FOSTER DEE SNELL Foster D. Snell, Inc., New York, N.Y.
I/EC ANNUAL REVIEWS
Syndets and Soaps 1 9 5 7
SVNDET SALES c o n t i n u e
to increase
but not as sharply—this is impossible without eliminating soap from the industrial picture. T h e small increase for 1957, about 8 % tonnagewise, m a y result partly from the disproportionate increase in 1956. Soap, however, decreased about 6 % . T o n n a g e of lower-cost forms went down, higher-cost u p ; actual dollar sales of soap increased. During the past 3 years, soap sales have declined steadily a n d syndet sales have risen. Although total sales for all syndets increased only moderately, liquid products again m a d e large gains— for the first 9 months of 1957, 3 1 % above the same period in 1956. This indicates the popularity of light-duty
liquids for dishwashing, m a n y of which are now packaged in lacquered cans instead of glass to facilitate distribution a n d handling. I n this country, liquid syndets a r e one tenth the total tonnage a n d one sixth the dollar volume of all built syndets. Soap still dominates in only two fields—industrial a n d toilet use. I n dustrially, power laundries consume the greater portion because of price. T h e y buy bulk soap in chip form a n d a d d inexpensive builders, such as sodium metasilicate, which a r e bought separately at bulk chemical prices. M a n y laundries use syndets for silks and woolens but only a few to a larger extent. I t will take a long time for syndets to crack this market, b u t it could be done with a n agent nearly
Sales of Soaps and Syndets Millions of Pounds 0 500
1000
150G
2000
2500
3000
From the Association o f American S o a p a n d G l y c e r i n e Producers, Inc.
SOAP
m m m m
HM*l?
EEEÏE ΓΠΣΩ SOAP
6 5Ο
œsm 5EE5E ΚΠΕ SOAP VALUS
ΙΟ Ο
ggnâB Ε71ΤΤΠ
100 0 Millions of Dollars
200
300
CED
500
500
cheap enough to compete with tallow soap. But in toilet soap a n d household bars, price is not so important. I n 1957, the 10,000,000 pounds of Dove, Zest, a n d Vel Beauty Bar sold in 1956 will surely be 3 times greater. All a r e more or less in national distribution now. Zest contains much soap, Dove a little, and Vel Beauty Bar none. Economically, these bars m e a n m u c h to the soap industry. I n 1956, 3 8 % of the tonnage a n d 5 0 % of the dollar value of soap was in b a r form. Therefore, it is n o surprise that soap companies which did n o t also sell syndets a r e folding. T h e major examples have been owned by packers—not A r m o u r of course, because of Dial. T h e r e fore, more soapers a r e expected to fail. T h e field for syndets is much larger t h a n that for soap could have been. I t includes petroleum processing a n d secondary recovery, fluffing-up of concrete, textile operations, fruit washing, metal cleaning a n d cutting, cosmetic manufacture, a n d agricultural sprays a n d fertilizers. I n a t r e a t m e n t especially valuable in making p a r c h m e n t paper, syndets cut the processing time for purifying sulfate or kraft cellulose and bleached sulfite cellulose. I n cleaning ships' tanks, another new use, soap does not stand u p in service b u t dodecylbenzenesulfonate does. Stability in the presence of calcium a n d magnesium opens u p new uses almost daily. Interest in ultrasonics as â competitor of syndets a n d soap h a s abated, b u t last year, two appliance manufacturers were working feverishly. N e w designs in spin-dryers m a y improve the mechanical detergency of washers. Mechanical a n d chemical detergency complement each other. Benzene, propylene tetramer, a n d sulfuric acid continue as the principal r a w materials of anionics. Benzene has been stabilized at 36 cents a gallon for the last 2 years. About VOL. 50, NO. 1 ·
JANUARY 1958
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the middle of 1957, however, dodecyl benzene went u p half a cent a pound over the m i n i m u m price of 12 cents at the beginning of the year. Seventeen petroleum companies are now producing benzene, but this furnishes only a third of the nation's requirements. Coke ovens still furnish the major portion (about 60%) and 7 to 8 % is imported. About nine tenths of our imports come from the Soviet Union or Soviet-dominated countries, but five years ago, practically all were from non-Soviet sources. A few domestic petroleum companies plan to expand benzene production, and two others expect to begin production in 1958. Continuous processes for sulfonating dodecylbenzene and for sulfating long-chain alcohols continue in both development and commercial stages. Five continuous sulfonation processes have been described, and two plants are manufacturing stabilized sulfur trioxide. Foreign plants are now producing sulfonates by continuous methods—Canada, Brazil, and J a p a n each produces 5,000,000 to 7,000,000 pounds a year of sulfonated hydrocarbons. T h e Japanese product is a syndet, the others are lubricating-oil additives. T h e growing d e m a n d for liquid detergents is causing dodecylbenzene suppliers to take a m u c h closer look at quality. I n light-duty liquid detergents it is desirable to have less than 2 % of inorganic salt, based on the sulfonate present. W i t h 1 0 0 . 8 % or 1 0 5 % sulfuric acid, the m i n i m u m salt content based on active ingredient is 9 to 1 0 % after removal of excess sulfuric acid by alcohol extraction. This desalting step can be eliminated by employing sulfur trioxide as the sulfonating agent. T h e light-colored products that can be produced by using stabilized sulfur trioxide now compel producers to improve correspondingly the purity of dodecylbenzene for the liquid detergent manufacturers. O n e petroleum company recently spent several million dollars for this purpose. Heavy-duty liquids for use in washing machines will supplant Tide-like products if they can match the granules in performance and cost with a modest p r e m i u m for convenience. But thus far, costs are m u c h higher—potassium phosphates cost nearly 5 0 % more t h a n sodium phosphates. Although speculation is high on the latest heavy-duty 42 A
liquid detergents for the household, only Lever Brothers with its heavyduty sudsing Wisk and low sudsing H u m , and A r m o u r with a reformulated Gee, were on grocery shelves. However, Procter & G a m b l e was test-marketing its heavy-duty liquid Biz this past summer. No comparable moves were m a d e by ColgatePalmolive, and Lever's Wisk was scheduled to be the first liquid heavy-duty detergent to r e a c h national distribution by mid or late 1957. Opinion is that heavy-duty liquids will not grow m u c h from their present level. I n late 1956, syndet manufacturers' inventories of polyphosphates were depleted by the large syndet sales, but in early 1957 they were brought back to normal. This was a t e m p o r a r y boost for phosphate producers since m a n y syndets are nearly 5 0 % phosphate. Optical brighteners have grown to a $15,000,000 market. Geigy and Ciba each have a new concentrated fluorescent brightener said to give brilliant-white effects on D a c r o n and also excellent results on acetate, Arnel, nylon, rayon, a n d cotton. While carboxymethylcellulose has been used for some years to promote soil-dispersing power and to minimize redeposition of soil, polyethylene glycols having molecular weights preferably from 6000 to 7500 a p p e a r
promising. Also, sodium or other alkali or alkaline-earth metal mahogany sulfonates are claimed to be suitable builders to improve the surface activity of dodecyl benzene sulfonate. Nonionics
A new chapter in the history of All was written. Monsanto transferred it as a spin-off to Lever Brothers. O n e factor causing a tight market for refined tall oil in late 1957 is that tall oil-ethylene oxide surfactants are the lowest cost nonionics for low-sudsing detergents. Users of refined unsaturated fatty acids who see tall oil as a cheaper source t h a n cottonseed or soya b e a n have a d d e d their clamor for tall oil to that of nonionic producers such as Monsanto, A d a s Powder, Blockson Chemical Division of Olin Mathieson, a n d Armour, who are already suppliers of tall oilethylene oxide condensates. T h e squeeze on refined tall oil will probably persist through p a r t of 1958 until costly refining equipment is installed and difficult refining opera- « tions are mastered. Alkylphenol-ethylene oxide adducts occupy a large segment of the ethylene oxide-based surfactant m a r ket, a n d in 1957, the most c o m m o n alkylphenols used in making these were octylphenol, nonylphenol, dodecylphenol, dinonylphenol, and
High pressure autoclaves like these are used at Procter & Gamble's Miami Valley laboratories to prepare on a small scale, raw materials from which synthetic detergents may ultimately be made on a factory scale
INDUSTRIAL AND ENGINEERING CHEMISTRY
neas of the h u m a n eye have been preserved as long as 2 years by dehydration in glycerol and storage in vacuum-sealed tubes at room temperature. Miscellaneous
Chilling rolls are used to make thin strips of Dove from the molten mix p r e p a r a t o r y to forming bars
pentadecylphenol. T h e alkylphenol nonionics a r e heading for higher sales in the light- a n d heavy-duty liquid detergents a n d in low-foaming l a u n d r y granules. A new plant of the General Aniline and Film Corp. is now on stream at Calvert City, Ky., producing alkylphenols and nonionics based on them. Soap
Prices for raw materials were stable. I n 1932, a processing tax of 3 cents a pound was applied on coconut oil to protect domestic fat producers. In 1957, however, Congress decided that it was more imp o r t a n t to t r a d e with the Philippines t h a n to protect our great tallow surplus. Consequently, the tax went off October 1. T h e tenth paper in a series on potential active agents from animal fats, originating at the Eastern R e gional Research Laboratory, has recently appeared. Glycerol
Continued increase in syntheticglycerol production is planned even though the a n n u a l capacity for one of its strongest competitors, pentaerythritol, is 93,000,000 pounds. Dow, whose process begins with propylene and chlorine, is building at Freeport, Tex., a second syntheticglycerol unit having a capacity of 36,000,000 pounds, which will double its capacity. Shell Chemical con-
tinues production at its two plants on about the same scale as last year. Olin Mathicson was granted a fast tax write-off certificate for construction of a $10,000,000 plant at Doe R u n , Ky. T h e Scientific Design Co. has obtained a license from Imperial Chemical Industries for making fermentation glycerol which, it is reported, can compete with the synthetic product if blackstrap molasses is priced at $25 to $30 a ton. M e a n while, despite rumors, no glycerol has come from the sorbitol process, and neither has Shell's peroxide process, reputedly the future low-cost method, gone into operation. Prices of refined glycerol, both n a t u r a l and synthetic, remained the same as a year ago, but crude glycerol increased a cent a pound. Presumedly, like the general pattern here, production abroad has decreased in those countries where syndets are making inroads into soap sales. Imports of crude have decreased about 6 % and refiners here face increased costs, particularly of labor. In resin coatings, as a h u m e c t a n t in tobacco, and as a plasticizer in cellophane, glycerol continues to find large-scale use. As a mine explosive, however, it is being replaced in p a r t by compositions such as those based on a m m o n i u m nitrate, organic nitrates, and liquid oxygen. M a n y new applications continue to be found for glycerol, although some are necessarily small-scale—e.g., cor-
According to the latest figures, Belgium leads the world in a n n u a l per capita consumption of syndets and soap—about 28.3 pounds. This does not mean that the Belgians are cleaner people but r a t h e r that use of hard water is widespread. Incidentally, Procter & G a m b l e has a new $2,000,000 plant in Malines, Belgium, for production of syndets. T h e United States is second in a n n u a l per capita consumption of soap a n d syndets, with 27.8 pounds used per person annually. Switzerland is third and the United Kingdom, having extensive soft water sources, is fourth. Scouring powders all contain syndets r a t h e r than soap so as not to be killed by alkaline-earth ions. Some of them are the proving ground for what m a y become the leading domestic dry bleach—i.e., either dichlorocyanuric acid, or its more soluble sodium salt. Although dry bleaches have had a miniscule market in the U n i t e d States, both the Westvaco division of Food M a c h i n e r y a n d Chemical Corp. and Monsanto a r e building chlorocyanuric acid plants of multimillion pounds capacity. Previously, dry bleaches in this country were based on calcium hypochlorite-sodium tripolyphosphate mixtures or on dimethyldichlorhydantoin, introduced by W y a n d o t t e Chemical, with which chlorocyanurics are expected to be strongly competitive. Syndets are still often blamed for foaming problems in sewage treatment. Studies indicate that foaming or objectionable taste and odor are probably caused by polypropylene benzenesulfonates, because of their resistance to biological degradation. Complex phosphates used as builders, or orthophosphate formed during reversion, increase coagulant requirements for water clarification. O n e of the newer uses of surfactants is in making clear, bactericidal ice. An amphoteric surfactant is a d d e d to water frozen for use in food preservation—e.g., fish. Such surfactants inhibit growth of harmful bacteria a n d constitute no t h r e a t to health. VOL. 50, NO. 1
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