The Surprising Economics of

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RESEARCH RESULTS . , . immediate& auailable All manuscripts listed here are being considered for possible publication in one of the I&EC quarterlies. They are available to I &EC subscribers at reproduction and handling cost, at any time prior to publication in a quarterly. Papers withdrawn from consideration will generally remain available for 90 days if authors approve. A Research Results Service manuscript should be treated as a personal communication. Reference to its content in any publication should have the author’s prior approval. Please use the printed coupon, and include payment with your order.

Ms. No. . . . . . . . . . . . .

O n the Dynamics of Heat Transport through a Plane, Uniform Wall

triaryl phosphate fluid. I’arious concentrations converted to theoretical amount of COz over Hopcalite a t 300’ C.

Ole Andreas Solheim, Chr. Michelsen Institute, Bergen, Norway

.Ils. 62-243

Some generalized transfer functions a r e presented. Lumping parameters into two sections provides adequate approximation of exact expressions (based on distributed parameters) for nearly all practical problems. Two numerical examples show use of curves and transfer functions.

Ms. 62-70?

38pages, including 28$gures, 2 tables

$4.00

Material for Nuclear Power Reactor Fuel Dissolvers

R. E. Burns and R. F. Mancss, General Electric Company, and D . C . Drenwn and C . L. Peterson, Battelle Memorial Institute An alloy composition has been developed which affords greater corrosion resistance to a wide variety of power reactor fuel dissolvents (nitric acid, sulfuric acid, neutral a n d acid fluoride solutions) than any known commercially available ferrous or nickel-base alloy.

Ms. 62-225

76pages, including Ifigurc, 8 tables

$2.00

Production of Uranium Dioxide by Flame Denltration

W . H . Hedley, R . J . Roehrs, and W . T. Trask, Jr., Mallinckrodt Chmical Works Continuous conversion of uranyl nitrate to UOz with attractive physical and chemical properties. System amenable to rapid start-up and shutdown. Feed rate a n d reaction chamber configuration important factors. Production rates as high as 242 lb. of U/hr. attained. More work needed to optimize assays in excess of 98%.

Ms. 62-238

74pages, including 3figures, 3 tables

$2.00

Effect of Formulations and Processing Variables on Propertier of lsophthalic Polyester Resins

R. R . Miron and D. F. Perciual, California Research Corporation Glycol, acid number, styrene content, fumaric acid, and maleic anhydride a n d concentration of double bonds considered as they affect clear, unfilled polyester resins. Optimum properties obtained by using isophthalic acid instead of phthalic anhydride, fumaric acid instead of maleic anhydride, and by processing resin to low acid number, high molecular weight.

Ms. 62-240

20pages, including Gfigures, 3 tables

$2.00

Catalytic Combustion of Aerosols

Jack G . Christian and J . Enoch Johnson, U. S. Naval Research Laboratory Laboratory reactor simulating CO/H2 burners on nuclear submarines used to study oxidation of aerosols of dioctyl phthalate, a petroleum base lubricating oil, and commercial

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75pagt-5, including Zfigures, 4 tables

$2.00

Preparation and Properties of Linoleate Esters of Sucrose

E . G. Bobakk, A. de .Wendoza, .4. Causa, H’. J . Collings, and G. Kapo, Case Institute of Technology Pilot plant process involving catalytic rransesterification bet\veen methyl esters of fatty acids and sucrose in dimethylformamide solvent. Can be controlled to accomplish degrees of esterification from one to about seven. Modification of purified esters can produce complex vehicles for paints and printing inks, such as emulsions, urethane polymers, and styrenared oils.

MS.62-248

3 0 p a g r s , including 5figures, 5 tables

33.00

Role of Surface Active Agents In Preventing Crack-Forming In the Drying Process for Silica-Alumina Hydrogel Bead

Hiroshi L’kihashi and Ryuzaburo Furuirhi, Asahi Glass Cornpan), Yokohama, Japan Bead breakage much reduced by immersing hydrogels in aqueous solution of surface active agents prior to drying. Yield of perfect gel beads (about 20% without pretreatment) increases to 7&80% with 20 to 30 minute immersion in 0.3% surface active agent solution. Permeability, adsorption on gels, and rate of drying measured; results related to mechanism of protective effect. .Ms. 6 2 - 2 5 4

30 pages, including 72figures, 4 table?

S3.00

A Technique for Removing Metal-Contaminants From Catalysts

R . .4. N i n n and H . Beuther, Gulf Research

e Derelopment Cornpan?

Chemical-washing treatment should prove useful in processing high metal-content residues and crudes by catalytic cracking or hydrodesulfurization. Relatively inexpensive complexing agents such as oxalic acid, acetyl acetone, and dioxane form water-soluble complexes with vanadium and nickel oxides. hletals recovered could partially defray cost of treatment.

.Ms. 6 2 - 2 5 5

20paqes, including 3/igures, 8 tables

52.00

Stress-Relaxation and Recovery Time for Grease and Polymer Systems .We1 .Wiles, D . II’. Miles, Hen71 Elring, and A . F . Gabr)sh, LSiiierjit) of L‘tah

Stress-strain up-and-down curves were obtained on polvvinvr chloride and on Bentone and calcium lime soap greases by repeated shearing, and noting recovery time for system. T h e polymer showed good recovery, grease systems only partial after prolonged rest. An empirical equation and two theoretical equations derived, one involving unimolecular, the other bimolecular kinetics, and used to fit stress-relaxation curves.

M s . 62-258

25 pages, including 7figures, 7 tables (Continued on page 76) VOL. 5 4

NO. 1 2

53.00

DECEMBER 1 9 6 2

73

The Surprising tconomics ot Deep Cold Processing -

I

c

It's surprising but true! When you process with deep cold, the compressor often has more bearing on yield and unit cost than any other processing component. Separation of ethylene and propylene from mixed gases by Altona Petrochemical Company, Pty., Ltd. at its Altona, Australia, plant illustrates the significance of compressor efficiency. This operation is typical of many in which gases are pressurized, liquefied, then fractionated for desired products.

Economics of feed gas compression In most deep cold processes, the feed gas compressors set the pace, providing both process and flow pressures. Throughput is highly dependent on compressor capacity and continuous-operation reliability. And unit cost of product is tied to capacity per brake horsepower of the compressors and to amortization of the installation. Where stream temperatures are critical, economy (from standpoint of power and heat exchange surface) may dictate external, integral or in-diaphragm cooling. For safety, units must be leak-proof. At Altona, feed is gas from pyrolysis units (Design molecular wt. 33.4). Three HS Clark centrifugals in tandem, driven by a 5300 bhp turbine, raise pressure to approximately 30 atmospheres. Engineering selection of compressor staging limited compression rise in temperature to less than 160"F,thus meeting process temperature specifications. Capacity per bhp and saving per square foot of floor are the highest available today. Driver investment and maintenance are low. Continuous operation between scheduled process shutdowns has been maintained without difficulty. Seals and systems have functioned perfectly.

After scrubbing, dehydrating, partial cooling, process streams are liquefied by refrigeration. Refrigeration may be developed by any of several closed-cycle systems and is usually applied through heat exchangers. At Altona a propylene-ethylene cascade system develops temperatures in the -40°F and -122°F ranges.

Economics of refrigerant compression

In closed-cycle refrigeration, system requirements are much the same as when pressurizing feeds, but go beyond in several respects. For example, liquid within

FOREGROIJND: Clark horizontzlly-spiit turbine-driven centrifugal, Model 2MS-8. compresslng ethylene refrigerant in closed-cycie a t Altona Petrochemical Company, Pty.. Ltd. plant i n Australia.

machines or impurities in refrigerant (air, lube oil, or low vapor pressure gases) can reduce capacity 20% or more, might even force shutdown. Should flow of coolant be interrupted, automatic control is needed to prevent relief losses of refrigerant. Effectsof cryogenic temperatures on metals, seals, lubricants and bearing materials must also be countered. Finally, to reduce power, to provide for intermediate levels of refrigeration, or to improve over-all heat balance, sidestream flows are often used. For this, the compressor manufacturer must be able to supply a wide selection of impellers and cases with proved performance. A 4890 bhp, fouv-stage, turbine-driven Clark centrifugal compresses propylene at Altona. I t has two inlet sidestreams. It also has an outiet sidestream which delivers vapor at an intermediate level, for other uses in the process. The 1200 bhp, two-stage, turbine-driven Clark ethylene unit at Altona has one inlet sidestream. Both units have continuously delivered design capacities of refrigerant since initial start-up.

NOT SHOWN: Tandem train of 3 Clark units in same b u i l d i n g which pressurize the process feed gases. (see text) Plant designed and constructed b y The Fluor Corporation, Ltd.

BACKGROUND: Clark unit, Model 3MX8-6, handling propylene refrigerant in closed-cycle. Note sidestream connections and C l a r k control panels.

N o relief or seal losses of refrigerant have been experienced. The reliability of these Clark units has helped APC maintain high yield at low unit cost.

Are you planning to process with deep cold? If so, consult Clark. Paragraph at right indicates the equipment and services within Clark capabilities. Make them your capabilities, contact: Clark Bros. Co. Overseas Div., 122 East 42nd Street, New York 17, N. Y. Clark Bros. Co. Div., Dresser (Great Britain) Ltd., 197 Knightsbridge, London S. W. 7 Clark Bros. Co. Div., Dresser (Nederland) N. V., Laan Van Meerdervoort 53 (1), The Hague Clark Bros. Co. Div., Dresser (France) S.A., 37 Ave. d’Iena, Paris 16 Clark Bros. Co. Div., Dresser Italy, S.p.A., Piazza Cavour 3, Milan * Nippon Clark (Sales agent in Japan), 4 Marunouchi 2-chome, Chiyoda-ku, Tokyo.

CLARK REFRIGERATION CAPABILITIES Clark i s expert at the application o f compression to refrigeration and is organized t o engineer, supply, and guarantee all elements of complete refrigeration systems anywhere in the f r e e world-power, piping, valves, controls, heat exchangers, evaporators, scrubbers, other components. In matching refrigeration systems to your requirements, Clark i s in a position t o recommend t h e m o s t

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suitable compression. T h e company produces a f u l l range o f horizontally and vertically split centrifugal units in capacities to 150,000 c f m (suction), pressures t o over 5,000 psig, f o r conv e n t i o n a l or g a s t u r b i n e d r i v e s . Clark also produces gas turbines to 10,000 blip and integrally or separately dricen balancedlopposed reciprocating compressors i n sizes u p to 11,000 bhp.

One of the Dresser Industries.

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RESEARCH RESULTS Hydroisomerization of Olefins

C. G. Frye, B. D. Barger, H . M . Brennan, J . R. Cole?, and L. C . Gutberlet, American Oil Company Unusual results obtained with multifunctional catalysts such as nickel sulfide and silica-alumina. Combination of equilibrium ratio of tertiary to secondary carbonium ions on surface and rate of hydride ion transfer to ions permits conversion of predominantly low motor octane number olefins to isoparaffins of high motor number.

Ms. 6 2 - 2 6 0

15pages, including afigures, 4 tables

$2.00

Bench Scale Continuous Nitration

A. J . Pribush and T . D . M u t a j i s , General Aniline and F i l m Corporation Techniques used in setting up small scale continuous nitrator, with type of information obtained, as a n example of bench scale use. Deals exclusively with practical and empirical, rather than theoretical, considerations. Pitfalls emphasized.

Ms. 6 2 - 2 6 1

20 pages, including 5 figures

82.00

Boron Stainless Steel as a Nuclear Poison in Chemical Processing Plant Applications

M. E. Weech, Phillips Petroleum Company Boron stainless steel plate nuclear poison permits use of process equipment of any size. Design methods to predict poison content and placement of plates (based on multiplication measurements) are a t a point where plate containers can be adequately specified. Poisoned vessel best selection where cell space is tight or new cell construction is being considered.

Ms. 62-262

I 1 pages, including 6 tables, 4figures

$2.00

Starch Vinylation: Determination of Optimum Conditions by Response Surface Designs

James W. Berry, Henry Tucker, and Archie J . Deutschman, J r . , Ufiiversity of Arizona A statistical study. Starch vinylated with acetylene (350-725 p.s.i.g. pressure range) in presence of potassium hydroxide to produce new starch derivative. Interrelationship of five variables determined. Comparison of predicted and observed values indicates surface design a good characterization of relation between variables and degree of substitution.

Ms. 6 2 - 2 6 3

2 0 p a g e s , including ZJgures, 5 lables

$2.00

The Simulation of Multicomponent Distillation

E. C. Deland and M . B. Wolf, The Rand Corporation New method for analysis of petroleum fractionating columna presented as part of continuing study in simulation of steadystate chemical processes. Presents clear example of conntercurrent flow in an “open” thermodynamic system. Results obtained with aid of analog computer, but work is continuing on digital machine so procedure will be generally available.

M s . 62-264

3 7 p a g e s , including QJigures, 2 tables

$4.00

Catalytic Dealkylotion of Tar Acids

John S. Berber and Leslie R. Little, Jr., Morgantown Coal Research Center New laboratory-scale glass dealkylation unit suitable for catalyst screening tests and evaluation studies. Three types used in dealkylation of low-boiling methanol solubles. Silica-alumina crushed to 16-20 mesh showed greater activity and yields of light phenols than pellet form. Cobalt-molybdenum gave low yields; cobalt fair, but with low total conversion.

Ms. 6 2 - 2 6 5

18 pages, including dfigures, 2 tables (Continued on page 78)

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VOL. 5 4

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DECEMBER 1 9 6 2

77

1 RESEARCH RESULTS

NEED A STEAM TRAP? SERIES 60 “Granddaddy” of all Yarway Impulse Steam Traps. Ideal for process jobs. Pressures to 400 psi Six sizes-%”to 2

$2

Basil Vassiliou and Robert Kunzn, Rohm @ Haas Company Pressurized COS solutions adequate as regenerants for sodium form of some resins, Solution of NaHCOa is a product of regeneration reaction and can be used, when degassed, as regenerant for weak base anion exchange resin. This, plus cheap sources of CO,, reduces over-all deionization costs. Ms. 62-267

74 pages, including 7figures, 7 table

22.00

Application of Contacting Studies to Analysis of Reactor Performance

E. V. Murphree, A . Voorhies, J r . , and F. X . Mayer, Esso Research C3 Engineering Combany, and Esso Research Laboratories

SERIES 120 Higher pressure ver. sion of Series 60. Pressures to 600 psi. Screwed or welding ends. Six sizes-%” to 2“. SERIES 40 High capacity applications. Lever-type valve. For shell and tube heaters, cooki n g coils, dryers, etc. Pressures to 600 psi. Five sizes -%”to 3”

Regeneration of Carboxylic Cation Exchange Resins with Carbon Dioxide

Residence time distribution curves used to determine performance level of a two-phase, fixed-bed catalytic reactor. Chemical and physical effects easily separated. A performance index is defined and used to compare hydrodynamics in different reactors.

M ~ 62-269 .

22 pages, including Bjigures

$3.00

Studies of the Fischer-Tropsch Synthesis. Poisoning of Iron Catalysis by HzS in Synthesis Gas

F. S. Karn, J . F. Shultt, R. E . Kelly, and R. B. Anderson, Pitlsburg Co. Research Center

SERIES 30 For light t o moderate condensate loads -tracer lines, main drips, etc. Replaceable disc-type valve and seat. Pressures to600 psi. Twosizes and %“.

Reduced fused iron oxide and reduced steel turning catalysts show linear decrease in activity with amount of sulfur fed to catalyst until about 60% activity is lost, and less rapidly with further poisoning. Activity of turnings continues steadily to zero, but fused iron oxide catalysts approach constant value of 5-1070 even when as much as 4 mg. S/g. Fe are added. Productivity of fused iron oxide can be maintained constant over moderately long periods by increasing temperature. Activated turnings ineffective after short periods, despite high temperatures.

M s . 62-270

23 pages, including 3figures, 3 tables

$3.00

Role of Fuel Reactivity in Sintering

L9endra N . Bhrany and Eugene A . Pelczarski, U. S. Steel Applied Research Laboratory

-%I’

SERIES 130 New compact combination-steam trap, strainer and blow-down valve in one s m a l l u n i t Saves time, space, money. Two sizes -3/’ and % ”

Oxidation kinetics of carbonaceous fuels appear to depend on total (BET) surface area of particles. A reactivity index based on oxidation characteristics of sinter fuels is particularly useful for evaluation of small samples. Best sintering rates with slow burning (relatively unreactive) sinter fuels.

Ms. 62-279

79 pages, incliiding Sjigures, 3 tables

$2.00

Optimal Distillate-Rate Policy in Batch Distillation

A . 0. Converse and G. D . Gross, Carnegie Institute of Technology

Whatever your steam trap need, there’s a YARWAY IMPULSE to exactly meet it-and a nearby Sales Representative to supply it. For a d d r e s s a n d f r e e c a t a l o g : W r i t e YARNALL-WARING CO., 100 Mermaid Ave., Phila. 18, Pa., U.S.A.

Dynamic programming used to determine optimum rate to produce maximum distillate of specified purity, in specified time. (A case with duration not specified also discussed.) Product yields of 4-570 over conventional achieved, Equations and algorithm developed are limited to binary no-holdup case, hut not to a particular vapor-liquid equilibrium relationship or number of trays.

Ms. 62-281

20pages, including djigures, 2 tables

22.00

Coated Pigments Technology

E . J . Dunn, Jr., and ,M. Kushner, A’ationai Lead Company Reactions a t surface of fine particles produce coatings by variety of techniques common to industry, illustrated by development of various inorganic coatings on silica. Should prove of significant economic advantage to paint, plastics, ceramics, storage battery, and possibly glass, industries. Circle No. 522 on R e a d e r s ’ Service Card

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M s . 62-282

17 pages, including 7 f g w e s , 7 table

22.00