Processing reactive chemicals

The standard mechanisms of collisional energy transfer for both small and large molecules have been treated extensively and a variety of scaling laws have been proposed to simplify the complicated body of data [58, 59, 75]. To conclude, one of the most efficient special mechanisms for energy transfer is the quasi-reactive process involving chemically bound intennediates, as in the example of the reaction ... 

The next step is to apply a number of loss control credit factors such as process control (emergency power, cooling, explosion control, emergency shutdown, computer control, inert gas, operating procedures, reactive chemical reviews), material isolation (remote control valves, blowdown, drainage, interlocks) and fire protection (leak detection, buried tanks, fire water supply, sprinkler systems, water curtains, foam, cable protection). The credit factors are combined and appHed to the fire and explosion index value to result in a net index. 

Flame Retardants. Bromine compounds make up an important segment of the market for flame retardants used in polymers. Additive flame retardants are added to polymers during processing reactive flame retardants react chemically to become part of the polymer chain itself. In addition to the compounds Hsted in Table 3, a number of proprietary mixtures and phosphoms—bromine-containing flame retardants are also sold (see Elame RETARDANTS, HALOGENATED, FLAAffi RETARDANTS). 

Distribution of the monomer units in the polymer is dictated by the reactivity ratios of the two monomers. In emulsion polymerization, which is the only commercially significant process, reactivity ratios have been reported (4). IfMj = butadiene andM2 = acrylonitrile, then = 0.28, and r2 =0.02 at 5°C. At 50°C, Tj = 0.42 and = 0.04. As would be expected for a combination where = near zero, this monomer pair has a strong tendency toward alternation. The degree of alternation of the two monomers increases as the composition of the polymer approaches the 50/50 molar ratio that alternation dictates (5,6). Another complicating factor in defining chemical stmcture is the fact that butadiene can enter the polymer chains in the cis (1), trans (2), or vinyl(l,2) (3) configuration ... 

The electrochemical process industries are confronted with a wide range of hazards. These include electrical hazards, various explosion hazards, and the hazards associated with exposure to reactive chemicals. 

Stanley M. Englund/ M S / Ch E / Fellow American Institute of Chemical Engineers Process Consultant, The Dow Chemical Company (retired). (Section Editor, Section 16 Introduction Hazard Analysis Storage and Handling of Hazardous Materials Reactive Chemicals Combustion and Flammability Hazards Hazards of Vacuum Hazards oflnei t Gases)... 

Reactive Chemicals Reviews The process chemistry is reviewed for evidence of exotherms, shock sensitivity, and other insta-bihty, with emphasis on possible exothermic reactions. It is especially important to consider pressure effects— Pressure blows up people, not temperature The pumose of this review is to prevent unexpected and uncontrolled chemical reactions. Reviewers should be knowledgeable people in the field of reactive chemicals and include people from loss prevention, manufacturing, and research. 

Understanding the Reactive Chemicals and Reactive Chemicals Systems Involved The main business of most chemical companies is to manufacture products through the control of reactive chemicals. The reactivity that makes chemicals useful can also make them hazardous. Therefore, it is essential that people who design or operate chemical processes understand the nature of the reactive chemicals involved. 

Such mishaps can be worse if the chemistiy is not fuUy understood. A chemical plant can be inherently. safer if knowledge of the chemistiy of the process and the reactive chemicals systems involved is used in its design. 

Reactive System Screening Tool (RSST) The RSST is a calorimeter that quickly and safely determines reactive chemical hazards. It approaches the ease of use of the DSC with the accuracy of the VSP. The apparatus measures sample temperature and pressure within a sample containment vessel. Tne RSST determines the potential for runaway reactions and measures the rate of temperature and pressure rise (for gassy reactions) to allow determinations of the energy and gas release rates. This information can be combined with simplified methods to assess reac tor safety system relief vent reqiiire-ments. It is especially useful when there is a need to screen a large number of different chemicals and processes. 

Reactive chemical considerations for each key process step (enclose data if possible)... 

Reactive chemical hazards may arise from the inherent properties of the chemicals handled, used or disposed of and/or from their admixture or processing. 

Experience has shown that reactive chemistry hazards are sometimes undetected during bench scale and pilot plant development of new products and processes. Reactive chemistry hazards must be identified so they can be addressed in the inherent safety review process. Chemists should be encouraged and trained to explore reactive chemistry of "off-normal operations. Simple reactive chemicals screening tools, such as the interactions matrix described in Section 4.2, can be used by R D chemists. 

The number of reactions that can run away is enormous, Bretherick s Handbook of Reactive Chemical Hazards [1] lists about 4,700 chemicals that have been involved in hazardous reactions of one sort or another, and there are more than 20,000 cross-references to entries involving more than one chemical. It is an essential work of reference for the chemist, the process engineer, and everyone involved in process safety. All I can do here is give a few examples to illustrate the reasons why runaways occur. 

This chapter reviews the reported effects of different types of energy on chemical processing. Many of them are already known for a long time, but were, until recently, mostly used in nonreactive systems such as separation or drying. The focus here is on the (assumed) mechanism, reported effects, and known industrial applications of reactive chemical systems. 

Temperature control Adequately sized pressure relief Elimination of contaminants, including metallic residues, from process streams and equipment Selection of materials of construction compatible with the chemicaKs) in use, properly cleaned and passivated Elimination of ingress of reactive chemicals, e.g. water, air Date labelling and inventory control in storage Cleaning and inspection of reusable containers, tankers etc. before refilling ... 

Low temperature steam and formaldehyde Reactive chemical Indicator paper impregnated with a formaldehyde-, steam- and temperature-sensitive reactive chemical which changes colour during the sterilization process Gas concentration, temperature, time (selected cycles)... 

For processes under development, the most cost-effective means of avoiding potential risk is to eliminate those materials that are inherently unsafe that is, those materials whose physical or physico-chemical properties lead to them being highly reactive or unstable. This is somewhat difficult to achieve for several reasons. First, without a full battery of tests to determine, for example, flammability, upper/lower explosivity limits and their variation with scale, minimum ignition temperatures, and so on, it is almost impossible to tell how a particular chemical will behave in a given process. Second, chemical instability may make a compound attractive to use because its inherent reactivity ensures a reaction proceeds to completion at a rapid enough rate to be useful that is, the reaction is kinetically and thermodynamically favoured. 

Free radicals are short-lived, highly-reactive transient species that have one or more unpaired electrons. Free radicals are common in a wide range of reactive chemical environments, such as combustion, plasmas, atmosphere, and interstellar environment, and they play important roles in these chemistries. For example, complex atmospheric and combustion chemistries are composed of, and governed by, many elementary processes involving free radicals. Studies of these elementary processes are pivotal to assessing reaction mechanisms in atmospheric and combustion chemistry, and to probing potential energy surfaces (PESs) and chemical reactivity. 

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