nonmetals. The conventional jacket is less susceptible to crevice corrosion and provides better thermal shock protection. However. ©2003 Factory Mutual Insurance Company. Oxidizing agents may accelerate or retard corrosion depending on the characteristics of the metal. bolts. etc. and/or effective process safety management programs been in place. If non-repairable materials of construction are used (e. by unbalanced cooling from high temperature or by external modifications (rivets.g. and >70% sulfuric acid are common oxidizing acids. if not properly lubricated. 3. materials selected should be evaluated under proposed conditions whenever possible. Equipment stress may be caused during fabrication. hydrochloric. can increase abrasion and friction resulting in erosion. graphite). or velocity. both internal and external. sea mist. wears away metal surfaces. Supercritical process conditions are particularly challenging due to accelerated corrosion from the high temperatures and pressures. reducing flow rates. may exhibit deterioration similar to corrosion. Pressure Vessels. Galvanized steel should not be welded to stainless steel unless the galvanizing is completely removed from the area. Essentially every metal alloy has environmental conditions that produce stress corrosion cracking. Steel cracking from caustic is an example. Temperature also indirectly affects corrosion rates by impacting the solubility of air (oxidizer) and material phases. This will ensure shorter down times and help protect customer marketshare. All rights reserved. Formic. Glass-lined reactors are commonly supplied with a conventional jacket or with a half-pipe jacket constructed by welding a half-pipe coil around the outside of the tank. Equipment arrangement may also affect corrosion. Friction caused by metal pieces sliding over one another. Improper agitation and pumping can generate an excessive amount of bubbling that results in mechanical damage.16 Illustrative Losses Chemical processing and related industries continue to experience incidents involving process chemistries and process equipment. then it is prudent to order complete sets of spare components such as tube bundles and wear parts. External chloride corrosion may result from external insulation materials. and minimizing directional changes can minimize erosion. the chemical hazards been completely understood. such as plastics. and road salt.). Reduced oxygen concentrations accelerate corrosion. chemical spills.. Chromic. . affect corrosion rates. However.7-46 17-11 Page 54 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets High temperature and hot spots increase corrosion rates.

Applicability of Materials in Oxidizing and Reducing Acids Illustration courtesy of Te-Lin Yu Consultancy ©2003 Factory Mutual Insurance Company. All rights reserved. 17.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 55 Fig. .

Data Sheet 5-23. Data Sheet 6-9. Emergency and Stand-By Power Systems. Protective Grounding for Electric Power Systems and Equipment. Data Sheet 7-50. Data Sheet 6-17/13-20. Data Sheet 7-80. ©2003 Factory Mutual Insurance Company. Emergency Venting of Vessels. Ammonium Nitrateand Mixed Fertilizers Containing Ammonium Nitrate. All rights reserved. Data Sheet 7-32. Data Sheet 7-0. Data Sheet 7-2. Acetylene. Data Sheet 7-45. Electrical Testing. Data Sheet 12-2. Static Electricity.7-46 17-11 Page 56 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 4. Storage of Liquid/Solid Oxidizing Materials.0 REFERENCES 4. Industrial Ovens and Dryers. Organic Peroxides. Data Sheet 7-72/12-10. Lightning and Surge Protection for Electrical Systems. Loss Prevention in Chemical Plants. Compressed Gases in Cylinders. Physical Operations in Chemical Plants. Process Furnaces. Oxygen. Data Sheet 7-74. Hydrogen. Pressure Vessels. Causes and Effects of Fires and Explosions. Data Sheet 5-10. Data Sheet 5-20. Electrolytic Chlorine Processes. Data Sheet 7-94/12-22. Waste Solvent Recovery. Data Sheet 7-44/17-3. Data Sheet 7-59. Data Sheet 7-13. Instrumentation and Control in Safety Applications. Data Sheet 6-11. Spacing of Facilities in Outdoor Chemical Plants. Flammable Liquid Operations. Fume Incinerators. Ammonia Synthesis Units. Catalytic Steam-Hydrocarbon Reformers. Data Sheet 7-91. Data Sheet 7-99/12-19. Mechanical Refrigeration. Data Sheet 5-11. Data Sheet 7-51. Data Sheet 6-10.1 FM Global Data Sheet 5-8. Rotary Kilns and Dryers. Data Sheet 7-47. Data Sheet 7-43/17-2. Data Sheet 7-34. Elements of Industrial Heating Equipment. Data Sheet 7-82N. Distilleries. . Data Sheet 7-52/17-13. Data Sheet 7-49/12-65. Inerting and Purging of Equipment. Data Sheet 7-89. Data Sheet 6-0/12-1. Heat Transfer by Organic and Synthetic Fluids.

and standards in effect today dealing with the chemical process industries. 1984 UK Control of Major Accident Hazards (COMAH). Maintenance. Processing. Division 1 and Division 2 ©2003 Factory Mutual Insurance Company. Processing. 1999 UK Management of Health and Safety at Work Regulations. regulations and standards. and Storage of Zirconium 485: Storage. is provided below. Operation. Handling. and Repair of Tanks in Production Service RP 500: Recommended Practice for Classification of Electrical Installations at Petroleum Facilities Classified as Class I. Handling. Inspection. and Handling of Combustible Particulate Solids 655: Prevention of Sulfur Fires and Explosions 4. as well as organizations that develop standards. 1992 (under the 1974 Health and Safety at Work Act) USA: American Institute of Chemical Engineers (AIChE): CCPS Guidelines for Hazard Evaluation Procedures CCPS Guidelines for Chemical Process Quantitative Risk Analysis CCPS Guidelines for Technical Management of Chemical Process CCPS Guidelines for Pressure Relief and Emergency Handling Systems CCPS Guidelines for Safe Automation of Chemical Processes CCPS Guidelines for Chemical Reactivity Evaluation and Applications to Process Design CCPS Guidelines for Preventing Human Error in Process Safety CCPS Guidelines for Process Safety Fundamentals for General Plant Operations CCPS Guidelines for Engineering Design for Process Safety CCPS Guidelines for Implementing Process Safety Management Systems CCPS Guidelines for Safe Process Operations and Maintenance CCPS Guidelines for Process Safety in Batch Reaction Systems CCPS Process Equipment Reliability Database CCPS Inherently Safer Processes: A Life Cycle Approach American Society of Mechanical Engineers (ASME): Boiler and Pressure Vessel Code Section VIII American Petroleum Institute (API): RP 12R1: Setting. A list of well-known codes. All rights reserved. Processing.3 Other Codes. 1989 Revised EC Directive issued as Seveso II (96/82/EC). Handling.2 NFPA National Fire Protection Association (NFPA): 30: Flammable and Combustible Liquids 30B: Manufacture and Storage of Aerosol Products 35: Manufacture of Organic Coatings 49: Hazardous Chemicals Data 70: National Electrical Code (NEC) 269: Standard Test for Developing Toxic Potency Data for Use in Fire Hazard Modeling 325: Guide to Fire Hazard Properties of Flammable Liquids. regulations.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 57 4. . Regulations and Standards Worldwide. and Volatile Solids 329: Handling Releases of Flammable and Combustible Liquids and Gases 430: Storage of Liquid and Solid Oxidizers 432: Storage of Organic Peroxide Formulations 481: Production. Gases. European and UK: EC Framework Directive from Article 118A of the Treaty of Rome. 1996 UK Control of Industrial Major Accident Hazards (CIMAH). and Storage of Titanium 482: Production. and Use of Lithium Metal 491: Guide to Hazardous Chemical Reactions 654: Prevention of Fire and Dust Explosions from the Manufacturing. Processing. there are numerous codes.

Zone 1. Zone 0. Application of Safety Instrumented Systems for the Process Industries National Association of Corrosion Engineers (NACE): numerous Standards and technical publications US Occupational Safety and Health Administration (OSHA) — Process Safety Management (PSM) 29 CFR 1910.1 Acronyms and Abbreviations AIChE — American Institute of Chemical Engineers AIT — autoignition temperature ARC — accelerating rate calorimetry ARSST — advanced reactive system screening tool ASME — American Society of Mechanical Engineers AST — adiabatic storage test ASTM — American Society for Testing and Materials BLEVE — boiling liquid. and Stray Currents Std 510: Pressure Vessel Inspection Code Instrument Society of America (ISA) — S84. expanding vapor explosion CARAT — Chemical Accident Risk Assessment Thesaurus CART — calculated adiabatic reaction temperature CCPS — Center for Chemical Process Safety CHA — chemical hazard analysis CHETAH — Chemical Thermodynamics and Energy Release Evaluation (ASTM) CMR — catalytic membrane reactor CODATA — International Council for Science Committee of Data for Science and Technology CSTR — continuous stirred tank reactor DDT — deflagration to detonation transition DI — deionized DIERS — Design Institute for Emergency Relief Systems (AIChE) DIPPR — Design Institute for Physical Property Data (AIChE) DSC — differential scanning calorimetry DTA — differential thermal analysis FEMA — failure mode and effect analysis FTA — fault tree analysis HAZOP — hazard and operability study IMRCF — inert membrane reactor with catalyst on the feed side IUPAC — International Union of Pure and Applied Chemistry LEL — lower explosive limit LFL — lower flammable limit LOC — Limiting Oxygen Concentration MCC — mixing cell calorimetry MIC — microbial induced corrosion MOC — management of change MOCC — minimum oxygen concentration for combustion NACE — National Association of Corrosion Engineers NFPA — National Fire Protection Association NIST — National Institute of Standards and Technology OD — outer diameter ©2003 Factory Mutual Insurance Company. and Installation of Pressure-Relieving Devices in Refineries RP 750: Management of Process Hazards RP 752: Management of Hazards Associated with Location of Process Plant Buildings RP 920: Prevention of Brittle Fracture of Pressure Vessels RP 2003: Protection Against Ignitions Arising out of Static. Selection. All rights reserved.7-46 17-11 Page 58 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets RP 500: Recommended Practice for Classification of Electrical Installations at Petroleum Facilities Classified as Class I. Lightning. and Zone 2. .01. RP 520/1: Sizing. US Environmental Protection Agency (EPA) — Risk Management Program (RMP) 40 CFR 68 APPENDIX A GLOSSARY OF TERMS A.119.

All rights reserved. independent of the ignition source. proportional to the concentration of the solute. Enthalpy (∆H): the heat content of a substance or the heat of reaction. Boiling Point Elevation: an increase in the boiling point of a solution. but physically different. Adiabatic: a condition where no heat is exchanged between a system and its surroundings. Anion: an atom or molecule with a negative charge.2 Definitions Activation Energy (Ea): the critical energy needed for a reaction to occur. Entropy (∆S): the degree of disorder in a chemical system. Failure Modes and Effects Analysis (FMEA): a hazard identification technique where all known failure modes are considered and potential undesired outcomes are detailed. They are not isomers. Anode: the negative electrode at which oxidation occurs. Condensed Phase Explosion: an explosion of a liquid or solid. but is recovered unchanged at the end of the reaction. Cathode: the positive electrode at which reduction occurs. Enantiomers: isomers that are mirror images of each other. Arrhenius Equation: k = Ae-Ea/RT where k is the rate constant A is the frequency factor Ea is the activation energy R is the gas constant T is temperature Autoignition temperature (AIT): the minimum temperature required to initiate self-sustained combustion in air. Catalyst: a substance that increases the rate of a reaction. Autoxidation: self-heating via slow oxidation. Reaction systems that result in greater disorder have positive entropy. increasing the chain length decreases the AIT. Activation Entropy (Sj): the relative position or orientation of the molecules needed for a reaction to occur. Corrosion: the loss of metal due to chemical or electrochemical attack. Compounds that release energy when formed usually have a negative enthalpy. They have identical physical and chemical properties except toward optically active reagents. . Chemical hazard assessment: formal process for identifying and quantifying reactive chemical hazards. For straight chain hydrocarbons. ©2003 Factory Mutual Insurance Company.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 59 PFR — plug flow reactor P&ID — process and instrumentation diagram PHA — process hazard analysis PSM — process safety management REITP2 — Revised Program for Evaluation of Incompatibility from Thermodynamic Properties RSST — reactive system screening tool SIL — safety interlock level SOP — standard operating procedure TFR — tubular flow reactor UEL — upper explosive limit UFL — upper flammable limit VCE — vapor cloud explosion VSP — vent sizing package A. Diastereomers: molecules that are chemically similar. Critical Point: the highest temperature and pressure at which a pure material can exist at vapor-liquid equilibrium.

Oxime: a derivative of ammonia. the LOC is 9-11% oxygen. Oxygen is the most common oxidant. Heterogeneous Equilibrium: equilibrium involving more than one phase. external temperature is compared to internal temperature to determine onset temperature. . Mitigation: reduction of risk through action. due to its higher specific heat. Oxidant: any material that can react with a fuel producing combustion. Carbon dioxide is soluble in many liquids and will react with many alkalines. For most hydrocarbons where oxygen is the oxidant and nitrogen is the diluent. All rights reserved. where P is pressure V is volume n is the number of moles of material R is the gas constant T is temperature Avogadro: V1 N2 = V2N1 where P. Hazard Analysis: the systematic identification of chemical or physical characteristics and/or processing conditions and/or operating conditions that could lead to undesired events. Gas Laws: Ideal: PV = nRT. Metallocenes: metallocenes are single-site catalysts that provide greater control over molecular chain length and structure. usually by affecting the required activation energy. by volume. T are constant Boyle: P1V1 = P2V2 where n.7-46 17-11 Page 60 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets Fault Tree Analysis: a hazard frequency estimation based on a logic model of the failure mechanisms of a system. it adjusts to minimize the disturbance. Inhibitors are also commonly called negative catalysts or reaction poisons. Isoperibolic calorimetry: a system where the controlling external temperature is constant. Le Chatelier’s principle: when a system is disturbed. C = NOH ©2003 Factory Mutual Insurance Company. the LOC is about 13% oxygen.T∆S Inhibitor: a substance that retards a chemical reaction. Onset Temperature: temperature at which a self sustaining chemical reaction can occur. P are constant (volume varies directly with temperature) Dalton: Ptotal = p1 + p2 + … where T. V are constant (total pressure equals sum of partial pressures) Flammable Limits: minimum and maximum concentrations of a flammable vapor or gas/air mixture that will propagate a flame (flash) when ignited. Therefore. Where carbon dioxide is the diluent. by volume. Homogeneous Equilibrium: chemical equilibrium established in one phase. ∆G = ∆H . Gibb’s Free Energy: a thermodynamic quantity measuring reactivity by combining enthalpy and entropy. It is also a substance that is responsible for the oxidation of another substance. internal temperature changes are quickly manifested as pressure and volume changes. Hazard and Operability Study (HAZOP): a method used to identify potential process hazards and operating problems using guidewords. Minimum Oxygen Concentration for Combustion (MOCC): see Limiting Oxygen Concentration. The currently accepted test method for determining flammability limits is ASTM E 681. They are used in polyolefin production. Limiting Oxygen Concentration (LOC): the concentration of oxidant below which flame propagation can not occur. its use in inerting is limited. Note: lower flammable limit (LFL) and upper flammable limit (UFL) are often used interchangeably with lower explosive limit (LEL) and upper explosive limit (UEL). Isothermal: a system where the (internal and external) temperature is constant. Oxide: a compound of oxygen and another element. T are constant (volume varies inversely with pressure) Charles: T1V2 = V2T1 where n.

Risk Analysis: a qualitative or quantitative estimate of risk. There are 40 known naturally occurring zeolites and more than 150 synthetic zeolites. usually a solid with metallic and non-metallic elements. The higher the vapor pressure at standard temperature and pressure. Risk: the probability that an event will occur times the magnitude of the consequence. All rights reserved. solid in liquid.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 61 Oxirane: another name for an epoxide ring. Worst Credible Case: an event or combination of events that could result in a runaway reaction that would create the largest or fastest pressure excursion. These inorganic materials are frequently used as a catalyst in environmental applications (reduction of NOx.g. Racemic modification: an equal mixture of enantiomers. Analogous to saturated hydrocarbons in structure. It is optically inactive. . it is ratio of the gas in the solution/solvent to the gas above the solution/solvent. Solvent: see Solubility. e. VOC removal) and are seeing increased use in the chemical processing industries. liquid in liquid. Solute: the substance that is dissolved in a solution. gas in liquid. A. it is the upper concentration limit of the solute in the solvent. Silane or silicon hydride: general formula SinH2n+2. accelerating reaction rate which results in rapid increases in temperature and pressure. Salt: any substance that yields ions other than H+ and OH-. Stereoisomers: isomers that are different from each other only in the way they are oriented. Solubility: the ability or tendency of one substance to blend uniformly with another. Zeolite: a member of a family of minerals called tectosilicates. For liquids and solids. the easier a liquid will evaporate. Vapor pressure: the pressure exerted when a solid or liquid is in equilibrium with its own vapor. The heat generated exceeds the heat removed by the cooling system and/or vaporization. Reductant: a substance that is responsible for the reduction of another substance.3 Chemical Functional Groups -C-C-C=C-C≡C-C=C=C-C=C-C=CAr-R RCHO R1R2C=O -C=C-C=O R-OH Ar-OH RC=O RR’C=O -COOH RCOOH R(COOH)2 alkane alkene alkyne allene diene arene aldehyde ketone unsaturated carbonyl alcohol phenol acyl carbonyl carboxyl carboxylic acid dicarboxylic acid ©2003 Factory Mutual Insurance Company. Runaway reaction: an uncontrollable. gas in gas. For gases.. Risk Assessment: use of risk analysis results to make business decisions. Spontaneous ignition: see autoxidation.

F. R. UK. Hazards X. AIChE. NY 1999 Donahue. 115. 1609-1616. 1987 Guidelines for Chemical Reactivity Evaluation and Application to Process Design. The Institute of Chemical Engineers Symposium No. All rights reserved. Rugby. Identifying Hazardous Chemical Reactivity. Center for Chemical Process Safety. Journal of Thermal Analysis. AIChE. 49 (1997). J. L. P. NY 1994 Guidelines for Process Safety in Batch Reaction Systems. International Conference on Hazard Identification and Risk Analysis Barton. New York. Center for Chemical Process Safety. 1989. . and Nolan. Process Safety in Fine and Specialty Chemicals. AIChE. A. E. Bretherick. International Symposium on Preventing Major Chemical Accidents. pp.7-46 17-11 Page 62 Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets R-O-R RC=OOR’ -C-C\ / O R-O-O-R R-X Ar-X RC=OCl R-NH2 R2NH R3N R-NO2 RN=C=O RC=ONH2 (RC=O)2NH C=NR R4NX ArN≡NX 2 3 5 5 5 6 fused aromatic rings fused aromatic rings member ring containing member ring containing member ring containing member ring containing ether ester epoxide peroxide alkyl halides aryl halides acid chloride 1°amine 2° amine 3° amine nitrate isocyanate amide imide imine quaternary ammonium salt diazonium salt naphthalene anthracene or phenanthrene pyrrole furan thiopene pyridine N O S N Miscellaneous: Isotatic — compound with all groups on one side of the chain Saturated — compound only having single bonds Unsaturated — compound having double or triple bonds Ar — a benzene ring R — a hydrocarbon X — a halogen APPENDIX B BIBLIOGRAPHY Baron. G. Center for Chemical Process Safety. New York. ©2003 Factory Mutual Insurance Company. New York. Vol. Hazards Caused by Trace Substances. NY 1995 Guidelines for Preventing Human Error in Process Safety. Reactive Chemical Hazards: An Overview.

A. G. Usborne Essential Chemistry. T. O’Brien. Philadelphia. Gerald J. T. John Why DIERS Technology Should be Used in Risk Assessment. CAMEO Today. 1989 Shanley. D. Chemical Engineering Progress. E. Process Plants: A Handbook for Inherently Safer Design. Robert H. Michael Biocatalysis Grows for Drug Synthesis. 1999 CD-ROM Rogers. and Melham. Screen Reactive Chemical Hazards Early in Process Development. Process Safety Progress. et al. January/February 1996. 1987 ©2003 Factory Mutual Insurance Company. Yoshida. PA 1998 Leggett. S. and Shanley. OK 1992 Jones. Rely on a Risk-Based Approach for Resource-Effective Facility Siting. Elsevier Science. Gifford. 30th AIChE Loss Prevention Symposium Mosley. Chemical Engineering Progress.2.Chemical Reactors and Reactions FM Global Property Loss Prevention Data Sheets 7-46 17-11 Page 63 Farr. and Singh. Te-Lin Selecting Performance Alloys. EDC Publishing. November 2000 Noronha. E. S. On the Estimation of Hazard Potential for Chemical Substances. International Symposium on Runaway Reactions and Pressure Relief Devices. G. D. Chemical Processing. Chemical & Engineering News. Vol. No.W. National Safety Council. No. Process Safety Progress. Perry’s Chemical Engineers’ Handbook. Safety of Reactive Chemicals. The Systematic Assessment of Chemical Reaction Hazards. Keltz. 19.18. C. 1 (2000). January 1982 Perry. et al. May 1999. Process Improvements from Incident Data. January 1999 Melham. 1995. 13-18 McCoy. October 1999. International Symposium on Runaway Reactions. All rights reserved. On the Estimation of Hazard Potential for Chemical Substances. R. Yau. Chemical Engineering Progress. Thermal Stability Hazards Analysis. Taylor & Francis. D. W. Tulsa. A. . Vol. et al. J. Jim Chemical Hazards Produced by Water-Reactive Substances.

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