TWITCHELL PROCESS.
The Twitchell process of saponification consists of causing an almost complete cleavage of fats and oils by the use of the Twitchell reagent or saponifier, a sulfo-aromatic compound. This is made by the action of concentrated sulfuric acid upon a solution of oleic acid or stearic acid in an aromatic hydrocarbon. From 0.5 per cent. to 3 per cent. of the reagent is added and saponification takes place from 12-48 hours by heating in a current of live steam. The reaction is usually accelerated by the presence of a few per cent. of free fatty acids as a starter. Recently the Twitchell double reagent has been introduced through which it is claimed that better colored fatty acids are obtained and the glycerine is free from ash.
The advantages claimed for the Twitchell process as outlined by Joslin[12] are as follows:
1. All the glycerine is separated from the stock before entering the kettle, preventing loss of glycerine in the soap and removing glycerine from spent lye.
2. The liquors contain 15-20 per cent. glycerine whereas spent lyes contain but 3-5 per cent. necessitating less evaporation and consequently being more economical in steam, labor and time.
3. No salt is obtained in the liquors which makes the evaporation cheaper and removes the cause of corrosion of the evaporator; also saves the glycerine retained by the salt.
4. The glycerine liquors are purer and thus the treatment of the lyes is cheaper and simpler and the evaporation less difficult.
5. The glycerine can readily be evaporated to 90 per cent. crude rather than 80 per cent. crude, thus saving drums, labor in handling and freight. The glycerine furthermore receives a higher rating and price, being known as saponification crude which develops no glycols in refining it.
6. The fatty acids obtained by the Twitchell saponifier may be converted into soap by carbonates, thus saving cost in alkali.
7. There is a decrease in the odor of many strong smelling stocks.
8. The glycerine may be obtained from half boiled and cold made soaps as well as soft (potash) soaps.
While the advantages thus outlined are of decided value in the employment of the Twitchell process, the one great disadvantage is that the fatty acids obtained are rather dark in color and are not satisfactorily employed for the making of a soap where whiteness of color is desired.
To carry out the process the previously heated oil or fat to be saponified is run into a lead lined tank. As greases and tallow often contain impurities a preliminary treatment with sulfuric acid is necessary. For a grease 1.25 per cent. of half water and half 66° B. sulfuric acid is the approximate amount. The undiluted 66° B. acid should never be added directly, as the grease would be charred by this. The grease should be agitated by steam after the required percentage of acid, calculated on the weight of the grease, has been added. The wash lye coming off should be 7°-10° B. on a good clean grease or 15°-22° B. on cotton oil or a poor grease. As has been stated the grease is heated before the acid is added or the condensation of the steam necessitates the addition of more acid. After having boiled for 1-2 hours the grease is allowed to settle for 12 hours and run off through a swivel pipe.
After the grease has been washed, as just explained, and settled, it is pumped into a covered wooden tank containing an open brass coil. Some of the second lye from a previous run is usually left in this tank and the grease pumped into this. The amount of this lye should be about one-third to one-half the weight of the grease so that there is about 60 per cent. by weight of grease in the tank after 24 hours boiling. Where occasions arise when there is no second lye about 50 per cent. by weight of distilled water to the amount of grease is run into the tank to replace the lye. The saponifier is then added through a glass or granite ware funnel after the contents of the tank have been brought to a boil. If the boiling is to be continued 48 hours, 1 per cent. of saponifier is added. For 24 hours boiling add 1.5 per cent. The boiling is continued for 24-48 hours allowing 18 inches for boiling room or the grease will boil over.
After boiling has continued the required length of time the mass is settled and the glycerine water is drawn off to the treatment tank. Should a permanent emulsion have formed, due to adding too great an amount of saponifier, a little sulfuric acid (0.1 per cent.-0.3 per cent.) will readily break this. During the time this is being done the space between the grease and the cover on the tank is kept filled with steam as contact with the air darkens the fatty acids.
To the grease remaining in the tank distilled water (condensed water from steam coils) to one-half its volume is added and the boiling continued 12-24 hours. The grease is then settled and the clear grease run off through a swivel pipe. A layer of emulsion usually forms between the clear grease and lye so that it may easily be determined when the grease has all been run off. To prevent discoloration of the fatty acids it is necessary to neutralize the lye with barium carbonate. The amount of this to be added depends upon the percentage of saponifier used. About 1/10 the weight of saponifier is the right amount. The barium carbonate is added through the funnel at the top of the tank mixed with a little water and the lye tested until it is neutral to methyl orange indicator. When the fatty acids are thus treated they will not darken upon exposure to the air when run off.
Fresh grease is now pumped into the lye or water remaining in the tank and the process repeated.
The glycerine water or first lye is run to the treatment tank, the fat skimmed off and neutralized with lime until it shows pink with phenolphthalein, after having been thoroughly boiled with steam. About 0.25 per cent. lime is the proper amount to add. The mixture is then allowed to settle and the supernatant mixture drawn off and run to the glycerine evaporator feed tank. The lime which holds considerable glycerine is filtered and the liquor added to the other. The evaporation is carried out in two stages. The glycerine water is first evaporated to about 60 per cent. glycerol, then dropped into a settling tank to settle out the calcium sulfate. The clear liquor is then evaporated to crude (about 90 per cent. glycerine) and the sediment filtered and also evaporated to crude.
As to the amount of saponifier to use on various stocks, this is best determined by experiment as to how high a percentage gives dark colored fatty acids. For good stock such as clean tallow, prime cottonseed oil, corn oil, cocoanut oil and stock of this kind 0.75 per cent. saponifier is sufficient. For poorer grades of tallow, house grease, poor cottonseed oil, etc., 1 per cent. saponifier is required and for poorer grade greases higher percentages. The percentage of fatty acids developed varies in various stocks, and also varies with the care that the operation is carried out, but is usually between 85 per cent.-95 per cent. Due to the water taken up in the saponification process there is a yield of about 103 pounds of fatty acids and glycerine for 100 pounds of fat.
The Twitchell reagent has undoubtedly caused a decided advance in the saponification of fats and oils and has been of great value to the soap manufacturer, because with a small expenditure it is possible to compete with the much more expensive equipment necessary for autoclave saponification. The drawback, however, has been that the reagent imparted a dark color to the fatty acids obtained, due to decomposition products forming when the reagent is made, and hence is not suitable for use in soaps where whiteness of color is desired.
There have recently been two new reagents introduced which act as catalyzers in splitting fats, just as the Twitchell reagent acts, but the fatty acids produced by the cleavage are of good color. The saponification, furthermore, takes place more rapidly. These are the Pfeilring reagent and Kontact reagent.
The Pfeilring reagent is very similar to the Twitchell reagent, being made from hydrogenated castor oil and naphthalene by sulfonation with concentrated sulfuric acid. It is manufactured in Germany and is being extensively used in that country with good success.
The Kontact or Petroff reagent, discovered by Petroff in Russia, is made from sulfonated mineral oils. Until very recently it has only been manufactured in Europe, but now that it has been found possible to obtain the proper mineral constituent from American petroleum, it is being manufactured in this country, and it is very probable that it will replace the Twitchell reagent because of the advantages derived by using it, as compared to the old Twitchell reagent.
The method and equipment necessary for employing either the Pfeilring or Kontact reagents is exactly the same as in using the Twitchell process.