July, 1929
ISDCSTRIAL A S D ESGINEEEZING CHEXlSTRY
sition of the final prodiicts. It is an ambitilms project. The result of the first two years’ work has been published in part. The projerts in force for the third year contain a considerable numbw of iteins of great interest t o the cracking section of the industry. One of the difficulties in fundamental research o n petroleum and its products lie. 111 the differences betlveer- crude oils. The properties of a crude oil or of its products before and aftpr cracking are distinct from those relating to another oil; still oils of a similar type will yield similitr products. Beyond that each individual crude oil must be separately investigated. It is possible that when cracking conditions reach the upper temperature limit for the production of liquid products in reaqonable quantity, the products obtained from almoqt any raw oil rvill b~ similar, but under liquid phase or semi-liquid pliase conditions the products of cracking may vary enormously, arid this is due wholly to tne chemical composition of the raw mnterial. Effect of Cracking on Engine Test of Oil The effect of different conditions of cracking on the engine test of an oil is interesting. A shale retorted in the usual way produced gasoline. kerosene, gas oil, and wax distillate. The gasoline had an antiknock value of +0.1 equivalent to an
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addition of 6.6 per cent of benzene t,o the standard zero spirit. The gas oil cracked in the liquid phase produced a gasoline with nn antiknock test of -0.1 and the gas oil and wax distillate when passed through a vapor-phase cracking unit produced a gasoline which gave an engine test equal t o 60 per cent of berizene in a straight-run spirit, the same straightrun spirit being used as a zero standard in all cases. Literature Cited (1) (2) (8) (4) (5) (6) (7)
(8) (9) (10)’ (11) (12) (13) (14) (15) (16)
Beale, Coxon, a n d Dunstan, British P a t e n t 293,889 (July 16, 1928). Birch, IND.ENG.CHEM., 20, 4 i 4 (1928). Brame and Hunter, J . Inst. Petroleum Tech., 13, 794 (1927). Brooks, I N D . EX. CHEZI., 18, 1198 (1926). Brooks, Non-Benzenoid Hydrocarbons, p . 157. Brownlee, British Patent 141,753 (1971). . CHEX, 20, Burrell, Fuel Science Practrce, 7, 416 (1928); I N D ENG. 602 (1928). Dunstan, Cantor Lectures, R o y . S O L .A r t ? , 1928. Dunstan and Pitkethly, J . Inst. Petvoleurn Teciz., 10, 728 (1924). Egloff, World Power Conference, London, 1828. Garner, J . I n s l . Pelroleurn Tech., 14, 695 (1928). Hill, Henderson, and Ferris, IICD. EXG.CHEM.. 19, 128 (1927). Moore a n d Hobson, J . Inst. Pelroleurn Tech., 11, 589 (1925). Morrell and Egloff, Oil Cas J , 2 5 , 156 (1937). Ormandy and Craven, J . Inst. Pelroleurn Tech, 11, 533 (1925); 13, 311, 8 4 4 (1927). Sachenan and Tilitscheyew, Petvoleurn Z., 23, 521 (1927); J . Insl. Pelroleurn T e c h . , 14, 761 (1928).
Triethanolamine Oleate for Oil Sprays’ George L. Hockenyos DEPARTMENT OF HORTICULTURE, USIVERSITYO F
ILLIXOI$
URBANA, ILL.
HE last fern years have seen a rapid development in the with comparatively large droplets in suspension has been use of oil emulsions for insect control. This may be debated for some time. D e Ong(2) concludes that the work of attributed to the effectiveness, cheapness, and con- Griffin(5) hae decided the question in favor of the quick-breakvenience.of oil emulsion sprays and t o the fact that certain ing type of emulsion. The recent introduction on the market of Triethanolamine scale insects such as the San Josi. scale seem t o have developed an immunity t o the lime-sulfur sprays so long considered the in commercial quantities and a t a comparatively low price led to its use as a base for cutting oils in the form of the oleate standard control measure. Deyelopment in this field has been along three line.: (1) soap. The facts that this soap is reputed to emulsify large boiled oil emulsions made by boiling cheap alkali soaps with quantities of oil and that it is said t o have good penetrating oil and water; (2) cold mived emulsions prepared by emulsi- or softening qualities when used as a base for shaving soap fying the oil in water by use of an inert material as calcium suggest its desirability as an emulsifying agent for spray caseinate, glue, or hydroxide of copper or iron; 1:3) miscible emulsions and as a base for miscible oil sprays. oils, which when stirred in water, become emulsions. The miscible oils have found special use in greenhouse in- Properties of Commercial Triethanolamine and Its Mixture with Oleic Acid sect control, where the amount used a t any one time is likely to be small. Britton(l)* classifies the miscible oils into four “Commercial Triethanolamine” is the trade name for a groups: (1) lubricating oils with sulfonated vesetable oils product containing approximately 70 to 75 per cent triethanoland alkali; (2) sulfonated mineral oils; (3) lubricating oils amine, 20 t o 25 per cent diethanolamine, and 0 to 5 per cent with soap dissolved in phenols; (4) lubricating oils with soap rnonoethanolamine. It boils a t approximately 277” C. and dissolved in alcohol. 150 mm. It is a nearly colorless liquid of faint, ammoniacal The grade of oil used in any oil sprays should vary with the odor, fully soluble in water, and strongly basic. Mixed with nature of the insect and plant and with the season. I n gen- oleic acid it forms a stiff jelly which is easily liquefied by gentle eral, light oils are more destructive t o both insect and plant, heating. but are effective for only a short time; heavier oils, on the The soap is soluble in mineral oils, but considerable water other hand, are effective for a longer time and the cumulative is produced by the reaction of the Triethanolamine and oleic effect on both plant and insect is greater. For winter spray- acid, and some is present in both reagents. This settles out ing of dormant plant s heavy lubricating oils h:tve become quickly from oil solutions upon standing, but may be removed standard practice, nhile for soft-bodied insects, such as by boiling in a n evaporating dish. When foaming ceases, aphids attacking tender summer foliage, oils as light as kero- heating should be stopped to prevent decomposition of the sene are used. For most summer spray probleins and for soap. This soap-oil solution is not clear, but is quite satisgreenhouse pests the Comparatively light lubricating oils of factory for preparing emulsions. the highly refined, saturated type seem the b w t answer. The question whether an emulsion should be quite stable Preparation of Emulsion with fine droplets in colloidal solution or “quick breaking’’ Small quantities of emulsion for experimental purposes 1 Received January 31, 1929 e Italic numbers In parenthesis refer t o literature c:ted a t end of article. were made by putting the soap-oil solution in a large test
T
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I N D USTRIAL A N D EXGINEERING CHEMISTRY
tube, adding the desired amount of water, and inserting a test-tube brush. By plunging the brush back and forth through the solution for a few seconds, an excellent emulsion was produced. Equally good emulsions were produced by simply putting the oil, Triethanolamine, and oleic acid separately in the water and emulsifying. A little experimentation showed that excellent miscible oils could be made by melting the Triethanolamine-oleate soap and boiling out the water, adding oil and alcohol, and clarifying with oleic acid. Quantitative Relationships OIL EmmroN-In each of several test tubes 1 cc. of oleic acid was placed. Amounts of Triethanolamine varying from 0.25 t o 1.5 cc. were added in separate tubes and 5 cc. of oil and 20 cc. of water added. These were emulsified and diluted to 5, 2, and 1 per cent emulsions. The maximum stability was obtained by using the Triethanolamine and oleic acid in the ratio of 3 to 4. It was also found that an amount of benzene equal to the amount of oleic acid used increased the solubility of the soap in the oil and made a better emulsion. Experiment showed that perfectly stable emulsions could be made with 1 part Triethanolamine, 1.2 parts oleic acid, 2 parts benzene, and 150 parts mineral oil of the heavy paraffin oil type. Even with 250 parts of this oil the emulsion was stable enough t o be used in spraying operations, provided soft water was used. With hard mater not more than 125 parts mineral oil should be used. A light grade of paraffin oil gave nearly as high emulsifying values, but a light oil sold as “flushing oil” gave values of only 75 parts of oil to 1 part Triethanolamine and 1.2 of oleic acid. No benzene was used in this case. Para-dichlorobenzene and carbon tetrachloride were found to have but slight deleterious effect on the emulsion when dissolved in any of the three types of oil mentioned up to 10 per cent by volume for the carbon tetrachloride and 10 per cent by weight for p-dichlorobenzene, The value of such insecticides applied in oil solution as sprays remains t o be seen. Preliminary tests showed these emulsions to have excellent spreading and adhering qualities, even on the waxy-leaved plants such as cyclamen and rose. Best adhesion and spreading is obtained if not more than 10 to 20 parts of oil are used for 1 part Triethanolamine and 1.2 parts oleic acid. If the soap is used in not less than this proportion wax-protected insects are thoroughly wetted. MISCIBLE OIL-In determining the use of Triethanolamine oleate in miscible oil production, the method of testing presented by Hart(4) was followed. It was first necessary, however, to find the proportion in which Triethanolamine and oleic acid reacted. This was done by mixing in various proportions and boiling the soap to free from water. It was soon found that a clear soap solution that dissolved readily in oil, leaving no water to settle out, was obtained when 1 part of oleic acid reacted with 1.2 to 1.3 parts of Triethanolamine. A proportion of 1 part to 1.25 was taken as the average value and this soap was used in all further work. It was found that 1 part of soap in 4 parts of heavy paraffin oil required 2 parts of alcohol to make a uniform fluid solution. Absolute aIcohol gave a clearer mixture than did the 95 per cent commercial and was used in all the experiments to determine the values outlined by Hart. An attempt to determine the oleic acid miscibility number by Hart’s method indicated that it was around 80, but the color of the soap tended to hide the point of clearing. It r a s then decided to consider the minimum oleic acid emulsion number as being equal to the oleic acid miscibility number. The four values for heavy paraffin oil were found to be:
Oleic acid-miscibility number Oleic acid-emulsion number Emulsion spread Mineral oil number
Vol. 21, No. 7 1;; 77 1920
For the light paraffin and flushing oils the first three values were the same, but the mineral oil numbers were 1560 and 720, respectively. For spraying purposes these mineral oil numbers do not indicate the correct amount of oil to use with the soap, because the hard water used in spraying tends to use up part of the soap. Since absolute alcohol gave a better oil solution than did 95 per cent alcohol, it was thought desirable to substitute some other water-free solvent for the alcohol. Of several materials tried only carbon tetrachloride gave good results. This liquid was not nearly so good as alcohol, however, in the light oil. I n the heaiy oil it gave fairly good results. Conclusions These experiments indicate that an excellent miscible oil may be made by boiling 5 parts of oleic acid with 6 parts of Triethanolamine and adding 15 parts of free oleic acid and 5 parts of alcohol. This may then be dissolved in up to 40 parts of light or 100 parts of heavy paraffin oil. Preliminary experiments show no injury to plants other than the oily gloss which usually results from oil sprays. Good kills on mealy bug and red spider resulted both with oil emulsion alone and with oil emulsions having p-dichlorobenzene or carbon tetrachloride dissolved in the oil. The only plant injury was due to excessive dosage of the light flushing oil, which is not so highly refined as the other two oils. The most promising method of using the very light oils seems to be to make a solution of 3 parts of Triethanolamine, 4 parts oleic acid, 6 parts carbon tetrachloride, and 30 parts of oil. Such a solution is uniform though rather cloudy. It does not settle out or separate for several days and, although . not miscible in water, it is very easily emulsified. If these materials are to be made on a commercial basis, they should have their acid and alkali values checked on each shipment by the method suggested by Trusler.(S) Further Work The highly important questions of stability in hard waters and of relative toxicity to plants and insects have not been answered in this preliminary work. The writer hopes to continue the investigation and to include some work on the use of oil emulsions as carriers for oil-soluble, water-insoluble materials, such as p-dichlorobenzene. Literature Cited (1) Britton, J . Econ Entomol , 21, 419 (1928). (2) De Ong, I b z d , 21, 697 (1928). (3) Griffin, Richardson, and Burdette, J Agv. Reseavch, 34, 737 (1928). (4) H a r t , IND. ENG.CHEM.,21, 25 (1929). (5) Trusler. J . 012 6’Fat I n d . , 5, 338 (1928)
Manufacturers Open Paper Research Laboratory Last year the rag content paper manufacturers sent two research associates to the Bureau of Standards to work on some fundamental research problems connected with the permanence of high-grade papers. As an outgrowth of that work, these manufacturers have now opened an up-to-date, well-equipped paper research laboratory a t 44 Vernon St., Springfield, Mass. This laboratory will specialize in the study of fundamental problems relating to the industry, giving particular attention to the new developments in the chemistry of cellulose and the extension of chemical control in the manufacture of high-grade papers for permanent records. The laboratory is in charge of Jessie E. Minor.
