Form No, 22-154.01 Silicone antifoams in chemical processing by K. W, Farminer Dow Corning Limited, Barry, Glamorgan, U.K.Silicone antifoams in chemical processing k.W. FARMINER® Foam has long been recognized as an undesirable feature in many industries because it can seriously impair product quality and reduce production capacity. Solutions to a number of problems are described THE PRESENCE OF FOAM can seriously impair the ‘operation of chemical processing equipment. Even in simple, stirred reactors excessive foam can seriously reduce batch sizes and make secondary processes, such as monomer recovery, both difficult and expensive, Again foam in such Units is recognizable since the vessels are normally equipped with sight glasses. In more complex operations, such as continuous gas-liquid mass transfer equipment, where columns and separators are involved, foam is not always recognised as contributing to problems encountered. The presence of excessive foam in this 1ype of operation can affect product separation efficiency, cause latge overhead losses, limit plant throughputs and in serious cases can ‘cause damage to downstream equipment or heavy environ: mental pollution There are two probleris, however, which often beset the plant operator; recognizing foam as a cause of a particular problem, and deciding w hich antifoam, {rom the consider able selection available, will solve it, The author quotes examples from his company’s experience, Foam and foam control Pure liquids do not normally produce true foams. A true foam is a coarse dispersion of a gas in a small amount of liquid such that the bulk density of the dispersion approaches that of the gas rather than the liquid. Bubble froths may be Formed in viscous liquids by pas injection but these disperse rapidly as the liquid drains. True foaming, therefore, occurs ‘only when the liquid between the bubbles thins to a lamella instead of rupturing at the point of closest contact. Thermo: dynamically this sort of behaviour by a pure liquid is energetically unfavourable, Liquids do, however, foam, some very badly. Foaming in such eases can be explained by the presence of stabilising Solute that is positively absorbed at the surface. Such solutes, often present as impurities, possess both “hydropho- bie" and “hydrophilic” character and are in fact surfactants in a particular system, These surfactants concentrate at the surface with their “hydrophilic” portion in the continuous phase and the “"hydrophobic part” trying to emerge into the gas phase, The lower forces of attraction between the hydrophobic ends of the molecules will produce a new surface of lower surface tension than previously. In the case of water the presence of a surfactant system will seduce the surface tension from 72 to around 30 dynesfem, ‘The positive absorption of the surfactant at the interface means that work is required to move it to the bulk. The increase in free energy resulting from such a transfer will, if large enough, make it energetically more favourable for the foam to persist. In order to destroy the foam, an antifoam additive must be incorporated into the system that will displace the Foam stabilizer from the interface, or will form mixed films with it, The foam stabilizing mechanism will thus be destroyed and the foam will collapse. In order to spread on the film lamella the antifoamy must have low surface tension and to ‘operate efficiently it must be insoluble in the foaming ‘medium. There have been several discussions of the exact ‘mode of action of antifoams and of the many different types. available, Most organic antifoams for aqueous systems consist of an insoluble oil compounded with a surfactant to increase spreading. ‘Antifoams based on polydimethyl siloxane fluids have most of the desirable Features necessary for controlling foam in many media—fast knockdown. long lasting action. high efficiency, low cost and ease of handling. These silicone fluids are clear, colourless liquids with surface tensions of 20-22 dynes/em. When compounded with silica they may be used, either alone or emulsified to improve dispersibility, as predictably efficient foam control agents, The criteria for successful foam control are therefore: (1) A lower surface tension than the foaming medium 2) tasolubility in the foaming media. (3) Dispersibility in the foaming media Sour and acid gas scrubbing The use of amines or carbonate solutions to remove hydrogen sulphide or carbon dioxide from gas streams is widespread in the oil and petrochemical industries. The incoming gas to an amine of carbonate gas-scrubbing, unit is usually” a hydrocarbon mixture, or derived from a hydrocarbon, This gas contains, in addition to the carbon dioxide andjor hydrogen sulphide, impurities such as liquid hydrocarbons, well-head inhibitors, valve greases and other materials, The presence of these trace impurities will cause Foaming in the absorber * + * since they ean concentrate in the absorbent system. ‘The antifoam must be added to the absorbent stream and in many plants there is a separate antifoam addition point for feeding antifoams to the top of the absorber. Alterna- tively the antifoam can be metered into the suction of the absorber feed pump, The alkaline character of absorbents requires that a special antifoam emulsion, such as Dox: Corning DB 31, should be tused for dealing with this problem. In laboratory and plant {rials such emulsions have proved superior to other silicone types and to a wide variety of non-silicone antifoams in Refinery processing The use of aatifoams in refinery processing. has been well documented © 7. Some major applications are: Crude processing. Certain crude oils—notably Kuwait crudes--have a tendency to foam badly. This tendency can seriously affect operation of gas-oil separation equipment at CHEMICAL PROCESSING.the refinery and reduce the efficiency of the crude distillation unit. Foam may be controlled by adding low concentrations (1-2 parts/million) of high viscosity polydimethy! silicone fluid (Dow Corning 200/12.500, or 200/60,000), suitably dispersed in kerosene or a similar fraction, to the crude oil before it enters the gas-oil separation or crude unit. Early addition of antifoam to the system has often proved beneficial to the operation of the desalter. Since the polydimethyl siloxane is of relatively tow volatility it will cexit from the column with the heavier fractions. Vacuum units. Foam can impair the operation of such a unit and the addition of polydimethy! silicone fluid will control this foam. However, the antifoam should be injected with the reflux at the top of the column and not with the column, feed. The low volatility of the silicone will ensure that it leaves the unit with the heavier bitumen fractions. Asphalt production and handling Propane deasphaiters. Foam in the strippers ofa deasphalting twit will eause heavy fractions to be carried into the recycle system. The addition of antifoam compound (Dow Corning MSA) either to the fash drum er to the strippers will eliminate this problem. “Asphalt blowing. When hot asphalt comes into contact with ‘water serious foaming can osvur. When asphalt is blown, any water in the air will cause excessive foaming: addition of antifoam compound will eliminate this. Similar problems can oceur when asphalt is processed and/or emulsified for tse in road oF roof construction, Delayed coking, Foam always occurs in delayed coking drums during the coking process and can cause blockages in the overhead lines. Addition of 10_partsmillion poly- dimethyl siloxane (Dow: Corning 200/12.500), predispersed in Kerosene, will control foam, The antifoam may be added at one of three points (1) directly 0 the drum ‘when foam is visible (2) before the furnace this has the added advantage of prolonging tube life: and (3) the antifoam may have already been added either to the crude oF vacuum units. 1s ultimate destination willbe the delayed coker. Petrochemical operations Aromatics (BTX) extraction. There are three well-known processes for extracting aromaties from hydrocarbons, these fare Udex, Sulfolane and Arosolvan. Basically similar in concept these plants consist of a liquid-liquid extraction system in which the feed is contacted with a solution ‘capable of absorbing the aromatics. The mixture of absor- bent and aromatics is then separated by distillation and the absorbent recycled for re-use, Addition of an antifoam compound (Dow Corning Antifoan MSA or Q), prediluted in toluene or xylene, to the stripper feed will eliminate solvent loss and has been kno'vn to double unit throughputs. Acrylonitrile production. Foam can seriously impair opera- tion of separation units in acrylonitrile production. In the first separation column, which contains water, hydrogen ‘eyanide, acrylonitrile, acetonitrile and other impurities, addition of an antifoam emulsion (Dow Corning DB 31) usually by steam injection octosee 1973 prediluted in water will eliminate the foam. Ethylene oxide units. There ate to foaming problems associated with ethylene oxide units. One, in CO, removal, hhas already been discussed, The second problem oceurs when cihylene oxide is separated from the water in which it has bbeen absorbed. The aqueous phase contains glycols which are formed during the reaction. These are extremely surface active and can cause excessive foaming. The remedy is to feed antifoam DB 31 emulsion to the top of the stripper. ‘The antifoam will exit with the waterJimpurities stream and will eventually be recycled. Monomer recovery PVC production. Agents used to disperse vinyl chloride in ‘water have high foaming potential. In order to recover vinyl chloride from pve reactions @ vacuum system is used and the unreacted monomer actually boils out of the pve/water dispersion. Excessive foaming can occur at this stage and Solid pve particles can be carried into the vacuum lines and block the compressor. Two remedies are available: (1) Add the antifoam compound before starting the polymerization (2) Add the antifoam emulsion to the vessel befire starting the recovery process (at the end of poly merization) Both methods are used either separately or, better stil together for optimam foam control during palymerization and during stripping, Synthetic latices. Synthetic latices are produced by emulsion polymerization of butadiene and styrene and in some cases acrylonitrile, The monomers are emulsified or dispersed in water by means of high surfactant concentrations and polymerization initiated by addition of peroxides ete Production of synthetic latices by polymerization is normally only continued until 90 per cent of the monomer has been converted. The reaction is then stopped and the residual monomers recovered in two stages. Butadiene is First recovered and styrene removed in the second stage The latices are often of high pH (9 or more) and wre heated. Under these conditions special antifoam emulsions [Dow Corning DB 31) should be used. These may be added either by metering pump to the column or in doses to the latex before commencing recovery Chlorinated solvent systems The only areas where the polydimethyl siloxane-based antifoam is ineffective is where itis dissolved by components, of the foaming system. An important example of such a system occurs in the processing of chlorinated hydrocarbons, Under these conditions @ fluorosilicone fluid must be used, such as Dow Corning FS 1265 fluid. Such fluids may be prediluted in a solvent such as Cellasolre acetate or methyl! isobutyl ketone. 1 ies Sa Ba 938 8. on fie TE Sta Te