INDUSTRY & BUSINESS
Makers plan new detergent formulas Phosphates being phased out as detergent base; enzymes and linear alkylbenzene sulfonates are also under fire For the moment, the roar about phosphates in detergents has subsided to a mutter, and industry and research organizations are getting on with the job of finding replacements. The merits and suspected ecological faults of phosphate-built detergents have already been argued to a fare-thee-well. The argument continues, and agreement among ecologists, politicians, producers, and the like, is nowhere in sight. Regardless of the merits of the case, the question is probably no longer whether the phosphate content of detergents will be reduced. Replacement, at least in part, is inevitable. The questions now are by what, by how much, and by when. To the chemical industry, it's also a question of how to make a virtue of necessity. Phosphates or no, U.S. consumers are still going to buy several billion pounds a year of something to wash their clothes with, and they'll probably continue to buy it from the same people they've been buying it from all along. The big detergent makers are likely going to get their share, even if they have to scratch harder for it for a while. Among other segments of the chemical industry, however, there promises to be much jockeying for a piece of the action. The stakes are high— about $1.5 billion a year—and the competition will be sharp. Favorite. At present, the sodium salt of nitrilotriacetic acid (NTA) is the odds-on favorite to replace polyphosphates. NTA comes close to being the detergent industry's equivalent of the only game in town. Procter & Gamble, for instance, has committed itself to replacing 25% of the phosphates in its detergents with NTA. P&G says that it has already made the substitution in 33% of its packaged detergent volume—corresponding to a 70 million pound annual reduction in phosphates—and expects to have made another 300 million pound-per-year reduction by January 1972. Lever Bros, says that it has made commitments to "purchase substantial quantities of NTA" but gives no specifics on phosphate removal except to note that its liquid heavy-duty laundry detergent "all" is now phosphate-free. 18 C&EN AUG. 17, 1970
Several smaller manufacturers in the U.S. and Canada are also using NTA, at least to the extent that they can get it. Rosy. Increasing interest in NTA all adds up to a rosy outlook for NTA makers. W. R. Grace's Hampshire Chemical division, pioneer in domestic production of NTA, has tripled its
original 20 million pound-per-year capacity at Nashua, N.H., and has additional expansions under way. Monsanto, currently the largest NTA producer, is doubling capacity of its 75 million pound-per-year plant at Chocolate Bayou, Tex., and is building a 200 million pound-per-year facility at Texas City.
Soap: f
some companies' answer
Johnny Standley s old song about Grandma's lye soap (allowing how it was good for everything in the home and how that its secret was in the scrubbing, for it didn't lather or foam) admittedly overstates the case. Soap, under proper circumstances, is an excellent cleansing agent What's more, it's readily biodegradable, relatively nontoxic, and needs no added antideposition agents. Despite the ascendancy of synthetic detergents, soap is still big business: more than 800 million pounds per year, worth more than $300 million. Soap still accounts for about 15% by weight of the total soap /synthetic detergent market, almost 25% in terms of money. In one major product line, bath and toilet bars, soap has so far resisted major incursions by the synthetics. Even if soap leaves a ring around the bathtub, most people still seem to prefer the "feel" of toilet soap to thai of the syndet bars. Soap's virtues notwithstanding, there are elements of truth in the song. Grandma probably had hard water. In hard water, soap doesn't foam until enough has been added to soften the water by precipitating the calcium, magnesium, and other "hardness" ions. The precipitate is a gummy curd of insoluble soap. Only a minor nuisance in the bathtub, this curd is a major problem in the laundry. It forms a dulling film on clothing and can clog the washing machine. There are ways to get around this difficulty; it is technologically possible to get excellent results doing the laundry with soap. As a practical matter, environmental considerations aside, it is much easier to get equally good results with synthetic detergents. That's probably the main reason why syndets, with less than 10% of the market in 1948, overtook soap in 1953 and why they have been increasing their lead ever since. Of course, it's no longer possible to set environmental considerations aside. Makers and users of phosphate-based detergents are accused of crimes against nature, and many voices are calling for the elimination of phosphates from cleaning products. Some people are seriously advocating a return to soap as the solution to the "phosphate problem." At least two companies—Church & Dwight, a producer of baking soda (sodium bicarbonate), and Culligan, a soft water equipment maker—have seen in soap a way to board the antiphosphate bandwagon and use it to boost demand for what they sell. Church & Dwight has been running an advertising campaign aimed at homemakers who are concerned about the environment. For one thing, the firm reminds housewives that baking soda is good for more than baking. If it isn't "good for everything in the home," it comes close, according to Church & Dwight. The company is distributing colorful cardboard "Dial to Easier Living" guides telling how to use sodium bicarbonate for more than 50 different household tasks, including scouring pots and pans, cleaning false teeth, and deodorizing kitty's litter box. The guides, like the ads, emphasize that Arm & Hammer baking soda, unlike conventional household cleaners and scourers, "contains no phosphates." Church & Dwight stresses that its other main product, sodium carbonate, can also help slow down eutrophication.
Students advise shoppers in Evanston, III., about evils of phosphates in detergents
to phosphate-containing detergents "At last," one ad begins, "something you can do about water pollution." By switching from phosphate-containing detergents to soap and sal soda, "you will be helping save our nation's waters because phosphates promote algae pollution— killing fish, stagnating water, and turning lakes into swamps." Having thus appealed to nobler instincts, the ad gets down to specifics: "Just add y 3 cup washing soda as machine is filling. Add clothes to washer and then add laundry soap. Use i y 2 cups for front loading machines and V/3 cups for top loaders. In hard water, add V* cup washing soda to first rinse. The results: no polluting phosphates, plenty of white, bright clothes." Fair enough. Soap is a very good cleaning agent in soft water. Sodium carbonate is a good water softener. Although it works by precipitating the "hardness" ions, rather than by sequestering them (as do the complex phosphates), the precipitate is a granular one that settles harmlessly to the bottom of the washing machine, not a floating curd that gums up the clothes. The soap/sal soda combination was widely used before synthetic detergents and phosphates came along. However, that was before the prevalence of automatic washing machines. It remains to be seen whether very many people nowadays will be willing to go to all the trouble—especially waiting around to toss the extra a A cup into the rinse (necessary in hard water; otherwise, the soap remaining in the wet clothing, even after spin-extraction, would still form curds). The Culligan approach avoids that particular shortcoming. The Northbrook, III., firm is now marketing a "phosphate-free" laundry soap as a sideline to its main business of "water quality improvement." Culligan also points out that soap is an excellent cleaner—in soft water—but that four out of five homes in the U.S. and Canada have hard water. Culligan offers home-installed water-softening equipment. In an offhand slap at Church & Dwight and other makers of packaged water-softening products, Culligan adds that, "softening water before it is used eliminates hard water problems not only in the washing cycle, but also in rinsing." Hard water was only one of the reasons, however, that the soap industry went all-out to develop synthetic detergents. Another, equally compelling reason was the increasing competition with the food and feed industries for a limited supply of natural fats and oils. William C. Krumrei of Procter & Gamble points out that current annual tallow production is about 5 billion pounds per year. To produce soap to satisfy the needs of this country would require more than half this supply, thereby providing a serious interruption in the food supply of humans and animals, he asserts. One may question the completeness of Mr. Krumrei's statistics—tallow is but one of many natural fats and oils—but as a generalization his point is well taken. With most of the world more concerned about malnutrition than about eutrophication, solving the "phosphate problem" at the expense of the world's food supply is not going to be acceptable. Whether phosphates disappear or not from detergents, it's unlikely that soap will rise again.
It's questionable how long W. R. Grace and Monsanto will be able to hold on to their NTA oligopoly. Stauffer, Ethyl Corp., and Standard Oil Co. (Ohio), all have actual or potential NTA processes. Stauffer and Ethyl Corp., as leading producers of detergent phosphate and tetraethyllead, respectively, are probably eager for new markets; however, none of the three has taken the NTA plunge as yet. Chain reaction. The expansions in NTA capacity have triggered a chain reaction: NTA breeds demand for hydrogen cyanide, which calls in turn for formaldehyde, most of which is made by oxidation of methanol. For example, Monsanto is adding 450 million pounds per year of formaldehyde, 150 million at Chocolate Bayou and 300 million at Texas City. Other big formaldehyde producers are also expanding. Acceptance of NTA is not unanimous. P&G is convinced, as a result of its own extensive testing, that NTA is safe "for use at the levels contemplated." Others are not so sure. Colgate-Palmolive is holding back on large-scale substitution of NTA until the compound is "proven safe." And even NTA's biggest boosters concede that, safety aside, NTA probably will still not be satisfactory as a total replacement for phosphates. Above the 50% level, there are major difficulties both in production and in use, and remedies for these difficulties have not been found to date. Polyelectrolytes have also been advocated as detergent builders. P&G says it's tried polyelectrolytes and found them lacking; when they're effective as builders, they're not biodegradable, and vice versa. Some detergent scientists disagree. Dr. I. A. Eldib, of Eldib Engineering and Research, Newark, N.J., says that he has developed successful liquid detergents built with biodegradable polyelectrolytes, as well as a powdered detergent packaged to be sold in vending machines in laundromats. Hadco Corp. has reformulated detergent products to include its own polyelectrolyte builder system, which, the Cleveland firm maintains, is nontoxic, biodegradable, and compatible with all surfactants. AUG. 17, 1970 C&EN 19
INDUSTRY THIS WEEK IN BRIEF
Corporate Spencer Kellogg division of Textron, Inc., has acquired assets of KellyPickering Chemical Corp. and Metal Organics, Inc., San Carlos, Calif. Companies will continue to operate under their former management as the Kelly-Pickering Chemicals department of Spencer Kellogg. Kelly-Pickering markets specialty resins, catalytic driers, and other chemical products. United States Steel Corp. has sold the industrial and marine coatings business of its USS Chemicals division to Porter Paint Co., Louisville, Ky. Business includes products sold under Tarset, Insul-Mastic, Pitt Chem, and Tarmastic trademarks as well as certain basic patents in coal tar-epoxy and marine fields. No manufacturing facilities are included.
Marketing The Fertilizer Institute's Fertilizer Index released for fiscal year just ended shows 1969-70 production up 7 % and domestic disappearance up 6 % . Year-end inventories were down 1 4 % for all 19 fertilizer products as a group, reflecting producer efforts to correct long-existing imbalances in supply and demand.
Industrial
Relations
AFL-CIO has demanded immediate consideration and passage of the Daniels bill on occupational safety and health (C&EN, April 13, page 22). The AFL-CIO executive council reaffirmed its wholehearted support of the bill at a recent meeting. Allied Chemical has eliminated jobs of 90 employees at its fiber division's technical center in Chesterfield, Va., which is being restructured along "functional lines." Some 50 of jobs eliminated were salaried positions involving technical and other professional personnel.
International Gulf Oil is planning uranium complex on Wollaston Lake, Saskatchewan. Mining complex will cost up to $50 20 C&EN AUG. 17, 1970
million, if Canadian government approves plans on completion of current engineering studies. Venture is 9 0 % owned by Gulf subsidiary Gulf Minerals Resources Co. and 1 0 % by Gulf Oil Canada, Ltd. Portion of any profits would go to New Continental Oil Co. of Canada and others who sold mineral rights to Gulf. Sumitomo Chemical Co., Japan, raised both sales and net income by 2 4 % during first-half 1970 over same period 1969, earning $8.4 million on sales of $305.1 million. Firm's fastest growing market was fine chemicals, with sales up 3 1 % from last year; industrial chemicals—accounting for a quarter of Sumitomo's business—were up 2 2 % . Firm predicts 1970 sales will pass $625 million. Conoco Chemicals division of Continental Oil Co. is considering site near Zeebrugge, Belgium, for construction of oil-soluble sulfonates plant with 50 million pound-per-year capacity. Plant, expected on stream in 1972, will produce calcium and magnesium oil-soluble sulfonates and rust-preventive concentrates. Plant will be operated by Conoco Chemicals Europe, S.A., headquartered in Brussels, and will be first wholly owned Conoco Chemicals plant outside the U.S. Solvay & Cie has constructed chloromethanes plant at its works at Tavaux, France. Unit, scheduled to start up in 1971, will be largest of Solvay's chloromethane plants and will produce methyl chloride, methylene chloride, chloroform, and carbon tetrachloride. Speichim, French engineering firm in Paris, has been awarded $4.6 million contract by Spain's Fosforico Espanol, S.A., for engineering and construction of 100,000 metric-ton-peryear phosphoric acid plant at Huelva, Spain. Nippon Petroleum Refining Co., Japan, will build unit to recover sulfur contained in off-gases of its Negishi refinery. Unit will use France's Institut Francais du Petrole process and will be engineered by Mitsubishi Heavy Industries.
Resolving the detergent controversy to everyone's satisfaction may entail more than just switching builders. Enzymes are under fire, because of questions about biodegradability and toxicity. Linear alkylbenzene sulfonates (LAS) are being sniped at because they're only "biodegradably soft," not completely biodegradable. The final solution, if there is one, may be more general use of surfactants already in existence but limited to specialized applications, or it may require the development of completely new surfactants. Surfactant. Among those examining the new-surfactant route is Illinois Institute of Technology Research Institute, under contract with the Federal Water Quality Administration. Dr. Warner Linfield, director of the IITRI project, reveals that he and his colleagues are working on a number of new surfactants that function well in the absence of phosphate builders but using other builders, mostly inorganic salts, including sodium carbonate and sodium chloride. Emphasizing that the IITRI project is being done on a laboratory scale, not with finished products, Dr. Linfield declines to comment on the composition of the new surfactants or formulations at this stage of the institute's project. Major detergent makers are just as reticent about details of their research, but they are apparently busy. One industry official notes that "So many people have been working on phosphate removal that it's been very difficult to get enough standard test fabric." One firm that has been doing some talking is DeSoto, Inc., Des Plaines, 111. DeSoto has developed a new detergent to be marketed primarily by Sears, Roebuck & Co. According to DeSoto's technical director Robert Cooper, the product contains "no phosphate, no NTA, and no other materials believed to be pollutants." It does contain a "nonionic, completely biodegradable" surfactant and an inorganic base including, but not limited to, sodium carbonate and sodium silicate. DeSoto's new detergent was originally scheduled for introduction in mid-August, but Oct. 1 is now the target date. "Developing the manufacturing process has been moderately difficult," Mr. Cooper comments. Nonionics. Dr. Eldib is also boosting nonionics. In particular, he sees a glowing future for nonionic secondary alcohol surfactants. The nonionic market has mushroomed to $140 million per year since Union Carbide brought out Tergitol "S" in 1966, Dr. Eldib says, and the market is expected to reach $160 million by 1973. He contends that "conversion of nor-
mal paraffins to secondary alcohols and subsequently to nonionic surfactants could lead to profit growths now being ignored in most quarters of the industiy. Another not-so-new class of surfactants receiving renewed attention is the alpha olefin sulfonates. One firm that has been fairly active in the field is Stepan Chemical Co., Northbrook, 111. Stepan uses alpha olefin sulfonates for cosmetics and other specialties. Edward Knaggs, technical director of Stepan's industrial chemicals division, says that olefin sulfonates are at least close to LAS in terms of detergency, and, he adds, they also feel milder to the skin. However, he notes, increased use of olefin sulfonates as general-purpose or laundry detergents will depend mainly on availability and economics—both functions of the basic olefin processes. Chevron Chemical, a subsidiary of Standard Oil Co. of California, a major producer of olefins, has done some promotion of olefin-based detergents but, according to one spokesman, the company is not presently pursuing the market. The reason may be that the olefins that yield the best surfactants are those in the C 1 4 to C ] 8 range. With Chevron's cracked-wax process, the range tends to be broader. Coloration can also be a problem with the cracked-wax olefins. Gulf Oil, on the other hand, is actively promoting its alpha olefins for sulfonation, emphasizing their biodegradability and good performance in hard water. Gulf uses a Ziegler condensation process at its 100 millionplus pound-per-year plant at Cedar Bayou, Tex. With Ziegler olefins, coloration is less of a problem, and carbon-chain length control is also easier. Ethyl Corp. will also be a factor to reckon with when the firm's 250 million pound-per-year olefin plant, now under construction at Houston, goes on stream early next year. The company won't confirm or deny it, but some sources say the new plant will use a "modified Ziegler process" that gives exceptionally good control of carbon chain length, with resulting economic advantage in detergent use. Cheaper. It's too early to count the cracked-wax olefins out for good, however. They're usually cheaper, and Procter & Gamble has developed a method to reduce color formation by pretreating the olefins with a low concentration of sulfur trioxide and then removing color bodies with an adsorbent before proceeding with the conventional sulfonation process. P&G says that the process is applicable to all alpha olefins but particularly to those derived from cracked petroleum waxes.
And that's only part of the story. It's unique from the ground up—from concept to coverage. It answers scores of questions no other research tool can. The kind of questions you need answered. Only Science Citation Index (SCI®) can tell you quickly, easily, if your idea is original or if someone else has been there first. Whether a theory's been confirmed—or rejected. If a product's been clinically evaluated, or a patent's been cited. What other companies, institutions or researchers are working in a particular field. And what they're working on. If a product's been applied to a new field. What potential uses there are for a new synthesis. Or whether a development has been extended or a method improved. No other information system will answer even a few of these questions. SCI subject coverage matches its utility. It indexes completely over two thousand scientific and technical journals. Every article, review, letter, correction.
Four million individual entries are contained in the latest annual issue. All of them derived from the literature of the past 12 months. And you get all this quarterly, cumulated annually. Weekly up-dating service is also available through ISPs unique ASCA® system. In short, SCI is a must for information centers and corporate libraries in high technology organizations interested in cutting research time and costs. Want even more convincing reasons? Just return the coupon. A few of the many organizations subscribing to SCI North American Rockwell The Rand Corp. Varian Associates American Cyanamid Co. Chevron Research Co. Abbott Labs. Lincoln Labs.-M.I.T. Dow Chemical Co. Upjohn Co. Colgate-Palmolive Co.
|
RCA SquibbInstitute of Medical Research Sandia Corp. Bell Labs.
IBM R. J. Reynolds Co. McNeil Labs. Smith, Kline & French Labs. Westinghouse Electric Corp.
© 1970 ISI® "J D«f ^5 aU® INSTITUTE FOR SCIENTIFIC INFORMATION I 325 Chestnut Street, Philadelphia, Pennsylvania 19106, USA Telephone: (215) 923-3300. Telex: 84-5305. Cable: SCINF0 132 High Street, Uxbridge, Middlesex, UK Other offices in Washington, Ottawa, Paris, Tokyo
I i I I
Please send me full information on Science Citation Index®. NAME TITLE COMPANY/DIVISION ADDRESS
Science Citation Index!
CITY
Canynuaffoidtobe without it?
STATE
ZIP
COUNTRY .
TELEPHONE
The best Mend an R&D man
ever had. Science Citation Index® takes the tedium out o f literature searches. Leaves more time for creative thinking. N
>^\
EPTATION
SCIENCE
CITATION INDEX
.—..-«#
iSSL
INDEX
•M AUG.
17, 1970 C & E N
21
