Unwanted reactions

AH corrosion inhibitors in use as of this writing are oil-soluble surfactants (qv) which consist of a hydrophobic hydrocarbon backbone and a hydrophilic functional group. Oil-soluble surfactant-type additives were first used in 1946 by the Sinclair Oil Co. (38). Most corrosion inhibitors are carboxyhc acids (qv), amines, or amine salts (39), depending on the types of water bottoms encountered in the whole distribution system. The wrong choice of inhibitors can lead to unwanted reactions. Eor instance, use of an acidic corrosion inhibitor when the water bottoms are caustic can result in the formation of insoluble salts that can plug filters in the distribution system or in customers vehicles. Because these additives form a strongly adsorbed impervious film at the metal Hquid interface, low Hquid concentrations are usually adequate. Concentrations typically range up to 5 ppm. In many situations, pipeline companies add their own corrosion inhibitors on top of that added by refiners. 

To provide for suitable timing of the pH reduction over the wide range of temperatures that may be encountered, the instant films may use polymeric timing layers in which permeabiUty to alkaU varies inversely with temperature. In the integral films, where all components are retained within the film unit after processing and the moisture content remains high for several days, care must be taken to avoid materials that could migrate or initiate unwanted reactions even at reduced pH. 

Inadequate removal of solvent leading to unwanted reaction in downstream equipment or in subsequent steps. 

Unwanted reaction Clean and inspect equipment after each use Design with compatible materials contaminants. Maintain integrity of the system Design emergency relief system (ERS) for runaway scenario CCPS G-13 CCPS G-22 CCPS G-23 CCPS G-29... 

Thermal contrac- Drumming at proper temperatures tion vacuum ere-. integrity walls ated which can suck air moisture prevent water accumulation on drum etc., into drum creating unwanted reaction or collapse of the drum. CCPS G-3 CCPS G-15 CCPS G-22 CCPS G-29... 

Unwanted reaction due to contaminants in equipment or solvent wash. 

The released energy might result from the wanted reaction or from the reaction mass if the materials involved are thermodynamically unstable. The accumulation of the starting materials or intermediate products is an initial stage of a runaway reaction. Figure 12-6 illustrates the common causes of reactant accumulation. The energy release with the reactant accumulation can cause the batch temperature to rise to a critical level thereby triggering the secondary (unwanted) reactions. Thermal runaway starts slowly and then accelerates until finally it may lead to an explosion. 

Use materials of construction that enhance inherently safer operations. Corrosion leads to leaks incompatible materials can lead to unwanted reactions. 

Here are some other examples of unwanted reactions caused by contaminants [7] ... 

Hydrogenation of 3-pyridinecarboxylic acids is apt to be accompanied by extensive decarboxylation (2S), but this unwanted reaction can be prevented by carrying out the reaction in the presence of one equivalent of base (33,79). Ruthenium (33), rhodium (29), platinum oxide (2S,59), and palladium (30) have all proved effective catalysts for reduction of pyridinecarboxylic acids to the saturated acid. 

With steam generated at or close to the boiler design pressure it is inevitable that some of the steam-using equipment will have to be supplied at a lower pressure. In some cases the plant items themselves have only been designed to withstand a relatively low pressure. Sometimes a reaction will only proceed when the steam is at a temperature below a certain level or an unwanted reaction will occur above a certain level. For these and similar reasons, steam often is distributed at a relatively high pressure which must then be lowered, close to the point of use. Pressure-reduction stations incorporating pressure-reducing valves are fitted to perform this function. 

All drugs, in addition to their therapeutic effects, have the potential to do harm, i.e. to cause adverse/unwanted reactions (side effects). These may or may not be related to the principal pharmacological action of the drug. Examples of the second category are toxic effects of metabolites of a drug or immunological reactions. 

Frozen Foods. Corrosion caused by the reaction of foods with aluminum containers is unusual if the products are handled and stored at 0°F or lower. However, the inevitable bad handling of frozen foods during commercial distribution causes undesirable thawing. In this condition, not only does the food deteriorate, but it can also attack the container. Such unwanted reactions can be effectively controlled by using coated aluminum containers. Since aluminum is highly compatible with frozen fruits and citrus juices, it has been used extensively as a liner for fiberboard composite cans, as complete aluminum cans, or as ends in combination with steel can bodies in the frozen food industry. 

Avoid sequences which may lead to unwanted reactions at other sites in the molecule. 

What unwanted reactions would happen during attempted oxidation of (10) to (11) and reduction of (12) to (13). How might they be prevented ... 

Cyclic structures can form as a result of side reactions. One of the most common examples is the formation of diketopiperazines during the coupling of the third amino acid onto the peptide chain (Fig. 7). Intramolecular amide bond formation gives rise to a cyclic dipeptide of a six-membered ring structure, causing losses to the sequence and regeneration of the hydroxyl sites on the resin. The nucleophilic group on the resin can lead to fiuther unwanted reactions [14]. 

From an examination of Equation 8.1, it can be seen that several things can be done to improve the heat-transfer rate. Quite often the simplest approach is to increase the temperature differential, by using higher-pressure steam or a hot oil supply. In some cases this may have adverse effects, for example a very hot wall temperature may lead to fouling, or, worse, initiate unwanted reactions. This is likely to be more pronounced in cases where mass transfer is poor. In some instances this practice may... 

It is important that chemical engineers master an understanding of metabolic engineering, which uses genetically modified or selected organisms to manipulate the biochemical pathways in a cell to produce a new product, to eliminate unwanted reactions, or to increase the yield of a desired product. Mathematical models have the potential to enable major advances in metabolic control. An excellent example of industrial application of metabolic engineering is the DuPont process for the conversion of com sugar into 1,3-propanediol,... 

The possibility of a species reacting by parallel paths to yield geometric isomers or entirely different products is often responsible for low yields of a desired product. If circumstances are such that the orders of the desired and unwanted reactions are different with respect to one or more species, it is possible to promote the desired reaction by an appropriate choice of reactor type and reaction conditions. 

In this case the order of the desired reaction is higher than that of the unwanted reaction so the exponent on the concentration is positive. The instantaneous selectivity is promoted by employing high concentrations of reactant. Consequently, batch or plug flow reactors are most appropriate from a selectivity viewpoint. 

In this situation the order of the unwanted reaction is greater than that of the desired reaction, so the selectivity is enhanced by using low concentrations of reactant. A CSTR is appropriate from a selectivity standpoint. Unfortunately, this situation is the one in which the selectivity considerations work against the desire for a small reactor size. 

Chemical interaction considers the unwanted reactions of process substances with materials in the plant area. These reactions are not expected to take place in the reactor and therefore they are not discussed in the side reaction subindex. The Inherent Safety Index has utilized EPA s matrix (Hatayama et al., 1980) to classify the hazards of the chemical interaction in a process. The worst interaction that appears between the substances present in the plant area is used in the calculations for the Chemical Inherent Safety Index. 

Origins of Unwanted Reactions, Report M-2631 B. Rasmussen Reviewed only... 

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