TR.TinMP1 CAIV,DA l j Hj 1. 1 NATIONAL FISHERIES RESEARCH BOARD OF CANADA Translation Series No. 867 OTTAWA CANADA

A general retrospective and prospective review of train as a raw material

By Jürgen Spieckermann

Original title: Ein allgemeiner RCck- und Ausblick über den Grundstoff Tran. From: Seifen-Ole-Fette-Wachse, Vol. 91, No. 26, pp. 940-943. 1965.

Translated by the Translation Bureau (MJK) Foreign Languages Division Department of the Secretary of State of Canada

Fisheries Research Board of Canada Technological Research Laboratory, Halifax, N. S. 1967 , , ^^e /Yô. <ç^ d DEPARTMENT OF THE SECRETARY OF STATE SECRÉTARIAT b'ETAT BUREAU FOR TRANSLATIONS BUREAU DES TRADUCTIONS FOREIGN LANGUAGES VW DIVISION DES LANGUES DIVISION CANADA ÉTRANGÈRES

TRANDLATED FROM - TRADUCTION DE INTO - German English

SUBJECT - SUJET Train oil

AUTHOR - AUTEUR Jitrgen Spieckermann

TITLE IN ENGLISH - TITRE ANGLAIS al A general retrospective and prospective -Lteview of train oil asAravc material

TITLE IN FOREIGN LANGUAGE - TITRE EN LANGUE EITRANORE Q Ein a7lgemei.ner Riick- arh«ks Ausblidc uber den Grundstoff Tran

REFERENCE - REEFÉRENCE ( NAME OF BOOK OR PUBLICATION - NOM DU LIVRE OU PUBLICATION) Seifen - Ôle - Fette - Wachse Vol. 91 N:26 ( Soaps- '? - Waxes )

PUBLISHER - ÉDITEUR Verlag fiir Chemische Industrie H. Ziolkowsky K.G. CITY - VILLE Beethovenstr. 16 DATE PAGES 1965 940 - 943 Augsburg Germ.Eny 18 typed pages

REQUEST RECEIVED FROM Dr. R. G. Ackaian OUR NUMBER 7369 - 5 REQUIS PAR NOTRE DOSSIER NO Fisheries Research Board., Halifax DEPARTMENT of Fisheries TRANSLATORM.J. K-ru^;ynskl MINIST^RE TRADUCTEUR

YOUR NUMBER , 769 -18-14 DATE COMPLETED 7 April 1967 VOTRE DOSSIER NO REMPLIE LE I

DATE RECEIVED 21 March 1967 REÇU LE

fee A/0, S7 Seifen 61e Fette Wachs°, 91 Nr. 26 1965 pp. 940 - 943 (Soaps - Oils - Fats - Waxes) —

A general retrospective and prospectiveçview of train oil as raw material

1 . Jürgen Spieckermann • _.____ I

Liquid fats originating from marine-animais are called train oils and fonnthe group of marine-animal oils. They are obtained from the tissue of e.g. , wal- russes, seals,herrings, sperm wÉales, cod fish, sharks, etc. by pressing or by heating with boiling water or steam; they are light yellow to deep dark brown color and mostly of pungent, more or less unpleasant taste and odor.

4. The most important commercial train oils and countries pro- ducing them.

Whale train oil. Under the name of train oil are listed com- mercially fats from the Greenland whale, the southern whale, the finnwal, narwhal and other whales. Whale train oil is mostly brown and when purified, of glass-clear yellow color. The main hunting area is the Antarctica; Norway, England, The Union of South Africa, Japan, Argentina, Chile,

Translator's note: or perhaps nbeak whalen •••2 2

The Soviet Union and Holland participate in the hunt.

Plants located on land are found in Southern Georgia and

on a smaller scale in Norway and Greenland.

Cachalot train oil (sperm oil).

Sperm oil is obtained from the train oil of the

or cachalot. When stored in cold surroundings,

it precipitates a solid component - , which is

filtered out from the liquid sperm oil. The oil is light yellow, watery and almost devoid of odor. The main area

of hunting is the Antarctica, the West Coast of Africa and

Chile. As to participation in hunting see whale train oil.

Seal train oil.

Seal train oil is obtained from various species of seal. It is yellowish to dark brown and mostly of an unpleasant odor.

Countries of largest production are Norway, Green- land and Newfoundland.

Dolphin train oil.

The train oil obtained from the whole body of the black is of pale yellow color. From the soft fat from the head and jaws originates the jaw bone train oil; it is straw-yellow, watery and clear and of a not unpleasant

I . . . 3 3 (ç.;

smell. The main hunting area.is the Black Sea with Soviet Russia and Turkey participating in the hunt.

Herring train oil.

This fat oil is obtained by cooking, followed by pressing of the whole herring. Countries of production are Norway, Iceland, Canada, USA, Japan, England and on a smaller scale Germany, Sweden, Denmark and Holland.

Sardine train oil.

It is obtained by pressing whole sardines. Vari- ous products are on the market under the description sar- dine oil; they can differ from each other considerably: 1.Canadian sardine oil. 2. Japanese sardine oil. 3. Portu- guese sardine oil. 4. Spanish sardine oil and 5. Califor- nia sardine oil.

Cod liver oil.

Genuine is obtained from the livers of particularly the torske , "Stockfisch" or the"Kabeljau" and applied for medical purposes; the less valuable oils used for technical purposes corne from the remaining parts of

Translator's notes: '4' Could also be cusk

" "Stockfise is dried cod and "Kabeljau" is the general name for codfish; unless the author has, differing subspecies of codfish in mind,which I was not able to identify. •••4 4

‘ brown the body. The color varies from light and clearlAand clear to dark brown. Producing countries can be distinguished as fol- lows: a) technical oil: England, Japan, Newfoundland, Ice- land, Norway and Portugal. b) medical oil: Norway, Iceland, England and Germany.

Shark liver oil.

The oil obtained from the liver of the fish serves mainly medical purposes. The technical oil is pro- duced by pressing and cooking the other parts of the body. Producing countries are: Japan, Norway and Greenland.

Argentine .

This is a train oil obtained from different species of fish, very sensitive to cold and mostly solidifying easily. It is processed reluctantly because of its high ' saponifiability.

Japanese train oil.

This means a train oil which is produced from various fish species on some stretches of the Coast of Japan. The mixing ratio is completely irregular. It is easy flow- ing, with a relatively strong odor and looks reddish.

•••5 Train oil fatty acids.

I7uring train oil refining, depending on the ori- ginal material and method of refining, non-uniform, solid to liquid train oil fatty acids of deep dark to light brown color and mild o/dor are produced.

Recovered fish oil.

Under this description train oils are sold, re- covered in small quantities from Fuller's earth or other train oil residues. The origin cannot be determined.

Analytical characteristics of train oils.

Up to the present day, much confusion and, dis- agreement exist among scientists with regard to the chemi- cal structure of marine-animal oils. So far e.g., nobody succeeded in achieving a perfect quantitative separation of individual polyolefinic fatty acids. Even differentiation• of single train oils from each other causes still some dif- ficulties in analytical raw material control of the train oil industry since, on the strength of the cornmon investi- gation methods like specific weight, iodine number, acid number, saponification number etc., it must be decided fast and definitely whether or not an original shipment is in hand and can be accepted as unobjectionable. The specific weights of train oils do not differ greatly. They lie i ..,6 - 6 -

between 0.915 and 0.930; neither give the saponification

numbers and iodine numbers alone sufficient data for evalu-

ation of the train oil purity. Also the characteristic,

intensive color reactions shown with caustic soda, sul-

furic acid, nitric acid and phosphoric acid require a con-

siderable skill on the part of the analyst and can be

evaluated only in conjunction with other data as an aggre-

gate judgment. Diligence and accuracy alone do not suf- /941 fice; the train oil specialist must have something akin to

a sixth sense; perhaps this may sound amusing but there is

something to it, because the main thing i s to detect with a lucky hand and the means available any possible present

defects. Pure analytical experimental values of the most

important, unmixed original train oils obtained by steaming

or pressure are presented in the table which follows fur-

ther below.

The unsaponifiable components must be determined by the method of Fahrion and the iodine number after the method by Hanus; other prescriptions give false, deviating values.

Theunsaponifiable components according to Fahrion.

5 g of train oil or ether extract are saponified with 12 - 15 ml of 2-N alcohol and potassium hydrate solu- tion in a glass cup placed in a sand bath, with stirring

i ...7 - 7 - until dry; the soap is absorbed with 50 ml warm water and washed in a separating funnel with further 10 ml of alco- hol. The cooled soap solution is then shaken with 50 ma of ether and subsequently twice, each time with 25 ml of ether, in which way the unsaponifiable components are with- drawn. The combined ether extracts are shaken with 2 ml of

2 HC1 and 8 ml of water; after removal of the acidic water, follows washing with 3 ml of e KOH solution in 7 ml of wa- ter. Finally, after removal of the watery alcohol layer, the ether extract is distilled and the residue is weighed quantitively. For further evaluation of the commercial quality the following is considered:

1. Content of dirt and water. 2. Content of free fatty acid calculated as oil acid. 3. Content of oxy-fatty acid. 4. Solidification-opacity point (train oil stearin- portion) 5. Color and odor.

• ••8 a

Table

Unsap oni fi al ble Kinds of train oil components Saponification Iodine number Color reaotions in % ( lrahrion) number (Hanus) with sulfuric acid

Liver train oui a e m ah liver only: âod liver oil: a) teohnioal purpls b) mediainal purple purple-blue Fish train oils ob - part s Herring train oil dark brown Sardine train oil dark brown Pilchard train oil dark brown Blubber train oil of mamm Bhale train oil brownish Sperm oil unoertain Seal ttain oil brownish-feebly purple

Dolphin train oil brownish-feebly purple Other train oils Africa shark train Argentine fish train oil dark brown Japanese train oil Train oil fatty acide Extraoted train oils

As can be seen from the Table, true train oils

have all an iodine number over 110. This is brought about

by the presence of large quantities of unsaturated fatty

acids. In agreement with more recent literature data, a

complex mixture of fatty acids with 4-6 double bonds is to

be regarded as characteristic for all marine-animal oils

and not, as has been erroneously assumed earlier, a fatty

acid with 5 double bonds, the so called clupanodonic acid. - 9 -

Apart from that, saturated fatty acids also occur, as well as fatty acids with 1 double bond and traces of linolenic acid, linolic acid (about 0.0 to 4%) and in various cases also oxy-fatty acids.

Cod liver oil Herring oil

Fatty acids with 4-6 double bonds about 30% about 20% Fatty acids with 1 double bond about 49 - 53% about 55-60% Saturated fatty acids about 14 - 15% about 19-21%

In spite of much new information, the fact remains that with regard to fat oil there is none on which so little re- liable literature would be available as on train oils. This can partially be explained by the fact that in times of economic rise and abundance of raw materials, train oil is looked upon by different conservative proces- sing groups, not as basic, but only as auxiliary material; they are not willing to spare the time and do not have at their disposal suitable professional manpower qualified to tackle thoroughly and studiously this economically inter- esting raw material. • In times of crisis and lack of foreign currency, when different sources of raw materials are closed, atten-

. .10 - 10 -

tion is easily directed again to those so called auxiliary

materials in search for new local raw material bases.

Under such circumstances, often in a very shorttime, ap-

plicable basic materials appear which would take years

otherwise. However, immediately after such abnormal time

periods, nothing seems to be more urgent thab to put aside

again the collected information as substitute material

and-to go back to importing earlier used foreign materials,

disregarding that the judgment as to the value or worth-

lessness of the notorious substitute materials has been

clarified and on the other hand, many good budding notions

which germinated in between were recognized.

As a typical example, let us recall the soap

industry, which, after the I World War, engaged mutually in a cartel-like agreement to declare their products as

"warranted free of train oil". Only later the dislike of train oil as soap raw material was recognized as obsolete.

Also in the varnish, lacquer and putty indus- /942 tries, the substitute materials which emerged in the years 1914 - 1918 did no^ achieve much success.

Only shortage of linseed or linseed oil in the year 1935 and later, forced the German lacquer and putty industries to accept lacquer train oils as e.g. Haco-products and

Tranalkyd 2521.

This line was continued in Norway with much

i 0 ..11 b /

• - 11 -

better planning and more intensively; up to the present time, by detailed work-out, completely developed train oil alkyds are brought to the market. The train oils are e.g. decomposed by selective extraction with liquid propane, according to the solexol method. The thus obtained train oil fractions abound in acids with 4-6 double bonds and therefore the later pro- duced alkyds react easily with oxygen and dry very fast. Their resistance to rubbing off, weather, water and chemi- cals corresponds to that of linseed oil aLkyds. Although somewhat darker, they do not show any additional yellowing. Norway favors train oil alkyds with 50 to 70% oil content. Parallel also tall oil should be evaluated here, which also was ridiculed originally as auxiliary material and in-between has developed into a full value lacquer raw material.

The more thoroughly the various kinds of train oil are processed by train oil refining plants, the more efficient is their action in the processing for which they are used: e.g., by composition of standardized special train oils like special jute train oil, special leather train oil, special tanning train oil et. Whether train oils are cheap is decided pri- marily by the properties of the train oil and only secondarily by the prices. Often train oils appearing advantageous as

...12 F1-7) - 12 -

to price, corne out later during processing as much more expensive/ than the more essential train oils at higher prices. There is no doubt that the various train oil sorts are downright different in their action and that these differences can be put to full use in manufacture Only by a train oil professional who really has matered the technology of train oils.

General refining of train oil.

Under refining of train oil in a strict sense is understood: desliming, deacidification, bleaching and steaming (deodorizing). •

1. Desliming. Desliming is achieved successfully in steam heated conical tanks with agitator, at temperatures of not more than 100 °C; with strongly fowling, gas producing ma- terial at 30 ° C with addition of barium chloride and sodium sulfate. When much slime is present, the amount of sodium sulfate is increased to suit.

2. Deacidifying. Deacidification is also performed in steam heated conical tanks with agitator at temperatures of not above 100 ° C in two stages: preliminary deacidification at 60 ° C and after-deacidification at 90°C until the desired acid

• • •13 - 13 -

number is attained; sodium lye is used, followed by washing

with water at 90°C.

3. Bleaching.

Bleaching with Fuller's earth occurs in a heated

bleaching mixer under vacuum obtained by means of a slide

valve air pump. This is followed by filtration in a frame

filter press. Bleaching with hydrogen peroxide occurs in

an aluminum-clad vessel with agitator under heating with heating coils to about 70°C.

4. Steaming. _

By deodorizing,the undesired substances causing odor and taste are removed from the train oil and a suf- ficient stability is achieved. The main carrier of the malodor of train oils is a complex mixture of highly unsaturated fatty acids with 4-6 double bonds, amines

(originating from fish protein) and lower fatty acids.

Deodorizing proper occurs by introducing into the oil steam heated to 280 - 300°C and reduced to about 2-3 atm

(gage). The oil temperature does not exceed 200°C in such cases. In order to achieve good deodorizing, the over- heated steam is introduced during approximately 7-8 hours.

In case the temperature of the train oil drops during deodorizing, it must be controlled by steam in coils.

During deodorization, fatty acids evaporate; with the

i ...14 - 14 - blown in steam they enter in vapor form into a barometric condenser arranged above the roof and condense. To produce the required vacuum, a slide valve air pump of about 600 m.3 hour is used. The process, as such, is a forced * per distillation conducted at low pressures and increased tem- perature, by which the foreign substances to be separated are distilled with a stream of inert gas. For purely economical reasons, steam is used for this purpose, hence the expression "steaming". Cooling of the deodorized train oil occurs under vacuum in a surface cooler fol- eXx lowed by "polishing" (after-filtration) in a "polishing press °'19e. A further procedure for disposing of odors and brightening the train oils is catalytic hydration on a large technical scale, in which the train oil is converted into a solid saturated compound, losing completely its chemical and physical character. With the progress of hardening, melting points and specific weight increase, the iodine number and the refractive index decrease. The odor of the hardened train oils becomes sometimes offensive. Usually hydration is conducted with nickel catalysts. Im- portant brands of those hardened train oils are e.g.:

e Literally: "drag distillation" like Frendl "distillation d'eltrainement" Translator's notes:"Illegible in German reprint. Looks like 0-Kühler. My guess is Oberflâchen- Kûhler . surface cooler. ›,r , Translated verbatim. Could not locate appropriate English terms of the trade.

• •.15 - 15 -

Talgol^` , Talgol extra, Candelite, Candelite extra, Neo

Candelite extra"' , Nofalit.

It should be mentioned also the dissociation of train oil according to the Twitchell method or the medium pressure autoclave dissociation. The latter works with steam of 12 atm (gage) and zinc or zinc oxide as dissocia- tion agents.

Application ranges of train oil for technical utilization.

Whale train oil.

Grades I and II for solid fat or in- dustry.

Grades III and IV, now accumulating only in plants located on land, are used, after previous dissociation, for consistent fats, further for leather and textile auxiliary agents, jute and soap industries.

'riThale oil is suitable for production of coatings and artificial resins.

Sperm oil.

Laundry agents industry. Production of fatty al- cohol sulfonate after cold filtration at approx. -2°C to -6°C, in which the oil is brought to the required low temperature in a jacketed crystallizer with brine cooling and agitator.

Translator's note: * Illegible in German reprint. Names are guessed.

...16 - 16 - // ,

It is further applied in the leather and textile auxiliary agents industry, the baking agents industry, for drilling and cutting oil manufacture, for metal hardening in the needle industry; in the latter case particularly spermaceti is used.

Seal train oil. For high class leathers in the leather industry, in the jute industry when batching raw jute for powder su- gar bags and in fur dressing plants.

DolDhin train oil. For high class leather in the leather industry and in fur dressing plants.

Herring train oil. /943 Leather, leather oil and leather fat industry. e Degreasing agents,liKernbindemitteln adhesives and jute in- dustries. When refined, used as for fish frying stands etc. In the fish preserves industry it is used as pickling oil. Since this oil has poor drying properties, it is less suitable for the lacquer industry. Only after treatment, e.g. blowing air through it (oxidation) at an increased temperature, a highly viscous product is obtained which can be used as coating material component. This

Translator's note: literally grain glues or adhqsives. ...17 Could not locate neither translation nor explanation ^6-7

- 17 -

thickening occurs in an enclosed, steam heated vessel and by means of compressed air produced by a Roots blower.

Temperature control is effected by designing the heating coil to serve also as cooling coil.

Sardine train oil.

Used.for batching of raw jute for production of jute fabrics in the jute industry when der:iands as to odor are insignificant; further in the factice, "Kernbindemittell, * adhesives, linoleum, artificial resin, lacquer and putty industries. The oil itself dries to a sticky and water sensitive film. It can be improved by heat treatment, by steam distillation, as a result of which it dries faster and becomes harder. By heating and thickening at 280°C the drying properties are also improved.

Cod liver oil. a) technical'uses: leather and textile auxiliary agents industry. b) veterinary uses: as internal medicament. c) pharmaceutical uses: production of healing ointments. d) medical uses: filtered cold - as internal medicament.

Shark liver oil.

Linoleum and leather industry; filtered cold - aircraft engine industry, production of healing ointments.

4^See note on p.16 . ...18i r - 18 -

Summarizing, one should point out that the modern large industry, as result of its creative and progressive work, has granted full recognition to train oil as raw ma- terial; all the other conservative groups of train oil users, whose endeavours are still more or less in the nur- sery stage, should accept advice as to other possibilities from p.rofessional importers and refiners specialized in the raw material train oil, instead of sticking to tradi- tion for tradition's sake.