Brackish Waters Treated By Ion Exchange - Chemical & Engineering

Eng. News Archives ... According to Rohm & Haas, the high affinity of an anion exchange resin in the bicarbonate form for ... Published online 6 Novem...
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Brackish Waters Treated By Ion Exchange Weak electrolyte resins show high deionization capacity, can be regenerated at low cost A low-cost process to desalt brackish water has been developed by Rohm & Haas Co., of Philadelphia, Pa. The process, named the Kunin process after its inventor Dr. Robert Kunin of Rohm & Haas, uses a weakly basic anion exchange resin and a weakly acidic cation exchange resin. According to Rohm & Haas, the high affinity of an anion exchange resin in the bicarbonate form for mineral acidity is the crux of the process. This resin, Amberlite IRA 68 in the bicarbonate form, converts mineral acidity (chlorides, sulfate, nitrates, and other acidic ions) to bicarbonate alkalinity. The cation resin, Amberlite IRC 84 in the hydrogen form, changes this alkalinity to carbon dioxide, which is removed from the water being treated by the anion resin Amberlite IRA 68 in the free-base form. The bicarbonate- and hydrogen-form resins are then regenerated by conventional régénérants, such as ammonia or sulfuric acid.

Ion exchange has been a standard method for getting high-quality water for industrial use. However, the use of ion exchange resins in water conditioning was commonly considered limited to supplies with a total dissolved solids concentration of less than 500 p.p.m. When streams with higher concentrations were treated, the resins became exhausted too quickly and it was necessary to regenerate them too soon. This made the cost of treating the water high, and amount of water that could be treated efficiently was generally small. The Kunin process overcomes this problem, R&H says. Improvement in the capacity of the resins is responsible for raising the limit of total dissolved solids concentration treatable from 500 to about 3000 p.p.m. The development of a weakly basic anion resin with high regeneration efficiency is responsible for reducing the cost of this step in the cycle. Therefore, a higher volume of water can be proc-

Deionization Flow Follows This Pattern Raw water

Alkalization

Dealkalization

Carbonation (C0 2 recovery)

Clean water 72

C&EN

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19, 196 5

essed without expensive regeneration cost. The deionization plant involves a series of three ion exchange units. Brackish water passed through the first unit undergoes an alkalization reaction. The anion resin, IRA-68, exchanges the resin's bicarbonate ions for chloride and sulfate ions in the stream. The alkaline effluent then goes to the cation resin bed. Dealkalized. In this resin bed, the water is dealkalized by the cation resin in the hydrogen form—cations in the stream are exchanged for the resin's hydrogen ions. The effluent consists of carbon dioxide and water. The carbon dioxide is removed from the stream in the third unit by the anion resin in the free-base form. The bicarbonate form of the anion resin is obtained when the carbon dioxide-saturated effluent from the second unit is treated. As the third unit removes carbon dioxide from the stream, it conditions itself to take the place of the bicarbonate form of the resin in the first unit. The first unit is regenerated with ammonia or lime to convert the anion resin to the free-base form. The second unit is treated with hydrochloric or sulfuric acid to return the resin to the acid form. At this point, deionization of the brackish water stream is reversed. The third unit acts as the alkalization unit and the first unit acts as the carbonation unit. It would take about 400 cu. ft. of resin in each unit to treat a million gallons of brackish water (1100 p.p.m. sodium chloride as calcium carbonate) per day by the Kunin desalination process, R&H says. The treated stream would be handled in a three-bed deionization unit. Such units are now being used by utilities, pulp mills, petroleum refineries, and chemical plants. Cost of equipment in the Kunin process would be comparable to these units, R&H says. The cost of water treatment by the Kunin process varies with the solids concentration of the brackish water. However, when waters with 500- to 3000-p.p.m. total dissolved solids are treated, the process offers exceptional economies, the company claims. For example, the chemicals cost of conditioning water with 1100-p.p.m. total dissolved solids will vary from 11 to 22 cents per thousand gallons. This will depend on the availability and cost of the régénérant chemicals.

FOR A B R O A D E R R A N G E OF M A T E R I A L S T E S T I N G , HERE'S M O R E M U S C L E IN T H E I N S T R O N LINE

INSTRON'S NEW 20,000 lb. MODEL TT-D This new, extended-range uni­ versal testing instrument has a capability of 20,000 lbs. in both tension and compression. It provides the same features of accuracy and versatility inherhent in Instron's other Uni­ versal Testing Instruments. By virtue of its higher capacity, this new machine extends their advantages to an even broader materials testing range. To assure accuracy at the high load ranges, the TT-D uses a new crosshead guidance system for maintaining lateral stability — important when stiff axial align­ ment is required on the specimen. A standard feature is its cyclic loading capability for reverse loading tests from 20,000 lbs. tension through 0 to 20,000 lbs. com­ pression, and back, without backlash. But most important — all the proven features of the Instron design are included in this new machine. For example : an electronic weighing system with unusual selection of load ranges down to 2 grams full scale ; synchronously constant crosshead speeds, selectable over a wide range; a versatile cycling control capa­ bility ; low-deflection structure and load cell, to give

a "hard" machine for maximum specimen resolution. The TT-D has been developed as a modular addition to Instron's line of testing instruments, and is compati­ ble with a broad list of standard accessories and grips. It is available in either a single console design, or with a separate loading frame, as shown below. This load­ ing frame may be even used with the existing control consoles of other Instron floor model machines. Whatever your testing application, on any type of material, In­ stron has an instru­ ment that will get re­ sults with accuracy and ease — in a sur­ prising variety of ways. Write us for informa­ tion on the new model TT-D, or any other units in the Instron line, to Dept. 27E, Instron Corporation, 2500 Washington St., Canton, Mass.

Find out how other Scientists and Engineers in your field are using Instron testing instruments and systems. Consult the Yellow Pages of your metropolitan telephone directory for address and phone number of your nearest Instron Sales Office and Demonstration Center: Canton, Mass. Springfield, New Jersey . Wilmington, Delaware · Cleveland, Ohio · Park Ridge, Illinois . Atlanta, Georgia . Houston, Texas . Long Beach, Calif.

INSTRON I M C Τ D fl | | Ρ Ω Ρ Ρ Ω Ρ Λ Τ Ι Ω Ν I W O I n U l i U U n r U n A M U n 2500 WASHINGTON ST., CANTON, MASS. 02021

C&Ε Ν

73

here's SCIENTIFIC PROOF how

SORiTy SURESf ΑΓ GLOVIS increase hand safety and cut glove costs

Five liquid-proof glove materials were exposed in recent tests to 485 chemicals and compounds encountered in industrial operations. The ability of the gloves to stand up on the job—to continue to protect —AFTER contact with the deteriorating chemicals was carefully checked. Surety Sureseal® Gloves offered superior resistance over all four of the other glove types in more than onethird of the exposure tests, against 180 of the 485 chemicals. Sureseals ranked in the top two for chemical inertness

in 239 of the 485 tests. Against 48 of the more destructive chemicals, Sureseal Gloves were the ONLY ONES capable of prolonged contact. It's proof that Sureseal Gloves can cut your company's glove consumption and overall glove expenditures... reduce hand accidents and damage. A free sample pair will be furnished at request on company letterhead.

THE SURETY RUBBER CO. Box 97-U-4 · Carrollton, Ohio Export Div.: 138 E. Court St., Cincinnati, Ohio In Canada: Safety Supply Company, Toronto

IMIDAZOLE Now Available from BASF's SemiCommercial Production through BASF Colors & Chemicals, Inc. STOCKS MAINTAINED IN THE U. S. inquiries Tor literature and or samples (company letterhead preferred) should be addressed t
M»Mëi.Mi..»M\iM.ummM*\immmm!m 74

C&EN A P R I L

19, 1965

By comparison, R&H says, in conventional systems which use a strongly acidic cation exchange resin and a weakly basic anion exchange resin, the chemicals cost would be about 67 cents per 1000 gal. In addition, R&H says that the quality of the water obtained after treating is not as good as that obtainable by the Kunin process. R&H further says that in a conventional system a large volume of waste acid must be disposed of after each regeneration. For each volume of waste acid produced in the regeneration cycle of a conventional system, the Kunin process makes only 0.09 volume. Another feature of the process, according to R&H, is the ability of the bicarbonate form of the anion resin to pick up organic matter. The high capacity of the resin for organics means that there will be a reduction of organic content of the water being treated. Pilot Plant. Makeup water production for steam power plants by ion exchange resins has always been considered with great interest. Flashevaporation techniques have been used, but this approach is costly. For this reason, the Kunin process was put on pilot-plant operation at the central laboratories of Ente Nazionale per l'Energia Elletrica (ENEL) at Piacenza, Italy. A series of 105 pilot-plant runs were made to study the variables of the Kunin process in treating brackish water with 1500 to 3000 p.p.m. total dissolved solids. The variables in eluded flow rate, type and level of régénérants, pressure of the system, and influent composition. The efficiency of organics removal was also monitored. The effluent water obtained by the Kunin process had an average conductivity of 15 to 20 micro mhos, total alkalinity of 10 to 12 p.p.m., and virtually no hardness or chlorides. In addition, about 6 5 % of the organic matter present in the influent was removed. Laboratory evaluation of the ion exchange resins after a year's operation in the pilot plant shows that the process has not affected the physical or chemical properties of the resins. The Kunin process is not limited to brackish waters, according to R&H. The process can be used in the treatment of water low in hardness but high in mineral acidity. These waters usually require high acid regeneration levels to minimize sodium leakage.

This bulletin is published to keep you posted on Wyandotte key chemicals, their applications, and the many services Wyandotte offers. You may want to route this to interested members of your organization. Additional information and trial quantities of Wyandotte key chemicals are available upon request . . . may we serve you?

NEW DATA SHEET DISCUSSES THE USE OF PLURAFAC® BIODEGRADABLE SURFACTANTS IN A WIDE VARIETY OF PRODUCTS

Chemicals Outlook APRIL. 1965

This new data sheet is a comprehensive compilation of information about the Plurafac series, including much that is new. Detergency, biodegradability, dynamic foam height, surface tension and other important properties of this versatile new series of biodegradable surfactants are discussed in detail. In addition, the individual advantages of each grade (there are 11 currently available commercially, and the list is growing rapidly) are spelled out to aid formulators in grade selection. There are Plurafac grades for use in many different kinds of formulations—from liquids to solids, from products with low foam to those with medium high foam. The series offers a wide range of foaming properties, some of the members being among the lowest foaming biodegradable nonionics available today. It is possible to formulate anhydrous products which are dust-free, non-caking, and free-flowing through the use of Plurafac surfactants. All Plurafac grades are 100% active and stable in alkaline solutions, dependent only on the variables of contact time, temperature, concentration, etc. They are also stable in non-oxidizing acid mediums and are not precipitated by calcium or magnesium ions. Plurafac grades range from liquid through paste to flake and solid forms. High soil removal values are another mark of the Plurafac surfactants. Nonionic by nature, they are compatible with soap, anionic and cationic detergents, and other conventional formulating materials. They are neutral in solution, drain and rinse freely . . . leave no filmy residue after repeated washings. Write Department CO on your letterhead for your copy of this factfilled data sheet. Samples of specific grades are available upon request.

NEW TECHNICAL PAPER EXPLORES ACCELERATED AGING OF ELASTOMERIC SEALANTS A technical paper entitled "Accelerated Aging of Elastomeric Sealants" was presented by Wyandotte's research staff at the SPI Conference on Elastoplastic Technology at Wayne State University last month. The paper discusses recent research conducted at Wyandotte comparing the performance of several commercial elastomeric sealants, including polysulfides, silicones and urethanes,when exposed to extended water immersion and heat aging. In recent years a wide variety of urethane elastomers have been developed which have good chemical and water resistance, and have weathered well. Since elastomeric sealants are expected to perform for many years, aging characteristics are extremely important in evaluating them. The accelerated aging tests described in this paper were conducted to obtain information in the shortest possible time. The results will be correlated with natural weathering tests as they become available. This paper should be of particular interest to those working on architectural sealing and other sealant applications. To get your free copy simply write on your letterhead to Department CO.

WYA

IM D OTTE

INDUSTRIAL CHEMICALS G R O U P Wyandotte, Michigan · Offices in principal cities SODA ASH · CAUSTIC SODA · BICARBONATE OF SODA · CALCIUM CARBONATE · CALCIUM CHLORIDE CHLORINE · LIME · ETHYLENE GLYCOL · DIETHYLENE GLYCOL · PROPYLENE GLYCOL · URETHANE INTERMEDIATES · SODIUM CMC · SURFACTANTS · ETHYLENE OXIDE · PROPYLENE OXIDE DICHLORODIMETHYLHYDANTOIN · PIPERAZINES · OTHER ORGANIC AND INORGANIC CHEMICALS

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Two Routes to Epoxy Alcohols Found British Petroleum group makes compounds by catalytic autoxidation of olefins

149TH

ACS NATIONAL

MEETING

Petroleum Chemistry

Two routes to good yields of epoxy alcohols have been developed by chemists at British Petroleum's Chemi­ cals Division. These routes begin with various olefins. Eventually, they lead—by oxidation in processes com­ mercially feasible and by reactions characteristic of epoxide structures—to many trifunctional derivatives. Epoxy alcohols were first made dur­ ing studies of autoxidation of some methylpentenes by Dr. K. Allison and co-workers at BP, Dr. G. Foster, Dr. M. B. Sparke, and P. Johnson. They found that oxygen will convert the olefin to the unsaturated hydroperox­ ides under mild conditions of atmos­ pheric pressure, and temperatures of 50° to 60° C. They then found that, in the presence of vanadium com­ pounds such as vanadyl acetylacetonate, these hydroperoxides rearrange to a mixture of two isomeric epoxy al­ cohols. Speaking for Dr. Allison, Peter D. Holmes of BP (North America) Ltd., described the work on epoxy alcohols in a Symposium on Organic Sulfur,

Nitrogen, and Oxygen Compounds. Other chemists have made epoxy al­ cohols using classical methods, usually peracetic acid epoxidation of unsatu­ rated alcohols. One of these workers, Dr. G. B. Payne of Shell Development, synthesized them from the pentene-ols and studied the interconversion of the various stereoisomers of the two epoxy alcohols which can be made from 4-methylpentene-2. The recent work on equilibrium mixtures of these ma­ terials produced by the BP reaction scheme duplicated Dr. Payne's data. The two isomers may be readily interconverted with a base and may be sep­ arated by distillation. Dr. Allison bases a tentative mech­ anism for the process of making epoxy alcohols on known reactions of hy­ drogen peroxide and olefins and un­ saturated alcohols. Tungsten and vanadium oxides are known to cata­ lyze epoxidation and hydroxylation of these materials by hydrogen peroxide. The reaction is believed to involve at­ tack of a peroxide intermediate formed from hydrogen peroxide and the tran­ sition-metal catalyst with the olefinic double bond. This is an ionic reac­ tion analogous to that proposed for epoxidation and hydroxylation of ole­ fins with organic peracids. In addition to the two-step process

Epoxy Alcohol Chemistry Includes These Reactions CH^CMeCHOHCHoHMe

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C&EN

APRIL

19, 1 9 6 5

Me^CHOriCHOHMe

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of first making allylic hydroperoxide and then converting it to epoxy alco­ hols, a single-step process is possible. In it, compounds of metals of Groups IV, V, and VI catalyze direct autoxi­ dation of olefins to the corresponding epoxy alcohols. High selectivities to a particular epoxy alcohol are fav­ ored by mild reaction conditions, low conversions, and absence of acids and water. Yield also is influenced sig­ nificantly by olefin structure. As temperatures and conversions of ole­ fin are increased, selectivity toward epoxy alcohols decreases. Other kinds of oxygenated compounds form, ac­ cording to Mr. Holmes. Products. The BP group has made many different products from epoxy alcohols. For example, the oxirane ring undergoes typical epox­ ide reactions, often in a stereospecific way. Both epoxy alcohols made from 4-methylpentene-2 yield the same triol, but in differing stereoisomeric forms. This triol is a colorless, water-soluble, viscous liquid, similar to glycerol, with about the same low mammalian toxicity. Reaction with hydroxylic materials is of wide scope. Adducts of ethylene glycol are made in 1:1 and 2:1 ratios. Reaction with ammonia and simple amines may cause loss of the stereo configuration. Amino-diols reacted with fatty acids make excellent emulsifiers. The hydroxyl group reactions are limited by sensitivity of the com­ pounds to acid catalysts, and, in the case of one of the epoxy alcohols, by the tertiary nature of the alcohol group. However, a range of com­ pounds—all with an epoxide g r o u p has been prepared, which includes esters, diesters, ethers, urethanes, and carbonates. With simple isocyanates, the epoxy alcohols form crystalline materials, ac­ cording to the BP group. Toluene diisocyanate yields a viscous oil. Ketene gives a good yield of the acetate. To make higher esters, base-cata­ lyzed transes terification will work. Butyrates, laurates, and palmitates have been made, and these could be used as stabilizers for polyvinyl chloride. Difunctional esters, such as chloroacetates and phthalates, lead to terminally substituted difunctional products. Etherization with allyl bro­ mide gives an unsaturated epoxide. A corresponding reaction with epichlorohydrin gives a diepoxide.

.GAF PRODUCT

DEVELOPMENTS

CETYL VINYL ETHER improves rigid Polyvinyl Chloride three ways: Strength.. .Clarity... Processabil ity

Cetyl vinyl ether, a new addition to the GAF line of vinvl ethers, offers advantages in the oroduction of rigid polyvinyl chloride. A reactive monomer, it c o p o l y m e r i z e s w i t h

A n d , in eliminating the need for an external plasti­ cizer, a compounding step is saved. Cetyl vinyl ether also copolymerizes with a variety of other unsaturated monomers, including acrylonitrile, vinylidene chloride and acrylates.

vinyl c h l o r i d e to f o r m an internallyplasticized productwithexcellentclarity, impact strength, and extrusion characteristics.

Semi-commercial quantities are now available. For complete technical details, send the coupon to the GAF Commercial Development Department.

As an internal plasticizer at extremely low levels, cetyl vinyl ether resists migration and doesn't exude from the plastic. Moreover, impact strength of the GENERAL ANILINE & FILM CORPORATION

resin is not sacrificed.

Commercial Development Department CEN419 140 West 51st Street · New York, Ν. Υ. 10020 Please send me Cetyl Vinyl Ether literature Π and sample Π for (intended application)

Name Position Company Address City L

State

Zip

J

Extraction Simulated by Craig Apparatus Analogous bench equipment need not be used for scale-up to full-size liquid-liquid extraction 149TH

ACS

NATIONAL

MEETING

Industrial and Engineering Chemistry Simulation of plant-scale liquid-liquid extractions in a laboratory need not use miniature, continuous equipment analogous to the full-size unit. A Craig apparatus—an extraction train used for laboratory separations of complex mixtures—often can produce the same overflow and underflow compositions as would a plant-scale unit. The simulated product stream will have an impurities content almost identical with that to be expected from a given production column. To simulate the products of a continuous extractor, the stepwise Craig apparatus must be operated under conditions set by the design—actual or projected—of that extractor. Paul A. Belter, working at Upjohn Co/s Kalamazoo, Mich., laboratories, has developed a method for determining these operating conditions. He described them during a symposium on Bench-Scale Process Simulation. His approach can produce typical product during early evaluation of liquid-liquid extraction as a means to separate a feedstream. At this stage, Mr. Belter points out, the detailed data on feedstream properties required for mathematical prediction of product composition is frequently lacking.

While scaled-down continuous columns can be built for laboratory testing, their equivalence to full-size units is often questionable. The Craig apparatus is generally used in analytical work, such as isolating and recovering pharmaceuticals and biochemicals from mixtures of synthesis products. Its function is to apply a great many stepwise extraction stages to a feed mixture in a reasonably short time. A typical unit contains more than a hundred tubular glass contacting cells in tandem. The tubes are so designed that at the end of each extraction stage the light phase in each tube drains into adjoining tube. The heavy phase remains. The rows of tubes are mounted on a frame that rocks them back and forth during each contacting period, holds them motionless while the phases separate, then tilts them to allow the light phase in each to drain into the next tube. This cycle is carried out by an adjustable, automatic mechanism. A Craig unit's operation resembles that of an eluted chromatographic column. First, each tube is partly filled with heavy-phase (static) solvent. Portions of the sample are placed in the first few tubes in the series. Light-phase solvent is then added to the first tube. After the Craig unit has cycled through a contact and

separation stage, this light phase drains into the next tube and fresh light-phase solvent flows into the first tube. Like an eluent in a chromatographic column, the light phase gradually travels through the row of tubes. Components of the sample, each with its own distribution coefficient, travel at varying rates. The analysis ends when the desired components are isolated, each in a separate group of tubes within the series. Cut-off. A continuous, countercurrent extraction column doesn't produce such an array of high-purity components, but rather one overflow and one underflow stream. One of these contains an acceptable concentration of the desired component, plus some lesser quantities of other components of the feedstream. To simulate these two streams with the components separated in a Craig unit, the tubes are set apart in two groups and the contents of each group are combined. The blended contents of the first tube through the cut-off tube represent the underflow. The contents of the remaining tubes together make up the overflow. To simulate the operation of any given column, Mr. Belter's method determines how many extraction stages should be applied in the Craig unit. Once the Craig distribution has been carried out, the method specifies a cut-off tube. A complete analysis of the feed isn't necessary. All that must be known are the approximate weight percentages and the distribution properties of the desired component and of one other "key" component. The contami-

CRAIG. Upjohn's simulation work was performed on a Craig apparatus similar to this one

78

C&EN

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19,

1965

ANOTHER RESULT OF

CHEMICAL PROGRESS

Specialized service to fit your needs! An impressive and growing list of users have discovered the exclusive extra values which V-C can offer through specialization in phosphate chemicals. V-C specialists draw upon an unmatched reservoir of mine-to-end-use research and experience. V-C specialists can work with you on de­ velopment of custom-analyzed samples, or custom-blended special-purpose compounds — or our technical facilities are at your service when you require information or advice regarding the use of basic phosphate chemicals. Listed at right, for example, are a few special-purpose products developed by V-C to meet user requirements. Your use of phosphate chemicals is our specialized interest. When you want research service, samples, small deliveries, bulk shipments, or custom-storage inventories maintained for fast shipments of phosphate chemicals at the peak of quality and purity, your requirements are answered best by V-C specialists. Write for your free copy of Progress in Phosphate Chemicals: a useful reference manual on organic and inorganic phosphate chemicals, their description, typical analyses, uses and containers.

BRIGHT DIPPING ADDITIVES. Bright dipping additives (ADO)

and solutions (DAB), used with V-C phosphoric acid, improve brightness, finish and sparkle of aluminum, minimize fumes by requiring less nitric acid, and inhibit the interference of dissolved aluminum to assure the economy of longer bath life. FLAME RETARDANT. A flame retardant for rigid urethane foam (VIRCOL® 82) locks into the foam to become a permanent func­ tional part of the urethane polymer structure, and acts as an effective flame retardant throughout the life of the foam. CORROSION INHIBITOR. The water solubility and broad inhibition characteristics of VIRCO-PET® 30 provide long protection for aluminum and its alloys in water-cooled engines, heat exchangers, cooling towers and other industrial uses where the metal is in contact with aqueous and semi-aqueous solutions. COLOR INHIBITORS. Many chemical processors are finding the best answer to their color problems in the use of V-C phosphites. Certain of the V-C dialkyl and trialkyl phosphites are widely used to inhibit color in esterification and polymerization reactions. Call or write for information, technical data and samples.

V-C C h e m i c a l C o m p a n y A DIVISION OF SOCONY MOBIL OIL COMPANY, INC.

401 East Main Street · Richmond, Virginia 23208 · Phone: 648-0113

chemicals C&ΕΝ

79

nant closest in distribution coefficient to the desired component is usually chosen as the latter. Conventional trial-and-error calculations determine what solvent flow rates will give an acceptable separation of these two components in a column, and what weight fractions of each will be present in the product stream. The next task is to determine what group of Craig tubes, when their con­ tents are mixed, will give the same weight fractions. Applying statistical theory, Mr. Belter has derived equa­ tions to determine required number of stages and proper cut-off tube. These equations involve constants whose values are taken from statistical tables. The choice is governed by the desired product yield in the full-size column. These "yfeld constants" are thus the link between the continuous column and the stepwise Craig unit. This approach to simulation as­ sumes that no solvent interchange oc­ curs between phases, and that the distribution coefficients of the key components aren't affected by concen­ tration or the presence of other solutes. These assumptions are usually ade­ quate for the dilute solutions used in Craig operations, Mr. Belter says, but their correctness for countercurrent operation should be established for each system studied.

Need larger-than-laboratory amounts?

Ask EASTMAN •We may be able to custom-synthesize the organic compound you need in the a m o u n t you need —even if i t i s n ' t in our catalog. Distillation Products Industries, Rochester, Ν . Υ. 14603.

Phone 716-458-4080

and ask for Jim Fuess

Distillation Products Industries is a division of Eastman Kodak Company

lilMli

Not even a penny for upkeep

Alcohol Ends Emulsion Problems in Pipelines

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No surface protection is needed. First cost is the last cost.

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149TH

C&EN

APRIL

19,

1965

MEETING

Petroleum Chemistry

for75yearstheonly erma

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f % L D L· l m L· ïï\ L· Ο I \ J I N L·, nently satisfactory material for chemical laboratory table tops, shelving, sinks, splash backs, drain boards and fume hoods. Prompt delivery. ALBERENE S T O N E - A DIVISION OF THE GEORGIA MARBLE COMPANY. For FREE literature and technical assistance address: THE ALBERMAR COMPANY, 386 PARK AVE. SOUTH, NEW YORK 16, N. Y., DEPT. N. 80

ACS NATIONAL

Isopropyl alcohol may end a vexing problem for transporters and users of aircraft fuels. This problem is emul­ sion of water and dirt in the fuels by surfactants desorbed from product pipeline internal walls. These emul­ sions can clog filters and possibly cause engines to starve for fuel. Passed through the pipeline before the fuels, isopropyl alcohol will desorb enough of the surfactants to minimize emulsions in the fuels, according to Dr. George J. Kautsky and Dr. M. R. Barusch of California Research. The surfactants get on pipeline walls from automobile gasolines and diesel fuels carried in the pipeline. They are added to these products to inhibit corrosion, to prevent deposits in carburetors, to reduce injector

fouling in diesel engines, and to aid engine performance in other ways. Long pipelines are, in effect, giant chromatographic columns, Dr. Kautsky told a Symposium on Additives in the Petroleum Industry. They adsorb some of the surfactant from one kind of material passing through and desorb it to a material passing later. For their laboratory studies of adsorption and desorption of surfactants, the California Research chemists selected the amino-amide type. These surfactants are made by the reaction of aminoethyl or hydroxyethyl substituted ethylenediamines with carboxylic acids such as oleic or stearic acids. Because of the potential hazards, military specifications for water in fuels are tight. Frequently, Dr. Kautsky says, as little as 1 p.p.m. of surfactant in an aircraft fuel can cause the fuel to fail the military water reaction test (MIL-J-5624E). This much surfactant can easily be picked up by fuel passing through pipelines. Influence. In studying surfactant adsorption and desorption, Dr. Kautsky finds that the kind of fuel and concentration of water in it significantly influence the amount of surfactant which desorbs. JP-4 jet fuel proves to be a good desorber; wet JP-4 desorbs better than does dry. A number of polar compounds have been found effective in desorbing surfactants from pipeline walls. Of those tested at California Research, octylamine acetate proves most effective. However, its cost rules out its use in favor of the second most effective, isopropyl alcohol. Quantities of isopropyl alcohol needed are small. Field experiments confirm predictions based on laboratory studies. For example, Dr. Kautsky and associates have found that 3 bbl. of isopropyl alcohol will purge 100 miles of an 8-in. product pipeline. The isopropyl alcohol was put in the pipeline as an interface between shipments of gasoline and jet fuel. Such a pipeline could adsorb a minimum of about 2.5 lb. of surfactant, Dr. Kautsky calculates. H e assumes a monomolecular layer of an amino-amide surfactant and that the internal wall has a small amount of roughness. Much roughness and rust could increase the wall surface area many times. If the jet fuel desorbed 2 5 # of the surfactant, about 2500 bbl. of jet fuel would have 1 p.p.m. surfactant in it.

HERCULES

in tactical situations *$ The battlefield commander is the man on the spot. The responsibility is all his. He must be sure, certain in his knowledge that each tactical missile will work.

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Hercules provides that kind of assurance with high performance propulsion systems, highly reliable and with known

m*#%

reproducibility. Hercules motors, with fifty years of experience and over a billion pounds of production behind

Ϊ*'Ά

them, give the battlefield commander the power to do his job. From the first solid Navy Bullpup to the Army's Nike, Honest John and Little J o h n . . . from the antitank TOW missile to the Navy's surface-to-air Terrier and T a l o s . . . Her-

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cules has participated successfully in the development of the weapons designed to aid the battlefield commander. Pride in these accomplishments, which include Minuteman and Polaris missiles, is just one of the rewards of working for Hercules. Our Personnel Department has opportunities for a rewarding career in this exciting field for those who qualify. Address career inquiries to Manager of Technical Recruitment...

HERCULES POWDER COMPANY INCORPORATED

Wilmington, Delaware 19899 EQUAL O P P O R T U N I T Y

EMPLOYER XP64.dR2

APRIL

19, 1 9 6 5 C & E N

81

C&EN

COMMERCIAL CHEMICALS

PROGRESS REPORT

These items have all been mentioned editorially in C&EN in the past month. If you haven91 already sent for9 information on them, just check the appropriate key numbers on the coupon on page 84, and C&EN s Readers9 Information Service will forward your request to the manufacturer. Material

Company Ames Laboratories, Inc. Milford, Conn.

Amines

C60

Metal powders

C61

Cerac, Inc. Butler, Wis.

Acid (diphenylphosphinodithioic) Fluorine compounds (hexafluoropropylene and tetrafluoroethylene) Synthetic high polymer (Ficoll)

C 62

Lubrizol Corp. Cleveland, Ohio Peninsular ChemResearch, Inc. Gainesville, Fla.

C 63

Pharmacia Fine Chemicals New Market, N.J.

C 64

Ferrocenes C 65 (chlorocarbonyl and Ι,Γ-dichlorocarbonyl ferrocene)

Research Organic Chemical Co. Sun Valley, Calif.

Feature Intermediates for research and devel­ opment in pharmaceutical, chemical, drug, and polymer industries Chromium and vanadium powders for metallurgical applications and as catalysts Reacts as a mercaptan as well as an acid Gaseous compounds for introducing fluorocarbon group into a molecule Used to make gravity gradients for centrifugation, electrophoresis, and spe­ cific gravity determination For use in making high-temperature polymers and ferrocene intermediates

Available in commercial quantities unless otherwise noted.

BRIEFS An insulating lath board has been added to Monsanto's building prod­ ucts line. Designated Thermo-Lath, the new construction material is a sandwich board of polystyrene foam and a paperboard facing. It is de­ signed for use as a base for plaster on interior masonry and wood-frame con­ structed walls and ceilings. Accord­ ing to Monsanto, Thermo-Lath re­ duces sound transmission. It also re­ sists heat flow seven times better than does a 3 / 8 -in. gypsum lath.

A technically feasible method for re­ covering scandium from readily avail­ able domestic sources has been demon­ strated by the Bureau of Mines, U.S. Department of the Interior. Several thousand pounds of high-purity scan­ dium oxide can be recovered annually from a by-product sludge of molyb­ denum processing using hydrometallurgical techniques developed by BuMines. The bureau hopes to reduce the cost of producing scandium (now more than $1000 per pound) and expand its uses. Scandium is now used only in the form of an artificially radioactive isotope for analytical studies and as a tracer in oil-well drilling and pipeline applications. 82

C&EN A P R I L

19, 196 5

Previously undetected crystal struc­ tures have been found in group 5b metals alloyed with small amounts of other elements. Dr. Gareth Thomas and co-workers at the University of California (Berkeley) have been able to get diffraction-line patterns of tan­ talum, niobium, and vanadium alloyed with less than 0.2% of carbon, hy­ drogen, oxygen, or nitrogen. Such patterns are not detectable by x-ray or neutron diffraction. Dr. Thomas used an electron microscope and ro­ tated the metallic specimens. He hopes to determine the effect of these structures on the properties of metals.

NEW CHEMICALS Resin-bonded dry-film lubricant has been introduced by Fel-Pro, Inc., of Skokie, 111. The compound, C-300, can be used at temperatures from - 6 5 ° to 1200° F . The lubricant dries and cures in one hour without baking, the company says. It can be used with all types of metals, according to Fel-Pro. C 66

Sprayable, nonflammable solvent-type rubber cement has been developed by Imperial Adhesives, Inc., of Cincin­ nati, Ohio. Called Non-Flam, the

cement was developed to coat large areas of rubber, polyurethane, or bonded foam. The cement is also a heat-reactive adhesive that allows fabric and other material to be heatsealed to a precemented substrate by the addition of a heated nip roller, the company says. C 67

A copolymer converter film is being offered by Avisun Corp. According to the Philadelphia, Pa., company, the film retains all of the conventional properties of polypropylene, but has better impact and optical qualities. This film offers better clarity and stiffness than does polyethylene and longer shelf life and cold weather durability than does cellophane, the company says. C 68

Two-component sealant has been de­ veloped by Rubba, Inc. (New York, N.Y.). Called Rubba-Seal, the ma­ terial can be used to make products varying in flexibility, hardness, and elongation, the company says. It can be used at temperatures of —60° F. Rubba-Seal resists oils, acids, alkalies, and solvents. It can also be used as a water-proofing sealant for expansion joints and as an acid-resistant coating. C69

Silicone rubber sealant designed spe­ cifically for bonding and sealing ceramics and glass has been intro­ duced by Dow Corning Corp., Mid­ land, Mich. The sealant cures to a rubber by reaction with moisture from the air. Adhesive bonds can also be formed with aluminum, steel, stone, wood, and most plastics. Cure is usually complete in 24 hr., the com­ pany says. The sealant can be used for interior or exterior surfaces. C 70

ventional plastisol techniques, ac­ cording to the company. C 71

Neutron-gamma shielding material is available from Reactor Experiments, Inc., of Belmont, Calif. The material is a uniform mixture of polyethylene with pure lead and a boron com­ pound. The company says the poly­ ethylene attenuates fast neutrons, the lead shields against gamma radiation, and the boron absorbs thermal neu­ trons. C 72

Liquid system molding and coating compound which makes possible fab­ rication of rigid-vinyl parts is being marketed by Chemical Products Corp., of East Providence, R.I. Called Chem-o-set, the liquid system is con­ verted to a solid material with ther­ mosetting properties by using con­

Further information on keyed Chemical items is readily available . . .

Use handy coupon on page 84

| j

GANTREZ M fPVM) POLYVINYL METHYL ETHER now available in development quantitio

GRADES:

M-154-K40, 50% Solids, Water M-155-K53, 50% Solids, Water M-574-K40, 70% Solids, Toluene M-555-K53, 50% Solids, Toluene THESE GRADES ARE:

1. STABLE 2. UNIFORM 3. LIGHT IN COLOR USE PROPERTIES:

April 19, 1965

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1. Excellent adhesion to plastics, metals and coated surfaces.

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