I X D U S T R I A L A1YD EKGIA-EERTNG CHEMISTRY
542
Vol. 21, No. 6
The distillate is finally distilled in the presence of steam. With some types it is desirable to stabilize the overhead product from the distillation by using a small amount of fuller’s earth or activated clay in the still. Distillation over alkaline solutions and mild polymerizing agents also assists in stabilizing the final distillate and lowering the gum content.
to prevent condensation of the steam. A temperature of 121” to 135” C. is satisfactory. The final product may be further stabilized by treatment with a small amount of fuller’s earth and is improved in odor by subsequent washing with a dilute solution of sodium hydroxide. After a final waterwashing the treatment is complete.
Table XV-Pressure-Distillate Oil Derived from Cracking Hardwood Tars (A. S. T. M.) A. P. I. g r a v i t y . . .................................... 12.4
Table XVI-Distillation Analysis of Distillate from Hardwood Tars with Motor Fuel Boiling Range (A. S. T. M.) A. P. I. g r a v i t y . . .................................... 15.4
Specific gravity. ..................................... Initial boiling point:
.............................................. O C ................................................. O F . . .
En? O
0,9833
Specific gravity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Initial boiling point:
127 53
oint
8C . .. . ,.. i. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ........................................................
Per cent over 10 20 30 40 50 60
70
73.1 79.8 Water, per cent
. .
11.2
81 88 109 166 192 199 208 ~ 210 216
147
End aint.
02.. ............................................... 437 . . . . . . . . . . . . . . . . . . . 225
420 216
OC. . . . . . . . . . . . . . . . .
HzO
c.
F. 177 190 228 331 378 391 4nfi ~ 410 420
0.9632
......
cc.
Per cent omr
22 32 36
5 10 15 20 25 30 35 40 45 50
. .
The final product may be treated with a dilute solution of sodium hydroxide, which improves the odor. Final contact with a small percentage of fuller’s earth also assists in the stabilization. As an example of the treatment of a cracked distillate from wood tars, the following is shown for pine tar distillate. The cracked distillate is treated with 10 to 15 pounds of 60 per cent concentration sulfuric acid per barrel of distillate. The sludge is withdrawn. The distillate is then water-n-ashed and neutralized with about 2 per cent of a 10 per cent solution of sodium hydroxide alone or containing litharge dissolved in it. The treated cracked distillate is distilled over about 1 pound of fuller’s earth per barrel, using top steam and maintaining the temperature just above that required
F.
C.
166 173 180 187 203 245 293 318 345 357
74 78 82 86 95 118 145 159 174 181
c.
F.
Per cent over 55
366 375 381 388 39 1 395 402 411 431 437
60
65 70 75 80 85 90 95 98
186 191 194 198 199 202 206 211 222 225
Table XVII-Distillation Analysis of Gas Oil (A. S. T. M.) A. P. I. g r a v i t y . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.O Specific gravity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Initial boiling paint:
E F. C.
....
432 222
....
End point: O 0
F. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Per cent over 5 10 15 20 25 30 35 40 45 50 Trace of coke ~
F. 435 437 439 441 444 447 450 453 456 458
C.
Per cent over 55 60 65 70 75 80 85 90 95 98
O
1,066
F.
462 468 473 479 486 497 514 539 549 556
556 291 O
c.
239 242 245 248 252 258 268 282 287 291
~~~
Sulfonated Oxidation Products of Petroleum as Insecticide Activators’ M. T. Inman, Jr. KAYLABORATORIES. INC..WEST NYACK, N. Y.
HE continuous search for cheaper and more effective methods of controlling insect pests has given the chemists a very enticing problem. To a chemist not in intimate contact with entomological problems a general spray mixture for all troubles-a cure-all-would seem t o be the product to develop. Upon close study of the variables in spraying the many species of destructive insects, a product that would increase markedly the efficiency of any specific control would be well worth while. I n view of this fact a thorough study of the application of the oxidation products of petroleum to the insecticide field has been conducted for the past four years in cooperation with state entomologists and the Crop Protection Institute. As a result of this work a definite procedure in attacking softbodied sucking insects, such as aphis and leaf hoppers, was developed. By the addition of chemically treated oxidation products of Pennsylvania gas oil to a solution of nicotine sulfate, the efficiency of the poison was strikingly increased. For example, where these oxidation products have been
T
%ReceivedMarch 1, 1929.
added, a t the rate of 1 to 200, to nicotine sulfate spraying solutions, a satisfactory kill has been obtained with only onethird to one-fifth of the nicotine commonly employed when soap is used as a spreader. The underlying principle is, briefly, the increase of the efficiency, or the activation, of an insecticide by bringing about certain physical changes in the resultant spray mixture. This group of chemically treated oxidation products of Pennsylvania gas oil has been termed “activator” in explanation of its performance in the insecticide field. Properties Desirable in a C o n t a c t Spray
A spray intended for sucking insects should be: (1). Safe to foliage under all climatic conditions a t all effective dilutions with allowance for ample margin of safety. (2) Easily measured and handled. (3) Readily miscible with a variety of natural waters. (4) Toxic to the most resistant individuals of the species of insect sprayed. The final kill may be affected by the follow( a ) absolute lethal effect, ( b ) coverage on the ing properties:
liZ'D GSTRIAL AA;D ENGIATEERING CHEMISTRY
June, 1929
foliage, ( c ) adhesion to the insect's body, ( d ) penetration into an insect's body, ( e ) service as a carrier of other spray materials.
The Activator Principle
The exact function of spreading and wetting has not been clearly defined. One thing certain is that a material causing death of insects will work the more quickly and surely if it is able to make a definite close contact with the vital organs. Picturing, therefore, the waxy body of an aphis, what is the best method of introducing the insecticide? The spray mixture holding the toxic material must be of such rhemical and physical structure as to reach and enter the tracheae of the insect and thence gain access to its vital cells. Whatever may be the mechanism by which the poison thus conveyed is able to bring about the insect's death, the fact remains that the performance of the insecticide is profoundly influenced by the physical nature of the spray liquid. The function of the activator is to bring about precisely such desirable effects. The principle that it serves may be summed up as follom: (1) To wet the foliage and the insect's body effectively; (2) to carry the insecticide; (3) to penetrate t o vital cells; and (4) to exhibit in itself strong tosic qualities againqt the insect. Eritomological Technic
In studying the effwts of activators and the toxic substances combined with them, every care has been taken to secure maximum accuracy. Such factors as temperature, humidity, and the like have been recorded in detail throughout. In the laboratory experiments many duplications have been made, using thousands of insects. In all cases laboratory studies have been followed hy long series of field experiments under different climatic and geographical conditions. These results have been repeatedly checked and counterchecked. A complete entomologiizal report of this extensive research will be published shortly by the Crop Protection Institute. Process
A great number of samples have been made for field tests in this research. Eniulsions of oxidation products of various boiling-point ranges and the addition of chemical groups have given a great variety of results. Although sevtml of these have been encouraging, the product formed by the following process has given most satisfactory and consistent results in field tests: OSIDATIOX-A straight distillate of Pennsylvania crude of 38" BB. was reacted with oxygen by the James catalytic vapor phase oxidation process.2 The oil was vaporized and passed over a catalyst with a definite volume of air after 2
James, Tuans. A m In-2. Chem. E n g , 14, 189, 201 (1922), Bitler
a n d James, Chem. Met Eng , 35, 156 (1928).
543
which the oxidation products were condensed. This condensate consists of a mixture of alcohols, aldehydes, ketones, and acids, saturated and unsaturated, both simple and complex, together with unaltered hydrocarbons. The proportion in which these constituents were formed in the mixture can be controlled quite accurately by the screen temperature and oil and air flow. I n the final product about 75 per cent of the hydrocarbons have reacted. SULFONATION-SU1fUriC acid was added slowly to the oxidized gas oil, the mixture being cooled by means of a water jacket. The reaction mixture was then decomposed with water. This step removed the excess of sulfuric acid and hydrolized a great percentage of the sulfonates and all the sulfates. After settling, the dilute acid was drawn off. The product was then neutralized with sodium hydroxide and allowed t o settle to remove the salt solution. Chemical a n d Physical Properties
The product contains about 40 per cent oxygen, analyzed by the combustion method, and about 1.5 per cent sulfur by bomb and Eshka's mixture. Empirical chemical tests have been found quite satisfactory for control and assurance of a uniform product. The product has been held a t 50' and -18" C. for varying lengths of time with no evidence of chemical change. The physical properties, with particular reference to insect control, have been studied quite thoroughly. The activator is a clear maroon-colored liquid. It is easily miscible with water, forming an opalescent emulsion. The wetting, spreading, and other allied entomological properties have been outlined above. I n this regard a 1 per cent solution of the product is of itself toxic to various aphids, leaf hoppers, and red mites. The greatest field for service of this material is as an activator. For example, nicotine sulfate, not fully effective alone, is commonly used in the proportion of 1 to 800 with soap added as spreader. By omitting soap and using 0.5 per cent of the activator instead, the necessary concentration of nicotine is reduced as low as 1 t o 4000. F u t u r e Possibilities
Tests indicate that other materials of a high order of toxicity, such as pyrethrum, can be made more efficient by using an activator, although data in hand are not so extensive as those referring to the nicotine combinations. It is difficult a t this time to predict the extent to which the principle of activating insecticides will affect the control of other insects and the development of other spray materials. Its numerous applications should provide many interesting problems.
Termite Investigations Committee The extensive damage done by the termite, or white ant, has led to the formation of the Termite Investigations Committee, which will be supported in its investigations by a large number of Pacific Coast corporations. The general plan is to combine all the data relating to termites and termite damage on the Pacific Coast through the coljperation of these contributing organizations. A large number of scientific investigations will be furthered and directed by an advisory council consisting of members of the faculty appointed by the president of the 1.iniversity of California. A three-year progra~nis planned under eleven subcommittees chosen with respect to special phases of the investigation. The chairman of the subcommittee on chemistry is Merle Randall, University of California, Berkeley, Calif., and under this committee a laboratory has been established a t the university, with T . c. Doody as chemical engineer. This laboratory will study the
relative merits of chemical methods of termite control and the effectiveness of wood preservatives against these pests. The California State Insecticide Laboratory, directed by Firman Thompson, is in cooperation. Since the problem is of general interest, some of the tests will be conducted under the severe conditions of the Panama Canal Zone by T. E. Snyder, senior entomologist of the Bureau of Entomology, Department of Agriculture. The subcommittee on chemistry is anxious to gather the fullest possible information relative to preparations or methods for termite control. The names, addresses, and claims of manufacturers or agents for such preparations, and any service records available on their products as applied to termites are especiaIly desired. Any information on termites will be gratefully received and Put in the hands of the Proper subcommittee.
