INDUSTRIAL AND ENGINEERING CHEMISTRY
916
Its cold test was +5O F., a t which point it was perfectly clear. As according to the physical characteristics already determined this oil seems to correspond with high-grade lubricating oils, the possibilities of vapor-phase polymerization as a source of lubricants should be considered. It is possible so to regulate the conditions of cracking that the substances which polymerize to form them would be present in greater proportions. This point can be discussed in greater detail when the chemical nature of the polymers is more definitely known. COMPARISON OF TREATED AND UNTREATED PRODUCTS I n order to obtain a basis of comparison between products treated by this process and the corresponding untreated products, the following procedure was adopted. Equal portions of the same cracked distillate were run at the same time and under the same conditions through similar glass towers, one containing the catalyst and the other the same weight of Ottawa sand. To assure equal fractionation, both distillations were carried to the same point, above the desired end point; after which each polymer fraction was added to the Corresponding distillate and the mixture re-run, with a LeBel Hennfnger c & n n , to the same end point in each case. A comparison of the products shows: 1-There is no difference in the Engler distillations. 2-The specific gravity of the treated product is slightly higher than that of the untreated; representative figures are 0.7592 as against 0.7572; another case gave 0.7499 against 0.7467. 3-The color of the treated distillate is usually better when freshly prepared; it is always much more stable than the untreated. 4-The unsaturation, as measured by the sulfuric acid absorption method, is not appreciably different. This does not vitiate the conclusion that the more unstable unsaturated compounds are removed by polymerization, since the amount of polymer formed indicates that there would be a difference amounting to about 0.5 per cent, which is unmeasurable by this method. 5-The iodine number of the treated distillate is slightly lower than that ot the untreated:
Vol. 16, No. 9
The yield in this catalytic run was 286 barrels per ton of fuller's earth. CONCLUSION It is possible by vapor-phase treatment with an adsorbent catalyst, such as fuller's earth, to produce satisfactory gasoline and burning oils from pressure distillates. The advantages of the process over current practice are: 1-The apparatus and operation are simple. 2-The material used is available and inexpensive. 3-Finished products may be run directly from the cracking apparatus, except in the case of burning oils, where a subsequent doctor treatment may be necessary. 4-The losses are only a fraction of those obtained with sulfuric acid. 5-Burning oils obtained are superior to those obtained by acid treatment.
With the vapor-phase catalytic process success has also been met in stabilizing certain straight-run products, such as gasolines from California crudes, which are otherwise unstable.
Rapid Determination of Phosphorus in Phosphor Bronzes' By Leif Lindemann KONGSBERG VAABBNFABRIK, RONGSBBRD, NORWAY
OMPLETE oxidation of the phosphorus cannot be accomplished by means of nitric acid alone, although many of the published methods are based on the quantitativeseparation of phosphorus along with the metaStannic acid. This new determination is dependent upon the complete oxidation of the phosphides, preventing the hydrolysis of the tin and the precipitation of ammonium phosphomolybdate. Treated Untreated Place 0.5 gram of the malleable bronzes or 0.2 gram of the A 09.8 101.7 cast phosphor bronzes in a small beaker. Add 25 cc. of 100.1 101.8 100.0 102.1 hydrochloric acid (specific gravity 1.12) (approximately 5 100.2 102.0 parts water to 7 parts concentrated HC1) and 5 cc. of nitric Av. 100.0 Av. 101.9 B 87.5 94.5 acid (specific gravity 1.2), cover with a small watch glass and 88.6 93.7 warm gently until action commences; then remove from the AV. 88.0 Av. 94.1 heat until action slackens. (The reactionmust not be allowed In both cases the difference between the two is well outside to proceed too violently.) When solution is complete, heat the experimental error, as shown by the checks obtained, and is of the order expected from the small amount of polymer formed. nearly to the boiling point and evaporate the solution for 10 6-The gumming test is always greatly reduced by treatment. minutes to remove chlorine, dilute with 50 CC. of cold water, 7-Sulfur is not appreciably reduced when the catalyst is neutralize a little with 10 cc. of dilute ammonia (1: I), and a t fuller's earth alone. Fuller's earth with porous metals or metallic Once add 50 cc. o f a regular molybdate solution made by oxides mixed with it, or mounted on it, is more satisfactory. and loo adding to looe a m s o f mo1ybdicoxide400 cc*Of Kerosenes from cracked distillates made from gas oils moderately high in sulfur must be doctor-treated after the catalytic dis- CC. of concentrated ammonia and pouring the cold so1utiq.n tillation, where the clay alone is used. With high-sulfur oils, slowly, with constant stirring, into 1 liter of nitric acid (specific such as unmixed Mexican cracked distillates, the writers have gravity 1.2). there is any arsenic in the sample, been unable to get satisfactory results, even as regards stability not take place at a temperature of color, without the addition of a metal, except a t the expense the precipitation higher than 40' C. of lower yields per ton of catalyst. &-Burning (kerosenes). The treated distillate always gives Combined with the alkalimetric determination the method a burn test much superior to either the untreated or acid-treated determination the described is very rapid, F~~a distillates. Often the catalytically treated distillate passes the precipitate should be dissolved in dilute ammonia on the filter long-time burning specifications, which is unusual for a refined oil prepared solely from cracked products. One such case is and precipitated again with a little nitric acid and molybdate given below, which is especially interesting because of the differ- solution. ence in sulfur content between the acid-treated and catalytic B~ oxidizing the escaping gases in a nitric ac~d-potassium oils and the difference in their burn tests. Both samples were Permanganate solution by dissolving fine borings as dedoctor-treated * after the treatment mentioned, and the acidscribed, the writer has never found any phosphorus escaping treated sample was in addition clayed. Catalytic Acid-treated as hydrogen phosphide. Gravity Viscosl,ty/6Oo (Saybolt) Corrosion Doctor Color (Saybolt) Unsaturated (per cent) Sulfur (per cent) Long time burn
42.0° Bd. 485 sec.
Slight Sweet t-20
12.1 0.070 Yes
.
42.7OB6. 467 sec. None Sweet
ig.4 0.045 No
C
1
Received April 30, 1924.
New T a r 8 Effective in Poland-The new Polish tariff became effective a t the end of June, and provides for a reduction in the duty on textiles, sole and upper leathers, fertilizers, scrap iron, and paper.
