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T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
sugar and starch; amyl alcohol is produced by the fermentation of protein substances, and there is a bacillus for obtaining butyl alcohol from starch. The question accordingly arises, why should we not find or develop cultures for the production of propyl alcohol, and, especially, methyl alcohol? T t is known that n-propyl alcohol is among the products of the fermentation of starch by the anaerobic Amylobacter butylicum and A . aethyliEUWZ of Duclaux, and that it is also a secondary product of the alcoholic fermentation by Sacchaiomyces, occurring in most fusel oils; but no technical process has been devised for its zymochemical production. A similar condition exists with respect to methyl alcohol, which is among the products of the fermentation of glycerol by Bacillus boocopricus, of the bacterial fermentation of calcium glycerate, and of the fermentation of the juice of the sugar cane by a special (wild) yeast; perhaps extensive research would eventuate in the development of a commercially operable process. The desirability of systematic investigation of this nature suggests the initiation of attempts to find microorganisms for making certain higher alcohols in the factory. Some of these alcohols are excellent waxes, and, t o illustrate, cetyl alcohol and melissyl alcohol are too exorbitant In cost when separated from spermaceti and beeswax, respectively. It is indeed probable that a number of processes now based upon chemical reactions could be more efficiently conducted by bacterial agencies. The chemistry of the production and utilization of vegetable oils is susceptible of expansion in several interesting and profitable directions: I-Extracting oil by solvent processes which will make greater yields and yet not extract deleterious substances along with the oil, and which will not be subject to great fire risk. 2-Treating the residue (cake) t o free it from all traces of the solvent, t o make it a proper cattle feed. 3-Rkfining oils by methods causing least possible loss, and producing the highest grades of edible oils, tasteless and odorless, both liquid and solid 4-Utilizing the by-product of relining to the best advantage t o recover the fatty acids free from objectionable color and from foreign matter; and the further transformation of the finished product into the finest soaps and other useful merchandise. 5-Making cottonseed flour and bread therefrom that will be an acceptable and merchantable product. 6-Treatment of recovered fiber t o make an infinite variety of profitable merchandise. Research in the margarine industry will continue to have for its object the production of a food identical with butter, and it will involve the investigation of the following problems: I-The production of a synthetic fat similar in composition to a butter fat, or of a mixture of natural fats physiologically identical with butter fat. 2-The production of an artificial or synthetic milk. 3-The production of a suitable butter flavor. 4-The production of a margarine not inferior to butter in vitamines or accessory substances.
It has been well said that “the dyestuff factory cannot progress nor even exist upon the cast-off products of other factories. The history of the dyestuff industry shows that financial SUCcess follows the research laboratory.” About 175 dyes are now being made in the. United States from American raw materials and intermediates; these products are equal in shade, strength, and working qualities to those of the pre-war types and include members of all groups of colors formerly used in American mills; but owing to the pressure of other work during the past 3 years, American research chemists have not been able to devote energy to the discovery of new dyes. Present methods of testing dyes are empiric and subject to a wide limit of error. To illustrate, chemical analysis may show a dye t o be gg per cent pure and still inferior for dyeing to another sample of the same dye only 90 per cent pure. Dye tests are made in a manner that aims to duplicate, on a small scale, the actual application of the color. Slight differences in conditions, such as water used, may greatly influence the results of tests by two different laboratories.
Vol.
11,
No. 5
Colorimetric methods are more recent, but have many limitations, for the products of different factories may vary just enough to interfere with the use of the colorimeter. It is essential to devise methods to meet the objections mentioned and so facilitate the commercial development of the dye industry along proper lines of control. MELLONINSTITUTE
OF INDUSTRIAL
RESZARCH
PITTSBURGH, PENNSYLVANIA
THE FUTURE OF CELLULOSE ACETATE By H. S. MORK
Retrospect of the commercial history of cellulose acetate reveals that this material has had an up-and-down career. To the query why this should be so, the fundamental answer is cost; qualifying factors are patents and industrial “politics.” In general, the obvious characteristics of cellulose acetate products resemble those of cellulose nitrate products, whether films, fibers, plastics, or varnishes. The potent objection t o cellulose nitrate products for general industrial purposes (excepting explosives) is their easy ignition and high rate of combustibility. Concomitant with this property due to the combined nitric acid is the destructive effect produced on one or another type of supports by the liberation of even small quantities of such a strong acid as nitric acid under conditions of use favoring slight or partial hydrolysis of the cellulose nitrate. As a general proposition nearly everything (except explosives) that can be made from cellulose nitrate can be made from cellulose acetate. The manipulations necessary for conversion into commercial products are similar as to processes but vary as to chemicals required, viz., solvents, “softeners” or camphor substitutes, etc. Utility in some instances is governed by cost of conversion and final effect, or in other words, the properties of the products resulting from conversion. At the present time and as a result of chemical developments during the war, conversion costs of the two esters are not materially different. All this is aside from the initial costs of the esters. Cellulose acetate has always been more expensive than cellulose nitrate because acetic anhydride, the effective acetylating agent, has always been more expensive than nitric acid, the effective agent of nitration. Also cellulose acetate contains more combined acetic acid than the industrial nitrates do of combined nitric acid. The spread between the prices of acetic anhydride and nitric acid is now and has always been too great to permit cellulose acetate products t o be a direct competitor of cellulose nitrate products without regard to the differences in properties. It is the general belie€ that this difference in cost will always exist. On the other hand, statements have been made recently that it is not impossible to make cellulose acetate as cheaply as cellulose nitrate. That it has not been done does not necessarily mean that it never will be done. The recent large-scale developments in the manufacture of acetic acid from acetylene by way of acetaldehyde perhaps offer the best promise of very cheap production of acetic anhydride. By modification of this process it is possible to produce ethylidene diacetate, from which acetic anhydride can be made directly. If the manufacture can be conducted on a large enough scale and the process be brought up to a high state of efficiency, it is not impossible that acetic anhydride can be produced sufficiently cheap to make cellulose acetate a direct competitor of cellulose nitrate. The uses of cellulose acetate will be in part controlled by the development of this anhydride process or one equally as promising. The whole future of cellulose acetate is not by any means controlled by the necessity of price competition with cellulose nitrate products, for the obvious reason that the noninflammability of cellulose acetate products is a distinct and invaluable property. There are a large number of applications where
May, 1919
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
the dangers in the use of a highly inflammable material like cellulose nitrate justifies the higher price for a non-inflammable product. Some of these applications are developing by sheer force of virtue. Others are slow in reaching their justifiable use through commercialism or industrial “politics.” It is not necessary to elaborate on this point. Some day a holocaust will wipe out industrial “politics” and cellulose acetate will be found to he on deck, unless in the meantime something new has developed to take its place. The war has perhaps been the best booster of cellulose acetate, because in airplane construction it has developed its biggest use. Cellulose acetate dopes for shrinking airplane wing fabrics not only possess the desired property of noninflammability but have also demonstrated their superiority in durability and minimum degrading effect on the fabric. hTo one who has been close to airplane production seriously doubts that there is a big future ahead of it. Travel through thc air in heavier than air machines is industrial progress and nothing, therefore, can more than temporarily impede its development. If the present method of fabric wing covering is going to persist, then a large use for cellulose acetate is in prospect. Perhaps, however, one of the biggest uses for cellulose acetate in the future is in the production of artificial silk. The manufacture of artificial silk from cellulose nitrate has been a commercial enterprise of many years’ standing but cellulose nitrate silk cannot be marketed as such, on account of its extremely high inflammability. I t therefore has to be denitrated with the result that it loses its waterproof properties and on denitration becomes closely similar to viscose and cuprammonium silks and suffers greatloss OF strength when wetted. Cellulose acetate silk, on account of its relatively low inflammability, can be marketed without deacetylation and therefore all the waterproof properties of cellulose acetate are retained. Silks made from it are, when wet, about three times as strong as the other types of artificial silks, but aside from the waterproof properties, cellulose acetate silk has dyeing, or perhaps better expressed, has resist properties which give it distinct individuality as a textile fiber which practically affords it a market a t any price below that OF spun silk. The production of cellulose acetate silk in the United States has been retarded rather than helped by the war, because the silk industry had t o yield up its raw products to the airplane requirements. Now that the war has ceased and the production of acetic anhydride has been expanded in this country, cellulose acetate silk and other non-war uses of cellulose acetate ought t o come in for a new lease of life. ARTHURD. LITTLE,INC. CHARLESRIVERROAD CAMBRIDGE, MASS.
PHENOL By A. G. PETERKIN
Before the war this country’s consumption of phenol was about g,ooo,ooo lbs. per year. The bulk of it came from England, and was obtained from coal-tar distillates directly. A small part was synthesized from benzol. The general impression here is that this synthetic phenol was made in German plants, subsidized, and kept in existence by the Government for war purposes. The production in the United States during the war continually increased. At the time of our entry into the struggle i t amounted to 75,000,000 lbs. per year, and after that time plants were erected so that a t the end we had capacity to produce more than 150,000,000 lbs. Of this, not more than 2,000,ooo lbs. was obtained directly form coal-tar distillates by extraction with caustic soda. At the present time the consumption in this country is not much greater than 6,000,000 lbs. per year, about equally divided
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between the drug and disinfectant, the dyestuff, and the synthetic resin industries. This means that there was a t the time of the armistice a sudden cessation of manufacture and use on a comparatively huge scale, and stocks on hand altogether out of proportion t o the possibility of use in times of peace. I n private and government hands to-day there are a t the very least 30,000,000 lbs. of phenol. The Government wants to know what t o do with it. No adequate suggestion has as yet been made; perhaps some of you can answer the question. The Bureau of Public Health Service a t Washington has refused it as a gift; phenol has come to be a very specialized antiseptic; it has been displaced by cheaper, safer, and more powerful materials in the wider fields of disinfection. Before the war phenol sold a t about g cents per lb , and although our own coal tar was an inadequate direct source, England was able to supply both the United States and Germany with all they required in excess of their home production. The prewar price of say 8 cents was an exceedingly low one; it was not sufficient t o insure that all of the phenol available from coal-tar oils was extracted, or separated from the mixture of phenol and cresols which was extracted. On a basis of pre-war prices for labor and material, it is possible that phenol might be synthesized from benzol a t a cost of between I O cents aad 15 cents per lb. Were the present stocks absorbed, one or two synthetic phenol plants might operate in this country and insure a home production equal to our needs a t a cost no greater than a fair cost of imported phenol plus the present duties For the present the plants are idle-the wastage of war-and are likely to remain so, so far as the production of phenol is concerned. CHEMICAL DEPARTMENT
THEBARRETT COMPANY NEWYORKCITY
THE PREPARATION OF PURE ORGANlC CHEMICALS By H. T. CLARKE
Members of this Division will recall that a t the Cleveland meeting last fall Dr. C. E. K. Mees, Director of the Research Laboratory of the Eastman Kodak Company, announced that a department of the laboratory was being organized to supplement the work taken up by the chemical manufacturing department of the University of Illinois for the supply of the pure organic substances required for research which had before the war been obtained almost exclusively from Germany. At that time the department of Synthetic Chemistry, as this section of the Eastman Kodak Research 1,aboratory is called, had been in existence for too short a period to have afforded any tangible results, and we feel it our duty to take this opportunity of reporting progress to the Section, the members of which were so good as to give their approval and support to the undertaking. The work of the department falls into three main divisions: first, the synthesis of substances, for which there is an immediate or a potential dernand,which are not available on the open market; second, the purification of substances obtainable in technical quality from chemical manufacturers; and third, the distribution of the materials thus prepared and those purchased in pure condition from manufacturers and from individual chemists in university laboratories. As can readily be understood, it is our principal aim to bring our products to the highest state of purity it is possible for us to obtain, without consideration of yield or of labor involved, and products with the quality of which we are satisfied we designate as Eastman Organic Chemicals. We do not consider it desirable to print upon the label a specification of the purity of the contents of the bottle, but we shall be glad to furnish, on application, information, including the approximate date of preparation, relevant to the purification or testing of any substance supplied.
