IsoSiv Process Operates Commercially
DeionizaUon by
Linde process concentrates normal paraffins in C5 to C12 range to more than 95% with 99.8% recovery Linde's IsoSiv process for recovering normal paraflBns from hydrocarbon mixtures is now perking away commer cially at a 1000 bbl.-per-day (charge) clip at South Hampton Co/s plant at Silsbee, Tex. (C&EN, April 16, page 47). The process, licensed by Linde, uses molecular sieves to selectively ad sorb normals, pass iso and cyclic com pounds. IsoSiv can treat feeds such as light and heavy naphtha, kerosine, and gas oils, boosting C5 to C12 nor mals from 15 to 40% to more than 95%. And it can work up process de signs for feedstocks through C2oIsoSiv uses twin adsorbers that al ternately adsorb and desorb normal paraflBns in a pressure swing to give continuous product flow. Beyond this, Linde is cautious with process details. UOP's Molex process also uses sieves
to concentrate normals (C&EN, May 22, 1961, page 56). Molex, though not yet in commercial use, is available for license. It gives product having up to 95% C10 to C22 normal paraflBns from kerosine and light gas oil frac tions of petroleum. Recovery is about 85%. UOP has not revealed just how Mo lex works. The firm says only that it uses one adsorber to produce continu ous normal and non-normal product streams of constant composition. Although skimpy with process in formation, Linde has opened the log on some performance data, following three month's operation of the Silsbee unit. This installation gives 95.8% normal product (C 5 to C12) from a 360° F. end point feedstock having 27.7% normals, Linde's W. F. Avery
means:
INSTANT HI6H PURITY WATER Need 50 gph flows of 19-22 megohm water at multiple points of use? Or is your need 10,000 gph of centrally filtered and démineralized process water? Want automatic shutoff at pre-selected purity? And automatic regeneration, including rinsing and remitting in, at the turn of a single switch? Whatever your specifications, when the deionization system is by Penfield your equipment arrives at the site completely "packaged" — ready to deliver the pure water you need Instantly. There's nothing to assemble, no need even to test-run.* You Just connect to existing plant lines and start-up. Penfield service, too, deserves its "instant" reputation. 15 years of ion exchange pioneering means that Penfield has on file field-proved answers to most industrial water problems — usually can detail the system you need by phone, ship your completely "packaged" units in a matter of days. Try a phone call or letter and see for yourself. Clip this adv. so you won't forget •Resin charges are pre-rinsed and eacn PenfieM unit test-run before shipment
Mamrfactariog C i , tac 46b Britannia St., Meriden, Conn. Industrial Ion Exchange Systems · Filters WeirWashOfs • U 6 Deionizers < " ) t M i Ptnr. MPO. c o . INO.
Here Are the Costs of Recovering Normal Paraffins Using the IsoSiv Process
WEIGH
C5—Cu η-Paraffins Concentration in Feed 15 to 40% Liquid Volume 1000
ELECTRONICALLY ' Ametron Electronic Scale systems are custom engineered to fulfill the requirements of performance that wilt meet your exact specifications. They are flexible instruments requiring a minimum of maintenance. Ametron Scales weigh heavy loads and print the record of w e i g h t on tape, cards or bills of lading. Many new features have been added to the Cab- k Inet Model m Recorders. •
Writ· for tft« latest bulhtin, M 0 , illustrating «fectron/c wish· Inw systems. WRITE
1000 Bbl. per day—normals
10,000
r c
' STREETER-AMET COMPANY GRAYSLAKE,
APRIL
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ILLINOIS
1962
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C&EN PROGRESS REPORT
INDUSTRIAL CHEMICAL SPECIALTIES
Companies added these products to their lines during the past four weeks Material
Company Analytical Engineering Laboratories, Inc. Hamden, Conn. Arnold, Hoffman & Co., Inc. Providence, R.I. Atomic Laboratories, Inc. Berkeley, Calif. Chicago Gasket Co. Chicago, III. Dow Corning Corp. Midland, Mich. Lindberg Engineering Co. Chicago, III. Mann Research Laboratories, Inc. New York, N.Y. Marbon Chemical Division Borg-Warner Corp. Washington, W.Va. Process Chemicals Co. Santa Fe Springs, Calif. Thompson-Hayward Chemical Co. Kansas City, Kan.
Polar polymers (Series R) Dichlorotriazinyl dye (Procion Grey GS) Six radioisotope sources Filled Teflon compound (Ebolon) Solventless, opaque silicone resin (Sylgard 183) Protective flux for aluminum (Algard) Pure L-isoleucine Reinforcing modifier (Blendex) Cationic textile softener (Prosept 2355) Agricultural chemical emulsifiers (T-Mul Hf T-Mul L, and T-Mul Mal-8)
Suggested Uses Include As stationary phases of gas chromatographs For general dulling as well as shading Schools and other installations Improves resistance to wear and reduces cold flow Potting, embedding, or encapsulating circuits and components Prevents oxidation of molten aluminum in reverberatory furnaces Obtained from a special fermentation process For PVC sheet formulations A nonyellowing, free-flowing, flaked solid H and L for use in chlorinated insecticides and herbicides. Mal-8 for use in malathion formulations
Available in commercial quantities unless otherwise noted.
and M. N. Y. Lee told the First annual meeting of the National Petroleum Refiners Association in San Antonio, Tex. Recovery is 99.8%. At the same time, the non-normal stream is 99.9+% pure with 98.3% recovery. So far, the sieves haven't needed reactivation. They are still running near capacity at design throughput. The South Hampton unit has no built-in reactivation equipment. Though Linde doesn't amplify, it says that it has worked out reactivation procedures on a commercial scale. Linde has come up with some preliminary cost estimates, too. For instance, treating costs for a plant handling 1000 bbl. per day of 360° F. end point stock with about 28% normals (C 5 to C 12 ) are 25.2 cents per bbl. of charge. This equals 91.7 cents per bbl. of pure normal product. These costs are based on a 90% on-stream efficiency and include utilities, adsorbent, labor, and all fixed charges, including amortization. But they don't include process license fee. Investment costs for the same plant run an estimated $295,000. This includes equipment, adsorbent, direct 60
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and indirect labor, materials, and contractor's charges. Operating and overhead costs for Molex, excluding payout, will run 31 cents per bbl. of charge for a unit handling 4350 bbl. per day of either kerosine or a gas oil having 23% straight chain molecules (C 1 0 to C22). This cost equals 0.58 cent per lb. of normal product. Such a unit would produce 850 bbl. per day of normal paraffins. Erection costs would be about $2.5 million. Linde data indicate that an IsoSiv unit can produce 850 bbl. per day of normals (C 5 to C 12 ) for 65 cents per bbl. of normals (0.22 cent per lb.). Investment would be about $630,000. It's hard to compare the economics of the two processes using the published data. IsoSiv costs are based on treating a C 5 to C 1 2 stock. Molex data are for a C 7 catalytic reformate and also a C 1 0 to C 2 2 stock. Treating the latter stocks is harder and more expensive, UOP says. Linde has been working with IsoSiv for the past five years. It's one of many adsorption processes that Linde plans to license.
Nylon 11 Fiber Process Details Revealed French producer describes complete process from the castor oil to the fiber Seizing the opportunity presented by a meeting of fiber chemists in Germany, France's Société Organico has gathered into one public place all the information it can release about the synthesis and properties of Rilsan— nylon 11. Unlike the polyamides 3, 5, 7, 8, and 12 (see page 57), Rilsan is a commercial resin, mainly for specialty use. Last year it held about 2% of the world market. Rilsan went into commercial production in 1955 after six years of testmarketing, Dr. M. Genas of Organico told the symposium on Progress in the Field of Fiber- and Film-Forming Macromolecules, sponsored by the plastics and rubber division of the German Chemical Society, meeting in Bad Nauheim, West Germany. Organico makes it in six steps from castor oil via 11-aminoundecanoic acid.
Basically, the Organico process works this way. Castor oil (mainly mixed triglycerides of ricinoleic, oleic, palmitic, stearic, and dioxystearic acids, with the ricinoleic predominat ing) is converted by methanolysis to the methyl ester of ricinoleic acid. This then splits thermally into nheptaldehyde and methyl undecylenate. The ester is saponified to the undecylenic acid, converted to 11bromoundecanoic acid by adding HBr across the double bond between the two terminal carbon atoms, and ammoniated to 11-aminoundecanoic acid. The latter yields nylon 11 after polycondensation. Trickiest step is the addition of HBr, according to Dr. Genas. Nor mally, the bromine would add to the most highly substituted carbon—in this case, the C-10. But it can be directed to the end carbon by the "peroxide effect" using a nonpolar solvent and oxygen free radicals. In the Organico process, undecylenic acid in a toluene-benzene solvent flows down through a packed column, contacts a counterflowing stream of HBr in air. Result is 95 to 97c/r 11bromoundecanoic acid and only 3 to 5% 10-bromo, according to Dr. Genas. Monomer Heated. Polycondensation of 11-aminoundecanoic acid pro ceeds upon simple heating of the molten monomer, Dr. Genas says. Condensation and spinning are con tinuous. The 11-aminoundecanoic acid is suspended in water and various ad ditives mixed in. The suspension is fed into a reaction column with three compartments. In the first, the mon omer is melted, water is rapidly re moved, and polycondensation begins. In the second compartment, polycon densation continues, and the remain ing water is removed. The third compartment serves to define the necessary holding time for the reaction to yield a reproducible molecular weight distribution and acts as a reservoir for the spinning process. Adding phosphoric and phospho rous acids and some of their deriva tives before melting increases the melt viscosity and makes spinning easier, Dr. Genas says. Further, it also stabilizes the degree of polymeri zation by blocking the amino end groups and accelerates the polymeri zation, he adds. Properties. Rilsan as commercially manufactured has a melting point of about 190° C., compared to nylon 6's
ECONOMICAL COOLING OF GASES A N D COMPRESSED AIR • Cooling gases or cooling and remov ing moisture from compressed air, the Niagara Aero® After Cooler offers the most economical and trustworthy method. Cooling by evaporation in a closed system, it brings the gas or com pressed air to a point below the am bient temperature, effectively prevent ing further condensation of moisture in the air lines. It is a self-contained system, independent of any large cool ing water supply, solving the problems of water supply and disposal. Cooling-water savings and powercost savings in operation return your
equipment costs in less than two years. New sectional design reduces the first cost, saves you much money in freight, installation labor and upkeep. Niagara Aero After Cooler systems have proven most successful in large plant power and process installations and in air and gas liquefaction applications.
Write for Descriptive Bulletin 130.
N I A G A R A BLOWER COMPANY Dept. CN-4, 405 Lexington Ave., New York 17, Ν. Υ. Niagara District Engineers in Principal Cities of U. S. and Canada
Now Available
Low Molecular Weight Alkyl Aryl Sulfonate For Emulsion Polymerization If you are searching for a source of low molecular weight alkyl aryl sulfonate for evaluation as an emulsifier or stabilizer, consider Ultra's Sulframin® N A B . A n o n y l b e n z e n e sulfonate p r e p a r e d from close-cut C 9 fractions, Sulframin NAB offers a high d e g r e e of uniformity. N o w available from Ultra in commercial quantities. W r i t e for your free sample today.
ULTRA CHEMICAL WORKS, INCORPORATED Dept. AH-10, 2 Wood St., Paterson 4, N. J.
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225° C. and nylon 66's 265° C. Density is about 1.04 to 1.05, lower than that of nylons 6 and 66—about 1.14—because of the different ratio of CONH groups to CH 2 groups be tween the two types of nylon. Rilsan's ratio is 1:10, nylon 6's and 66's are 1:5. This smaller proportion of CONH groups also explains the lower water absorption of Rilsan (and the other higher nylons such as 8 and 12), ac cording to Dr. Genas. Rilsan picks u p only about 1% by weight of moisture in air at 6 5 % relative humidity and 20° C , about 2% when immersed in boiling water. These low values make it relatively hydrophobic compared to 6 and 66, Dr. Genas says. And it is one of the fiber's major plus factors in those uses it has found.
Cross-Linking Agents Give Smooth-Drying Cotton Finishes Ether linkages with cellulose provide crease resistance and crease shedding
JAM
BUSTER
Never again lab countertop congestion. Fisher's new extra-deep top puts 30.4% more working space at your disposal—and at a savings. Instead of splashback and reagent shelf, there's now a level top 3 0 " from front to back—room enough for today's complex lab instrumentation without crowding. The new top is completely compatible with Fisher units you now have . . . and ideal for island and peninsula arrangements. Best yet, extra-deep tops are less expensive than those with splashback and shelf (though such tops are still available). Fisher Unitized Furniture offers you more than just extra space. For instance: long life; simple installation; rapid delivery from continuous inventory. Get more facts in free lab planning kit. Write Fisher Scientific Company, 101 Fisher Building, Pittsburgh 19, Pa. j.245
FISHER SCIENTIFIC World's Largest Manufacturer-Distributor of Laboratory Appliances & Reagent Chemicals Boston · Chicago · Fort Worth · Houston · New York · Odessa, Tex. · Philadelphia Pittsburgh · St. Louis · Union, N. J. · Washington · Edmonton · Montreal · Toronto 62
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A British research laboratory has pro duced a new class of chemical crosslinking agents for cellulosic and other polymeric materials. These agents in turn have led to development by Tootal Broadhurst Lee Co., Ltd., of methods for producing smooth-drying finishes on cotton fabrics. One of the new reagents found particularly suitable for cotton fabric treatment is the di-sodium salt of tris (β suifato-ethyl) sulfonium inner salt. This salt, Tootal Broadhurst Lee says, reacts rapidly at room tempera ture under alkaline conditions to pro duce ether linkages with cellulose and to provide "highly efficient qualities ,, of crease resistance and crease shed ding in the wet state. This leads to satisfactory smooth-drying and noniron performance of fabric under mod ern laundering conditions. An exceptional advantage of the new reagent is that its reaction with cellulose is simply and reliably con trolled, Tootal says. Its sensitivity to processing variations is "significantly less than with many other textile finish ing processes such as treatment with conventional reactant resins." Although the sulfonium salt can be used alone for finishes where a high order of dry crease resistance isn't
needed, it is better applied with small amounts of resin or reactant to give maximum smooth-drying and creaseresist behavior under all conditions of laundering and wear. Recommended processing methods are applicable to both white and coloreds, says Tootal. Applications for patents covering these chemical agents and their use have been made in the main industrial countries. The proc esses are to be offered under license to other companies in the textile in dustry, and licenses have already been granted to several textile finishers in the British Isles. Arrangements have been made be tween Tootal Broadhurst Lee and Imperial Chemical Industries to manu facture and supply the sulfonium re agent to licensed textile finishers.
New GC Analyzes Gas Inclusions in Glass A gas chromatograph developed spe cifically for the analysis of gas in clusions in glass is now being mar keted. The manufacturer, John P. Mickel Associates, Inc., says the in strument is 100 to 1000 times as sensi tive as most commercial gas chromatographs for inorganic gases. A special crusher is used to pre pare samples for the instrument. Columns are supplied for analyzing Ho, 0 2 , No, CH 4 , CO, C 0 2 , NoO, NO, and SOo in a single sample. The unit is sensitive enough to detect compo nents in a 0.000015-ml. sample using a 1 millivolt recorder. Price of the instrument is $4500 with a standard column.
April 23, 1962
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