THE CHEMICAL WORLD THIS WEEK

Analytical Research Highlights Petroleum Refiners9 Meet ing C & E N REPORTS: American Petroleum Inst i tute Division of Refining M e e t i n g

Tl ' l .SA. - Most significant part of the pro­gram of the API refining division's six­teenth midyear meeting, as tar as the chei ι mal world is concerned, was the all-da) 16-papcr symposium on analytical re­search which opened the meeting. Two thirds of these papers dealt with instru­mental methods employing infrared and ultra.violet techniques for studying cata­lysts and fuel and lube oils.

T h e API subcommittee on emission spectroscopy has sponsored studies aimed to overcome limitations of spect rographs analysis of lube oils to permit application to used oils, oils of unknown base stock and unknown additive concentrates. Re­porting on results of these investigations, Ralph O . Clark, Gulf Research and De­velopment Co., said that the seven par­ticipating; laboratories studied the spectro­g raphs variables found in the Calkins and White method—sampling, excitation, densitometry, standardization, technique, and method of calculation—and although the objective of extending the utility of the method was not achieved, they were able· to determine optimum conditions for maximum precision.

A. new method for determinating vana­d ium ( a s a possible catalyst poison and corrosion accelerator) in residual fuel oils was described by J. B. Rather, Socony-Vaeuuni Laboratories, who read the paper in the absence of its authors. This method is particularly useful in petroleum labora­tories as the ash content of die oil is de­ten t lined m the course of determination ol the vanadium. A sample of the oil is carefully ashed and a 2 to 5 milligram portion of this ash is mixed in the ratio of I to 3 with a 1% titanium-silica mix­ture . T o this mixture is added approxi­mately twice as much spectroscopic graph­ite, and the resulting mixture is packed in a. graphite electrode and burned, yield­ing reproducible results on samples of oil containing O.00O4 to 0.35% vanadium, using the titanium as an internal standard. Th i s method is not affected by difference in itsh composition and provides a means lor correcting for variations in intensities of the emission spectra. The method may also he useful in studying corrosion of boilers fired with these oils and in geo­logical investigations of crude oil sources.

Kv a rapid and accurate spectrochemi-cal method, G. F . C. Wear of Standard Oil Development Co. reported in the au­thors ' absence that they were able to determine iron in used lubricating oils within the wide range of 3 to 3000 parts per million without varying the technique. To a homogeneous 20-gram sample of the oil is added one milliliter of the internal standard cobalt naphthena te solution; then

one milliliter of the resulting mixture is ashed directly on a specially designed electrode and the emission spectra is de ­termined. Since the amount of iron found in crank case drain ings is indicative of t h e amount of engine wear, this method may prove» useful to bodi engine designers and lubricant manufacturers.

In examining both new and used lube oils for metal contaminants, C. M. Gam-brill. Ethyl Corp., has developed two tech­niques accurate to within 1 0 % using special electrodes. With porous cup elec­trodes, barium, calcium, phosphorus, and /:inc additives can be determine in new oils. In the case of used oils, no t only the above but also lead and iron can be deter­mined by using rotating disc electrodes.

Automatic, recording ultraviolet instru­mentation was used lor development oi a new procedure for rapid estimation of tin-total aromatics content ol rioncrackeel petroleum fractions. This method, de­scribed by John F. Kinder, Sinclair, com­pares favorably with standard ASTM tests used by petroleum laboratories. Vernon Thornton, Phillips Petroleum Co., pre­sented the results of a study of the cor­relation bands in infrared spectra of pure paraffins, olefins, and alkyl benzenes .

In the evaluation of lubricating oils in service, J. B. Rather. Socony-Vacuum Laboratories, reported for the absent au­thors that a test for measuring t h e quantity of n-pentane and ben/one insoluble mat ter in oil has been des igned which is particularly applicable to measuring finely divided suspended matter in used lubricat­ing oils containing detergent additives. This rapid and inexpensive semimicro method requires only a one-grain sample, which is diluted with solvent containing a coagulant, enabling isolation of the in­soluble matter by centrifuging.

For the first time individual compounds formed within engines have been identi­fied. By using x-ray diffraction studies at the Fthyl Laboratories, Frances W. Lamb, first woman ever to address an API divi­sion oi refining meeting, has been able to determine the exact nature of engine de­posits and also determine t ha t they are formed at a much lower tempera ture than had previously been thought .

Three papers dealt vvidi oxygen deter­minations in organic materials. G. E. C. Wear , Standard Oil Development Co., has devised a new technique for directly de­termining oxygen in organic compounds by the use of an Unterzaucher-mano-metric method using a small sample. This manometr ic modification of the Unter-zaucher carbon-reduction me thod involves the oxidation of the carbon monoxide to carbon dicxide by means of copper oxide,

collection of the resulting carbon dioxide in a liquid nitrogen trap, and determina­tion of the carbon dioxide- manometrically in a standard volume. Morris Dundy, Texas Co., has developed a different tech­nique ior determinations ot the same sort, which also avoids the lalse high results obtained in the Inte izaucher method by the hsdrogen reduction oi iodine pent-oxide. The extraneous iodine is retained in an absorption tube containing crystals ot sodium thiosulfate Λ\Κ\ a suitable dry­ing agent. The sample can then be heated to elevated temperatures in a epiartz tube containing carbon black and an inert gas. The oxygenated material is converted to gaseous carbon mono\id<·, which is fur-ther changed to carbon dioxide. By ab­sorption of the carbon dioxide in a con­ventional Pregl micro absorption tube the percentage ot oxygen can be calculated.

Aimed at determining not the bound oxygen but the dissolved oxygen which might promote deterioration in petroleum fractions was the polarographic method reported by J. I I . Karchmer, Humble Oil and Refining Co., for the author, Maynard F. Hall, who was unable to be present. Based on the reduction of the oxygen molecule at a dropping mercury electrode in which the amount of current caused to How by the reduction is directly propor­tional to the amount of dissolved oxygen present, the method is capable oi deter­mining a few parts per million and is also applicable to organic lifiuids other than petroleum fractions. The test requires one to two milliliters of sample and a complete determination can be made in 10 to 15 minutes.

Although there was a separate sym­posium on treatment of refinery waste water, two analytical methods for use in approaches to this problem were presented in the analtyical research symposium. One of these was a semimicro benzene extrac­tion method requiring less dian an hour per determination and readily adaptable to multiple simultaneous tests. This method was described b y A. F . S. Mu­sante, Sun Oil Co. For determinations of less than 10 parts of phenol and 100 parts of oil per billion parts of water , C. E . Heaclihgiuii, Atlantic Refining Co., uses an infrared spectrophotometric procedure.

As greater emphasis is placed on chemi­cal processing b y the petroleum industry, waste water disposal problems are chang­ing in character . Among the papers on treatment of refinery waste waters was a description by H . Scliindler of a chemical treating plant in successful operation at the Daugherty refinery division, L. Sonne-born Sons, Inc. Two types of waste water arc that originating at t he plant for con­verting sludge to sulfuric acid and coke, and containing sulfur dioxide, and that from the white oil and petroleum sulfo­nates plants. This latter may be acidic or alkaline and contains water-soluble petro­leum sulfonates and some emulsified oil. By continuously combining these wastes

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THE CHEMICAL W O R L D THIS WEEK

to produce a blend with a pH of 5, neu­tralizing the mixture with hydrated lime to precipitate the petroleum sulfonates as water-insoluble calcium salts, and con­tinuously settling, it is possible to dis­charge 200,000 to 250,000 gallons per day of colorless neutral effluent free of oil.

liiwiïiiMiîiia

Only one full-time operator is required. For outstanding service to the API in

the fields of automotive research and con­servation of natural resources, G. G. Ober-fell, retired vice president of Phillips Petroleum Co., was awarded a certificate of appreciation by the division of refining.

More Acetylene t© Be M a d e With UCC Ox ida t ion Process /^PF.KATIONS involving a radically differ-"̂>^ ent chemical process for the produc­

tion of acetylene, used commercially for over a year at the Texas City plant of Car­bide and Carbon Chemicals Co., are due for expansion. The method employed is a partial oxidation process involving the high temperature reaction of methane and oxygen. The two highly reactive feed ma­terials are combined chemically to produce a gas mixture containing essentially acety­lene, with smaller percentages of carbon dioxide, methyl acetylene, diacetylene, vinyl acetylene, and other residual gases.

The Texas City unit is the first com­mercial installation of the partial oxidation process for acetylene production in the United States. It also has the largest acety­lene production capacity of any unit in the United States by any process other than from calcium carbide. Present plans are that the capacity of the Texas City unit will be greatly enlarged, but this will of necessity be subject to the receipt of governmental priorities and certificates.

The selection of the partial oxidation process for the manufacture of acetylene is the result of years of experimental work by various units of Union Carbide and Carbon Corp. covering several types of electric arc and thermocracking processes. In any electric process for the manufacture of acetylene, the electrical energy con­sumption represents a major item in the cost of operation. All known electric processes lor acetylene manufacture, in­cluding the various electric arc processes, require as much electric power per pound of acetylene produced as does the calcium carbide method. In addition, other electric arc processes for acetylene result in the production of an impure gas mixture, in which the required purification of the acetylene represents a difficult step involving additional operating costs. The partial oxidation process, on the other hand, requires appreciably less power than any known electric process for producing acetylene.

The Texas City acetylene installation in­cludes a purification unit which separates the acetylene from the gas mixture and raises the acetylene to high purity. After purification, the acetylene is used in the manufacture of vinylite resins, important plastics in the defense program.

V O L U M E 2 9 ( N O . 2 0 » » »

Initial experimental work on the partial oxidation process was started by Carbide and Carbon Chemicals Co., a division of UCC in 1945. This work proceeded through various stages starting with small single tube reactors, then progressing through the development of a commercial scale reactor and a pilot ρ ι irifi cation unit, and finally culminating in the construction of the present unit at Texas City. The unit was designed and built through the combined efforts of Carbide and Carbon and Linde Air Products Co., both divi­sions of Union Carbide. The completed plant utilized C&C's skill in high tem­perature chemical reactions and separa­tion of hydrocarbon gas mixtures, and the experience of Linde in large-volume oxy­gen production.

Used by Germans One installation utilizing the principle

of partial oxidation was built in Germany during World War II. The German in­stallation, however, was considerably smaller in capacity than the Texas City unit, and included no provision for puri­fication of the acetylene, which represents one of the difficult parts of the process.

It is expected that the partial oxidation process will play an important part in the chemical field since acetylene gas is a valuable raw material in the manufacture of so many industrial chemicals, such as vinyl chloride, acrylonitrile, and acetic acid. While many of these chemicals are also made from ethylene, there are several that are made from acetylene exclusively. These include vinyl acetate, trichloro-ethylene, and chloroprene and its polymer neoprene. Commercial operation of the partial oxidation process, however, prob­ably will be confined to large-scale in­stallations in areas having plentiful natural gas reserves, and to locations where the acetylene gas produced can be utilized di­rectly adjacent to the point of manufac­ture. At Carbide's Texas City plant the necessary basic materials, methane and oxygen, are available at relatively low cost. The process is, therefore, a natural out­growth of the company's need for acety­lene for the production of important indus­trial chemicals—especially its resin inter­mediates, vinyl chloride and vinyl acetate. The additional acetylene to be produced

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P A B S T A N D A R D 1 Z E D · 1951