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Biodegradability...the industry's need ECONOMICAL SOFT DETERGENTS WITH GOOD PERFORMANCE Accomplishing this vital change requires In protttably solving the problems gena combination of good products and erated by steadily increasing pollution good economics. Conoco Petrochemi—in ground water, streams, and r i v e r s cals, the industry's only supplier of an surfactant manufacturers are faced with entire line of major components for biothe necessity of developing surfactant degradable surfactants, can provide full formulations with: biodegradability. Conoco can tailor the Virtually complete biodegradability performance of its materials to each Performance at least equivalent to detergent-maker's individual needs. And present materials in processability Conoco surfactants equal or surpass and end use popular hard compounds in processing C o s t very c l o s e to c o n v e n t i o n a l and end-product performance. compounds
SIGNIFICANCE OF BIOGRADABILITY
New NALKYLENE plant at Lake Charles, La.
Foam from the faucet and suds in the stream pose definite problems. Such persistent froth results largely from the biological stability of conventional synthetic detergent materials. The significent value of soft detergents lies in the ability of natural bacterial action to break down the syndet molecules completely and quickly. Detergent people realize that biodegradability, per se, is usually a relative
t h i n g . C o n s e q u e n t l y , industry definitions vary with t e s t i n g p r o c e d u r e s . . . a n d p e H haps s o m e t i m e s with c o m p e t i t i v e pres-j sures, t o o . D e t e r g e n t researchers e m p l o y s e v e r a | analytical a p p r o a c h e s t o d e t e r m i n e dej g r e e of b i o d e g r a d a t i o n for syndets. Ir' t h e industry's t h r e e most w i d e l y usee tests, C o n o c o ' s straight-chain surfac-j tants show essentially c o m p l e t e biode-j gradability in minimum t i m e .
Activated Sludge Laboratory activated-sludge testing simulates conditions in large-scale sewagedisposal operations. Both continuous (dynamic) and batch (static) methods utilize sludge from waste-disposal plants, as the bacterial culture. The batch procedure, sometimes termed semi-continuous or fill and draw, has gained wide acceptance because it requires only simple and inexpensive equipment even though it offers limited throughput and does not as accurately duplicate actual sewage-plant conditions. In this test, the detergent sample is added to water, containing a synthetic nutrient medium and activated sludge,
in a vertical cylindrical chamber. A i r b u b b l i n g t h r o u g h the liquid agitates t h e mixture. A f t e r a 23-hour test p e r i o d , t h e air is t u r n e d off t o allow t h e sludge t o settle. The supernatant liquid is then s a m p l e d and analyzed. Conoco's biodegradable detergents average 95 t o 100% d e g r a d a t i o n over a weekly series of t h e s e one-day tests. These results c o r r e l a t e with b i o d e g r a d ability d a t a f r o m the unique, continuous a c t i v a t e d - s l u d g e s y s t e m in C o n o c o ' s Ponca City, O k l a h o m a , research center. This dynamic laboratory unit closely simulates c o n d i t i o n s f o u n d in f u l l - s c a l e s e w a g e - d i s p o s a l plants.
River Die-Away River water is added to detergent solution sample in a clean glass jar. Covered with a loose top, the liquid incubates at rest in the dark. Activating a magnetic stirrer for 1 minute gives adequate mixing before periodic sampling. Conoco
normally runs this t e s t 20 t o 30 days t o d e t e r m i n e t h e d e g r e e of b i o d e g r a d a b i l ity of various surfactant materials. In general, soft d e t e r g e n t s achieve essentially c o m p l e t e d e g r a d a t i o n in 5 t o 20 days under t h e s e c o n d i t i o n s .
Shake Flask After surfactant solution is measured into a shake flask, the sample is sterilized in an autoclave, cooled, and inoculated with an adapted,72-hour-old,mixed microbial culture. Loosely capped after
a d d i t i o n of environmental m e d i u m , t h e liquid incubates at 25°C d u r i n g c o n t i n uous a g i t a t i o n on a rotary shaker. B i o degradable detergents generally take 2 t o 5 days t o d e g r a d e in this test.
ANALYTICAL PROCEDURES
AutoAnalyzer system for detergent determinations
Kesidual-surtactant analysis lends itselT to either manual or automated analytical procedures. The best of today's automated analytical systems provides high accuracy and prodigious throughput as well. The trace quantities of active detergent components present in treated samples (20 ppm down to less than 0.5 ppm) have required the development of sensitive and reproducible techniques.
Conoco's chemists and microbiologists use standard methylene-blue colorimetry for determining anionic compounds. For nonionics, a special cobaltothiocyanate colorimetric procedure yields uniformly accurate results. Upon request, Conoco will gladly furnish detailed information on its tests and analytical techniques for determining detergent biodegradability.
Biodegradahiiit.Coiioco s response LEADERSHIP IN TECHNOLOGY
BRANCH-CHAIN NONYLPHENOL N.I.
STRAIGHT-CHAIN NONYLPHENOL N.I.
Pioneering efforts in the field of biodegradability have established firm foundations to support Conoco's leading position as the world's #1 supplier of soft surfactants and intermediates: Cooperation from the beginning with the Soap &. Detergent Association's biodegradability-research program Utilization of new practical procedures to test the biodégradation of synthetic detergents, such as Conoco's contin-
uous activated-sludge system Development of improved analytical techniques to assure accurate determinations of extremely low surfactant levels, such as the colorimetric cobaltothiocyanate method for nonionics. First deliveries of production quantities of linear intermediates—alcohols, ethoxylates, alkylates, sulfonic acids, and slurries—for commercial development of soft detergents.
COMPLETE LINE OF BIODEGRADABLE INTERMEDIATES
Shake-flask data
As early as 1952, Continental Oil was formulating plans to provide biodegradable materials for detergent manufacture. Now, some$30-million later, Conoco Petrochemicals is the only commercial manufacturer to produce the complete spectrum of "biologically soft" surfactants and i n t e r m e d i a t e s : primary straight-chain alcohols, their ethoxylated derivatives, linear alkylbenzene, and straight-chain sulfonic acids and
slurries. These materials lead to fully biodegradable anionic and nonionic detergent formulations of every t y p e heavy-duty or light-duty, low-foaming or high-foaming, liquid or solid. Formulations containing Conoco's full line of biodegradable surfactants equal or surpass conventional d e t e r g e n t s composed of hard, branch-chain materials—in foam stability, detergency, and solubility.
MAJOR RAW MATERIALS
ALFOL® Alcohols A complete range of ALFOL primary straight-chain alcohols provides a start for high-quality alcohol sulfates and for further reaction to make other surfactants of all three basic types: anionics (ether sulfates), nonionics (ethoxylates), and cationics (quaternary ammonium compounds). Present production at Conoco's 100-
million-pound-per-year ALFOL alcohol plant at Lake Charles, La., offers stable supplies of these superior fatty alcohols ranging from C* to C 2 0 in chain length. Versatility of Conoco's synthetic process allows optimum blending of different chain lengths for the best combination of performance and economy in surfactant use.
ALFONIC* Ethoxylates
Geneotogy of Biodegradability
Besides marketing ALFOL alcohols as nonionics in heavy-duty low-foaming detergent intermediates, Conoco Petroformulations. chemicals combines these alcohols with Conoco's low-mole ethoxylates— its own ethylene oxide to form soft ethALFONIC "Series 4" materials - react oxylates. Ethoxylation to a high-mole conveniently even with SOj, as well as EtO level yields ALFONIC "Series 6" with all commonly used sulfating agents, products, nonionic surfactants with an to make straight-chain ether sulfates. These superior foamers displace nonexcellent balance of performance prope r t i e s ( d e t e r g e n c y , s o l u b i l i t y , f o a m , biodegradable alkylphenol ether sulfates to give better performance as well characteristics). Also, these high-mole as full biodegradability. adducts replace hard alkylphenol
NALKYLENE ® Detergent Alkylate
CARBON-CHAIN LENGTH Conoco "Isodet" chart
Conoco Petrochemicals' new soft linear alkylate gives Conoco the industry's only complete line of detergents and intermediates, and forms the cornerstone of biodegradability on a national commercial scale. Over $7-million worth of new f a c i l i t i e s at Lake C h a r l e s and at Baltimore means that all hard detergents based on conventional ABS can now be reformulated to provide fully
biodegradable products. Sulfonation of Conoco's NALKYLENE products, using conventional techniques in conventional equipment, produces soft sulfonic acids and slurries. Readily adaptable to present-day detergent formulations, these materials can also generate entirely new formulations to meet the industry's increasingly severe performance standards.
TAILOR-MADE PRODUCTION Through imaginative interpretation of performance data, Continental Oil has learned how to tailor the composition of its materials to give optimum cost/perf o r m a n c e values. In d e t e r m i n i n g the best ratios of chain length and degree of ethoxylation in its nonionic ALFONIC adducts, Conoco chemists developed a
valuable visual concept—contour charts resembling weather maps or simplified terrain maps. These "Isosuds" and "Isod e t " charts show clearly the proper length of the linear alkyl structure and the correct ethylene oxide content to give maximum foam stability and detergency in surfactant compounding, j
Biodegradability...plus surfactant In assessing any new material, the user wonders basically about two aspects of his product p i c t u r e cost and performance. The cost/performance value of Conoco's biodegradable detergent materials can do more than merely equal the currently used branch-chain compounds, At equivalent formulation cost, soft surfactants and intermediates from Conoco produce detergent compounds that meet or surpass the performance of conventional products...and they assure biodegradability. Consider a typical light-duty liquid. In this example a Conoco soft formulation, with the same raw-material cost as a conventional nonbiodegradable product, gives better foam stability as measured by standardized manual dishwashing tests. Results-averaged over a period of extensive testing—record the number of plates washed, at 115°F with a detergent concentration of 0.05%, before the foam breaks:
In a typical heavy-duty product, the biodegradable formulation gives equal performance at equal cost. Detergency ratings show cleaning action on standard soiled cloths washed in a 0.125% solution at 120T: HEAVY-DUTY DRY DETERGENT Composition Hard Formulation Soft Formulation Alkylate 20% ABS 19% NALKYLENE 500 LAS Séquestrant 50 STPP 50 STPP Corrosion 5 Sodium 5 Sodium inhibitor Metasilicate Metasilicate Redeposition preventive 0.8 CMC 0.8 CMC Filler 15 Sodium 15 Sodium Sulfate Sulfate Whitening 0.1 Optical 0.1 Optical agent Brightener Brightener q.s. Water q.s. Water Detergency 50 ppm Hardness 7.6 7.4 300 ppm Hardness 6.1 6.6 (Least Significant Difference = 1.0 unit)
LIGHT-DUTY LIQUID DETERGENT Composition
Hard Formulation
Alkylate
18% ABS
Anionic
12
Foam Stabilizer
5
Hydrotrope
10
Soft Formulation 25% NALKYLENE 500 LAS
Aikylphenol Ether Sulfate
9
ALFOIMIC1014 Ether Sulfate
LDEA
6
ALFONIC 1016-6 N.I.
Sodium Xylene Sulfonate
10
Foam Stability (No. plates washed) 50 ppm Hardness 26 300 ppm Hardness 27
Sodium Xylene Sulfonate
Foam Stability (No. plates washed) 50 ppm Hardness 13 300 ppm Hardness 16
30 29
13 15
To speed your move into soft detergents, call upon Conoco for the industry's most complete technical-service facilities and for the only available full line of biodegradable surfactants and intermediates. ALFOL Alcohol Derivatives
HI
ALFONIC Ethoxylate Nonionics
ALFONIC Ether Sulfates
CONOCO Sulfonic Acid SA597
NALKYLENE Derivatives CONOCO Sulfonic Acid SA588
CONOCO Soft Slurries C-550/C-560
Household Detergents Heavy Duty, Dry
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Cosmetics Shampoos, C r e a m s , etc. Industrial Applications C l e a n e r s and Detergents Textile, Leather, Paper, and Rubber Emulsion Polymerization
Manager, Surfactant Sales Conoco Petrochemicals, 630 Filth Ave., New York, N.Y. 10020 I'd like to know more about Conoco soft-detergent materials. My particular interest;
Conoco Petrochemicals
Name/Title-
CONTINENTAL OIL COMPANY
Company—
Petrochemical Department 630 Fifth Avenue New York 20. N.Y.
