Humble Consolidates Refinery Control Rooms
One of 100 flow diagrams flashes on a projection screen, as a control room operator checks control of a refinery unit. Push-button flow diagram projection is just one of a number of advanced
control concepts designed into Humble Oil's new control room at its Billings, Mont., refinery. All told, they add up to a new degree of sophistication in control design.
and air-melted heats made in an induction furnace. The yield strength of 12-2 is 214,000 to 225,000 p.s.i.; conventional 187c maraging steel's yield strength is 240,000 to 268,000 p.s.i.; tensile strength of 12-2 is 227,000 to 236,000 p.s.i.; conventional 18% maraging steel is 250,000 to 275,000 p.s.i. Foote's investigations on the use of manganese in maraging steel showed that with 12.5% nickel content, a minimum addition of 1% manganese has little effect on mechanical properties. However, increasing manganese content from 1% to 2% results in an increase of about 60,000 p.s.i. in both tensile and notch tensile strength while retaining high ductility. Beyond 2.25% manganese, Foote says, tensile strength continues to increase gradually, but notch tensile strength and ductility begin to decrease.
Monsanto Gets Patents On Electrolysis Process
Production of 12-2 maraging steel heats should be similar to that of 18% nickel heats, Foote says, with three exceptions. First, manganese containing scrap can be used for charges. Second, care is required in making additions because of the higher vapor pressure of manganese; preferably, these additions are made to the ladle. Finally, the cost of producing 12-2 maraging steel will be lower. 42
C&EN
JULY
26,
1965
A total of 10 U.S. patents (3,193,475 through 3,193,483, and 3,193,510) on Monsanto's electrochemical process for making organics have issued. The company says that it expects an additional three to four U.S. patents and several foreign patents to issue within the next six months. Designed to hydrodimerize alpha,beta-unsaturated acids and their derivatives, the technique is perhaps most significantly used for hydrodimerization of acrylonitrile to adiponitrile (C&EN, Oct. 14, 1963, page 6 9 ) . Chemstrand division of Monsanto has nearly completed construction of the first commercial-scale plant at Decatur, Ala., based on the technique. Production of adiponitrile will be for captive use entirely, Monsanto says. In Monsanto's process, acrynloitrile in an aqueous quaternary ammonium salt solution passes through the cathode side of an electrolysis cell. The anolyte, separated from the cathode by a permselective membrane, consists of sulfuric acid ranging from 0.05 to 20% by weight. Electric current in the range of 15 to 40 amp. per square decimeter across the cell induces
The new control room is highly compact. It replaces three older buildings from which 15 refining processes had been controlled and includes the functions of what would have been a fourth control room. The fourth would have been needed for a new hydrocracking unit built at the refinery. The control room, designed by Esso Research and Engineering, includes the first installation of Honeywell's PVSI's— pneumatic vertical-scale indicating instruments. These are the pneumatic counterparts of the electronic instruments that pioneered the verticalscale indicating concept at Monsanto's Chocolate Bayou installation in 1962. The Billings control room console contains more than 500 control instruments and recorders. The control consolidation, Esso Research says, lowers chances of process upsets being transferred from one part of the refinery to another. It also is expected to yield savings in tankage and fuel. Honeywell supplied the consoles, built the control center, and installed the underground air lines.
hydrodimerization of acrylonitrile. Adiponitrile formed by the reaction on the cathode side of the cell is taken off through a bleed and refined. Unreacted acrylonitrile and catholyte are recycled to a surge tank. The quaternary ammonium salt solution increases the solubility of acrylonitrile in the catholyte. It also provides ions to increase conductivity through the cell. A 7 to 9.5 p H range is maintained on the cathode side to get the best yield of adiponitrile—usually better than 90%. Cation-exchange resins which are suitable for use in the permselective membrane are sulfonic and carboxylic types. These resins are commercially available and include sulfonated phenol-aldehyde resin products and sulfonated cross-linked polymers of styrene, as well as certain carboxylic resin types. In Monsanto's pilot runs, the cationic membrane consisted of a sulfonated styrene-divinylbenzene polymer supported on a glass fiber base. In general, the membrane should be selective to particles carrying a positive electric charge to permit the passage of cations. At the same time the membrane should be capable of preventing the passage of undesirable amounts of anions. The cation perm
selective membranes used by Monsanto consisted of a solid polymeric matrix with at least 1 milliequivalent of dissociable ionic groups, such as carboxylates, per dry gram of membrane. A suitable polymer is Dow's Dowex 50. Other types of membranes are also suitable—membranes of sulfonated vinyl chloride polymers and copolymers, for example. Monsanto says that in the past, various electrolysiis reactions for reducing or altering organic compounds have been known but could not be scaled up to commercial units at high current densities—more than 10 amp. per square decimeter of cathode surface. In contrast, according to Monsanto's patents, its process operates at current densities higher than 10. Further, it is possible to use cells with large effective electrode areas, either as a single electrode or as a series of electrodes. Commercial. While Monsanto will say nothing about the Decatur, Ala., operation, the company's patents note that in commercial practice it is probable that individual cells will draw at least 20 to 30 amp., most likely more than 100 amp. Commercial cells drawing more than 1000 amp. are being considered. To get suitable economics and to make practical use of high current densities without prohibitively high cell voltages, the patents state, it is essential to have low resistance in the cell by using high concentrations of electrolyte salt—up to 707c It is also necessary to have a small gap between the electrodes. For the gap, Monsanto prefers no more than 1 / 2 in. More effective operation of the cell is obtained when the gap is 1 / 4 in. or less, the patents state. Applied voltages of 5 to 20 volts for current densities of 15 to 40 amp. per square decimeter of cathode surface are suitable. In this range as well as at higher current densities it is preferable that the applied voltage have a numerical value of not more than one half of the numerical value of the current density in amperes per square decimeter, according to the patents. Any number of direct-current power sources can be used. The patents note that there are a number of means of varying the applied potential to regulate the current density and the cathode potential. Alternating current can be superimposed on direct current applied to the cell, if desired.
Directed-Vortex Mixer To Be Made in U.S. Gebruder Grun, K.G., of Lissberg, West Germany, plans to begin production of its directed-vortex mixer for dry powders in the U.S. early in fall. The firm has sold more than 150 mixers in Europe in sizes from 2 to 1500 cu. ft. Gebruder says it hasn't decided whether to set up its own facilities or to form a joint venture with a chemical process equipment maker to produce the mixer in the U.S. Directed-vortex mixers are expensive—they are also efficient. Gebruder admits that its mixer is probably more expensive than other dry-powder mixers on the market, but believes advantages outweigh initial investment for the directed-vortex mixer. The directed-vortex mixer, called Airmix, has a mixing efficiency of one part in 100,000. That is, 5 grams of an indicator substance can be homogeneously mixed with 500,000 grams of another substance, for example. Lead powder and soot have been mixed. Mixing times are 12 to 60 sec. Other advantages include low power requirements, little maintenance (few moving parts), and rapid and complete product discharge. Mixing takes place in a directed vortex of material and air. Practically all dry powders or granulated products can be mixed. The vortex is formed when compressed air passes through Laval nozzles on the perimeter of a mixing head. The air reaches supersonic velocities flowing through the nozzles and spirals up the sides of the conical mixing chamber, bringing the powders to be mixed into intimate contact. At the top of the cone, solids move to the center, and fall to the bottom where the mixing head jets carry them aloft again. Air pressure in the mixing head is 115 to 290 p.s.i. Depending on particle size and moisture content, from 220 to 510 p.s.i. air pressure is required in the air reservoir. The air flow is intermittent. Static electricity charges interfere with proper mixing since charged particles tend to collect. Steel rods through the mixing cone dissipate any static charges that build up, according to the firm. Nozzle size and angle in the mixing head depend on the materials to be mixed. To discharge, a pneumatic jack lifts the mixing head, and the mixed powders fall out the bottom.
Directed Vortex Mixes Dry Powders Dust release to sack filter for fines
Rotating dust separator
Air canal
If the mixed materials tend to bridge, a blast of air "livens" them so that proper discharge can continue. Gebruder Grun has U.S. patents 3,097,828 and 3,179,379 on the mixer.
Uses Expanded for FluoSolids System Dorr-Oliver has expanded the uses of its FluoSolids system by developing a method for disposing of wastes from neutral sulfite and neutral sulfite semichemical (NSSC) pulp plants. The Stamford, Conn., firm's liquor combustion system might also be useful in small kraft (sulfate) mills where a conventional kraft recovery system is too expensive. The first installation of the method will be at Green Bay Packaging, Ine., Green Bay, Wis. Cost of the FluoSolids system for Green Bay's 200 tonper-day plant is about $1 million. The system will handle about 250 tons per day of sulfite effluent. The neutral sulfite and neutral sulfite semichemical pulp industry accounted for about 5 to 6% (about 2 million tons) of the pulp produced in the U.S. last year. Kraft mills accounted for about 60% (31.9 million JULY
2 6, 1965
C&EN
43
tons per year) of the pulp produced. Usual practice in the NSSC industry is to dump the sodium sulfite black liquor, though a few plants burn the liquor in furnaces, or put it to other uses—vanillin manufacture for instance. Dorr-Oliver's process converts the black liquor to high-quality, 85 to 97% sodium sulfate granules (3 to 15% of the product is sodium carbonate). The black liquor undergoes two stages of concentration which bring the solids up to 44%. Sulfur from a ball mill is then added to bring the concentrated liquor to the desired percentage of sulfate. The concentrated and enriched black liquor is then pumped directly into the upper bed of a two-stage FluoSolids reactor where organic material is oxidized and the sulfites and sulfur are oxidized to sulfate. The bed consists of continuously growing sulfate pellets supported on a rising column of preheated air. Fines carried over into the stack gases are removed in a hot cyclone separator and returned to the bed; the hot gases are used in the concentrating system.
The hot sulfate pellets flow through a valved pipe from the upper bed into the lower bed where they are cooled and the incoming air is preheated. Sodium sulfate pellets are discharged by gravity at 200° F. The reactor requires an external heat source, such as fuel oil or gas, for start-up but then is self-sustaining. The economics of Dorr-Oliver's system are such that Green Bay expects to recoup its investment in the recovery system in from five to seven years. Economics of the process are enhanced when there is a ready outlet for the sodium sulfate. A kraft pulp mill is an ideal buyer, since kraft mills use 80 to 120 lb. of salt cake makeup per ton of pulp produced. In Green Bay's case, it already has a contract with a kraft mill to buy its entire output of sodium sulfate. Present price of salt cake is about $28 per ton, but the NSSC plant must get its salt cake to the kraft mill buyer. In the case of long hauls, the return to an NSSC mill would be somewhat less than the $28 price. Economies of the recovery process, however, are good, according to Dorr-Oliver.
Dorr-Oliver says its equipment will recover 1 ton of sodium sulfate for every 3 tons of pulp produced. Total cost of operating the recovery equipment is $2.25 per ton of pulp. Based on selling the salt cake at $28 per ton, the process would recover $9.33 of salt cake per ton of pulp at a recovery cost of $2.25. This cost includes labor, electricity, steam, elemental sulfur makeup, and maintenance. However, this figure does not include capital cost of the mill. Theoretically, the equipment could pay for itself in a few years. Thereafter it would bring a profit to a 200 ton-per-day pulp mill of several hundred thousand dollars a year, according to Dorr-Oliver.
NEW EQUIPMENT Hydrocarbon analyzer for measuring trace concentrations of hydrocarbons in gases and atmospheres is available from Beckmann Scientific and Process Instruments Division, of FulThe explosion-proof lerton, Calif. analyzer is designed for in-plant location and for operation in hazardous areas, the company says. E 30
A 150-ml. centrifuge bottle for highspeed centrifugation is available from Corning Glass Works, of Corning, N.Y. According to the company, the bottle will withstand centrifugal forces up to 15,000 G. It has an autoclavable polypropylene screw cap and a rubber adapter to fit standard centrifuge rotors. E31
Liquid scintillation counting system
is available from Packard Instrument Co., Inc., of Downers Grove, 111. The counter includes automatic external standardization and an IBM typewriter printout and incorporates completely separate channels of pulse height analysis, the company says. E 32
ARRANGEMENT. In this arrangement of a FluoSolids liquor combustion system for a 200 ton-per-day neutral sulfite semichemical pulp mill, the entire system could be built within a 3000-sq.-ft. area with an over-all height of 85 ft. 44
C&EN
JULY
2 6,
1965
Gas chromatograph has been developed by Perkin-Elmer Corp., of Norwalk, Conn. The dual-column 880 makes possible temperature program rates from 0.5° to 48° C. per minute. Moreover, special accessories allow sampling of liquids that would separate into two phases at atmospheric pressure, according to the company. E 33
How does your dispersant stack up against this one? \\
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Rayflo-C delivers powerful dispersing action for days
Insecticide (tribasic copper sulfate)
Insecticides are an acid test for dispersants. Because in short time most suspensions break down. Now comes Rayflo-C with long-lasting power. It holds suspensions up to 67 hours — and longer. Agitate it and you regain suspension for another long haul. At remarkably low cost. You use Rayflo-C where you require a powerful dispersant with longevity. In boiler water treatment. Soap dispersion. Industrial cleaners. Carbon black. Agricultural sprays. Ceramic deflocculants. It will disperse calcium and magnesium salts, soil and dirt.
Insecticide with Rayflo-C
see how Rayflo-C is readily modified to meet special situations. Like yours. Rayonier Research has the facilities, scientific manpower and experience to help you work out knotty dispersant problems, whether involving product or cost. Or both. Just clip the coupon. Rayonier Incorporated, Dept. S-01, 161 E. 42nd Street, N e w York, N.Y. 10017
Please send me samples and technical data on Rayflo-C. My area of interest is
Since it's a giant molecule (a polyflavonoid) you can NAME TITLE.
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COMPANY. ADDRESS_
C& EN
45
C&EN
INDUSTRIAL CHEMICAL SPECIALTIES
PROGRESS REPORT
These items have all been mentioned editorially in C&EN in the past month. If you haven't already sent for information on them, just check the appropriate key numbers on the coupon on page 48, and C&EN's Readers' Information Service will forward your request to the manufacturer. Product
High-purity pesticides
Company Applied Science Laboratories State College, Pa. Bio-Rad Laboratories Richmond, Calif. Bryant Chemical Corp. North Quincy, Mass. Cabot Corp. Boston, Mass. Cadet Chemical Corp. Burt, N.Y. Escambia Chemical Co. New York, N.Y. Fisher Scientific Co. Pittsburgh, Pa. Hartman-Leddon Co. Philadelphia, Pa. Hercules Powder Co. Wilmington, Del. Hughson Chemical Co. Erie, Pa. 3M Co. St. Paul, Minn. Olin Mathieson Chemical Corp. New York, N.Y. Rohm & Haas Corp. Philadelphia, Pa.
C60
C61 Hydroxylapatite powder (Bio-Gel HTP) Release agent C 62 (Bryco DSHV) Colloidal silica C 63 (Organ-O-Sil S-5) Methyl ethyl ketone peroxide catalyst (Cardox MDP-1) C 64 Polyvinyl chloride fusion resins C 65 (Series 4000) Atomic absorption standards C 66 Staining medium C 67 (Stainmount) Polypropylene formulations C 68 (Pro-fax PA-763) (Pro-fax PB-762) Epoxy adhesive C 69 (Chemlok 305) Polyurethane resins C 70 (Scotchcast) Polyether C 71 (X-5011) Acrylic polymer C 72 (Acryloid A-30) Chemical-resistant coating (Socony/Valdura 78-J-2) Heat-resistant coatings
C73
Linear alkylate sulfonates
C75
Acetylene black
C76
Socony Paint Products Co. Metuchen, N.J. Socony Paint Products Co. Metuchen, N.J. Ultra Division, Witco Chemical Co. Paterson, N J . Union Carbide Corp. New York, N.Y.
C74
Features For use as calibration standards for gas chromatography For the chromatography of enzymes, nucleic acids, and viruses For polyvinyl acetate and acrylic emulsion systems Imparts moisture resistance to many materials Gives longer pot-life when mixed with polyester resins Glossy vinyl coatings that can be applied rapidly Can be used to establish curves for any atomic absorption spectrophotometer Makes staining and mounting specimens in one step possible For appliance applications and injection molding Cures at room temperature for bonding elastomers and metals For electrical and electronic encapsulation applications Used as flame retardant in rigid urethane foams Demonstrates flexibility, adhesion, and abrasion resistance in vinyl topcoatings For protection of steel, nonferrous metals, masonry, and wood One for use on metal surfaces to 900° F., another to 400° F. Can be used as emulsifiers in latex polymerizations To impart thermal and electrical conductivity to rubber goods, plastics and coatings
Available in commercial quantities unless otherwise noted.
Mass spectrometer is available from Picker X-Ray Corp., of New York, N.Y. According to the company, the doublefocusing MS702 has a proven sensitivity down to one part per billion. It makes use of spark and other ion sources possible, the company says. E34
A sulfur dioxide analyzer is available from Scientific Industries, Inc., of Queens Village, N.Y. The instrument is for continuously analyzing and recording and will give full-scale deflection in 10 min. at concentrations as low as 10 p.p.m., the company says. E 35 46
C&EN JULY
2 6, 1965
NEW CHEMICALS Transition metal chlorides are available in research and development quantities form Alfa Inorganics, of Beverly, Mass. Included are anhydrous manganous chloride, cobaltous chloride, ferrous chloride, and chromium chloride. Uses as chemical intermediates, molten salt systems, and catalysts are possible, the company says. C 77
Dicyclohexyl carbodiimide is available from the Upjohn Co., of North Haven, Conn. The chemical has possible uses as an intermediate in pharmaceuticals,
agricultural and veterinary chemicals, and polymers, the company says. C 7 8
A silicone, cell-control additive for flexible urethane foam is available from Dow Corning Corp., of Midland, Mich. It makes good foam in spite of variations in physical mixing of formulations, or atmospheric conditions, the company says. C 79
1,3,4,-trifluoro-S-triazine in research and development quantities is available form Hynes Chemical Research Corp., of Durham, N.C. The compound is a volatile, highly reactive
triazine derivative for use as a chemical and pharmaceutical intermediate, the company says. C 80
ticles in the macromolecular range. C82
!0%
Ultraviolet light absorbers for plastics have been developed by National Starch and Chemical Corp., of New York, N.Y. The chemicals, named Permasorb, are functionally substituted benzophenones and are available in either monomelic or polymeric form, the company says. C 81
A
high-purity
sucrose
solution
/^-carotene beadlets for use as
a water-dispersible food color have been developed by the Chemical Division of Hoffmann-La Roche, Inc. The Nutley, N.Y., company says that the ^-carotene is in colloidal form and remains uniformly suspended. It is not affected by the specific gravity of beverages. The color produced ranges from yellow to orange. C 83
SINCLAIR PETROCHEMICALS ANNOUNCES NEOHEXENE
is
available from Elanco Products Co., a division of Eli Lilly and Co., of Indianapolis, Ind. According to the company, the solution is used as a density gradient for virus purification and ultracentrifuge separation of par-
• | I
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CH,•3 I
Cn3~C~"CH—CH2 1
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CH, July 26, 1965
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POLYMERIZATION-The absence of allylic hydrogen facilitates free radical homopolymerization or polymerization with other olefins.
Name: Company: Street:
City
Zone-
State
Your Title: YOUR FUNCTIONS (Maximum of 2, please.) A B C D E F
• Management • Process Research & Development • Product Research & Development • Basic Research • Plant Operations • Engineering Design & Construction
G • Analysis/Testing H • Marketing/Sales I • Purchasing J • Consulting K • Teaching—Student
CLIP COUPON—Fold along this line—fasten (staple, tape, glue) MAIL Your Industry:
A ( ) B ( ) C ( ) D ( ) E (" ) F ( ) G( ) H ( ) I ( ) J ( )
Engineering and Construction Food and Kindred Products Textile Mill Products Paper and Allied Products Government ' Chemicals and Allied Products Elastomers, Polymers, Plasticizers Drugs Detergents, Cosmetics, Specialties Paints, Varnishes, etc.
High-purity Neohexene is the latest addition to the growing family of new products available from Sinclair. The unique structure of Neohexene suggests areas of polymer and derivative preparation not heretofore available.
K ( ) Petroleum Ref., Asphalts, Lubricants L ( ) Rubber and Plastic Products M ( ) Independent Laboratories N ( ) Consultants 0 ( ) Primary Metal Industries P ( ) Fabricated Metal Products Q ( ) Machinery and Equipment R ( ) Transportation Equipment S ( ) Instruments and Controls T ( ) Education
FREE RADICAL ADDITION to carbon t e t r a c h l o r i d e and a c e t i c a c i d is accomplished in the presence of peroxides. ISOMERIZATION of Neohexene to tetramethyl ethylene may be accomplished simply by means of acid catalysis. HYDROBORATION leads to the formation of the primary alcohol of Neohexene. OXIDATION of Neohexene with molecular oxygen leads to good yields of the corresponding carbonyl compounds. EPOXIDATION is carried out by reacting Neohexene with peracetic acid.
Development quantities of 98% minimum purity Neohexene are currently available. For samples and literature write t o :
{Sinclair}
SINCLAIR PETROCHEMICALS, INC. Market Development Department 600 Fifth Avenue New York, N.Y. 10020 JULY
2 6, 1965
C&EN
47
