US1275405A - Hydrogenation of fats and oils. - Google Patents

Description

UNITED S TES PATENT ornicn.

nuns nnwan, ormnnon, AND ADOLF Lmnum, or wnxnamen, ENG-LAND assreuoas To run rnocrna AND autism oourm, or omcmmmr, 01110,

A CORPORATION OF OHIO.

HYDBOGENATION 0! BATH AND OILS.

1,275,405. Io Drawing.

To all whom it may concern: 7

Be it known that we, Sir JAMnsDEwAR, of 21 Albemarle street, London, England, and Anonr LIEBMANN, of the Whim, Weybridge, in the count of Surrey, England, both subjects of the ing of Great Britain, have invented new and useful Improvements in the Hydrogenation of Fats and Oils, of which the following is a specification.

It is known that the hydrogenation of un saturated fats andoils can be effected in the liquid state by the treatment of such fats and oils with hydrogen in the presence of catalysts such as platinum, palladium, iron,

copper, cobalt, and especially nickel. This process involves two operations, the production of the catalyst and the subsequent hydrogenation of the fat or oil.

The use of a finely divided metallic oxid in the presence of the fat or oil has also been suggested for the purpose of carrying out the operation of producing catalyst and hydrogenation of the fats and oils in one step. The temperature required is however very high and may lead to the formation of deleterious by-products.

Furthermore the use of organic salts such as formates, acetates, lactates of iron, nickel, copper and cobalt has been proposed as a source for the catalyst and a mixture of one of these compounds with the fat or oil has been described to yield on treatment with hydrogen saturation of the fat or oil. The results of the last mentioned process are however at the temperature described as suitable for the hydrogenation namely, 170 to'200 centigrade highly unsatisfactory.

We have already invented a process which is the subject of our application of even date herewith Serial No. 842,537 for the pro duction of metallic catalysts from their oxy-' gen compounds by reduction with hydrogen at a lower relative temperature than could hitherto be accomplished.

The last mentioned process can be applied with great advantage to the hydrogenation of unsaturated fats and oils inasmuch as it can be carried out with great rapidity and at a comparatively low temperature in the presence of an unsaturated fat or oil.

According to our present invention which consists in the hydrogenation of unsatuhydrogen to the molecule 1s Very rapid.

Patented Aug. 13, 1918.

Application med June a, 1914. Serial m. scam.

rated fats and oils in the liquid state we produce the catalyst and the hydrogenation of the fats or oils in one and the same operation and at the same relatively low tem perature by mixing the fats .or oils with a mixture of the oxids (either hydrated or anhydrous) or the carbonates of two or more of the catalytic metals viz :-nickel,

cobalt, or copper, or with a mixture of the oxids or carbonates of one or more of the said catalytic metals with palladium, platinum or silver, 1n a fine state of division, or with a mixture of the oxids or carbonates of one or more of the said catalytic metals with silver oxid, passing hydrogen through the mlxture while it is being stirred and jheating the mixture to a temperature at which the reduction takes place. -Hydro genation proceeds concurrently with the production of the catalyst and the conversion of the unsaturated body by the addition of This invention is of importance in the hydrogenation of fats and oils asby its use the production of the catalyst and the hydrogenation of the oil can be carried out as aforesaidin one operation at such a relatively low temperature that the fats or oils undergo practically no decomposition and the saturation proceeds with extreme rapidity;

We classify our invention according to the following types- A. Hydrogenation of fats and oils in a liquid state by treatment with hydrogen of an unsaturated fat or oil in the presence of mixtures of hydroxide, oxids, or carbonates of two or more of the catalytic metals viz :nickel, cobalt, or copper.

B. Hydrogenation of fats and ,oils in a liquid stateby treatment with hydrogen of an unsaturated fat or oil in the presence of a mixture of one or more of the metallic compounds as defined in A with finely divided palladium, platinum, or silver.

C. Hydro enation of fats and oils in a 'liquid state y treatment with hydrogen of an unsaturated fat or oil in the presence of a mixture of a metallic compound as defined in A and silver oxid.

D. Hydrogenation of fats and oils in a liquid state by treatment with hydrogen of ,an unsaturated fat or oil in the presence of the mixtures mentioned in A, B, and C produced on the surfaces of porous substances.

Although silver and silver compounds have hitherto not been considered as catalysts, for "the purpose of this invention they seem to exercise catalytic action.

The mixtures produced according to the types A, B C, and D may be used in varied proportions of the catalytic constituents and in difi'erent total proportions to the fat or oil to be hydrogenated. v

For the purposes of this specification the expression mixed catalyst is a generic term which we apply to the catalyst products resulting from the operations and substances mentioned in paragraphs A, B, C, and D.

. The process of hydrogenation according .to our invention can be considerably accelerated by bringing hydrogen of increased density into intimate contact. with the oil and catalyst and this can be very readily accomplished by working under a pressure which may be ten times or more than that of the atmosphere and the duration of the process is considerably reduced thereby.

The following examples will serve to illustrate "further how the invention can be carried into eflect but the invention is not confined to these examplesthe parts are by weight. y

Ewample I.

A solution of 892 parts of nickel nitrate (crystals) and of 9.8 parts of copper nitrate oxid thus prepared the metal contents of (crystals) is poured into a. hot solution containing 46 parts of potassium carbonate. The precipitate is collected on a filter, washed thoroughly until free from soluble salts and then dried on the water bath; it is then heated to a temperature below red heat until the weight is constant. parts of cottonseed oil are then stirred with a quantity of the which correspond to two per cent. of the veight of the oil. A very strong current of hydrogen is passed through the mixture which is then heated for 2 hours at about 190 centigrade while being continuously stirred. on cooling the oil is found to be hard and very nearly saturated, the iodin number which is the measure of saturation, vbeingreduced from 110.6 of the original oil to 20.4.. a

A similar experiment carried out with the same mixture of oxids and whale oil shows after an hour a reduction of the iodin value from 114.8 to 20.6 and after two hoursto1.9.

Example I I 100 parts of whale oil are mixed with a quantity of nickel and copper hydrates (containing ninety per cent. of metallic nickel and ten per cent. of copper). in prowhale oil is thus reduced from 128.8 to 32.3

and the oil is quite hard.

Ewwmple Ill.

Nickel and copper carbonates are pre pared in molecular proportions in the man ner described in Example I hereof and a quantity of the carbonate the metal contents of which amount to about two per cent. of the weight of the oil used is mixed with cottonseed oil and a very strong current of hydrogen is passed through the mixture, while it, is being continuously stirred and heated for two hours to about centigrade. The iodin value is reduced from 113 to 38.6, and the oil is hard.

Example IV.

44.6 parts of nickel nitrate (crystals) and .2 parts of palladium chlorid are dissolved in water with the addition of a little hydrochloric' acid. The solution is warmed and added to a hot aqueous solution containing 15 parts of causticpsoda and two parts by volume of 40 per cent. formalin. A dark gray precipitate is obtained, collected on a filter and dried on the water bath.

100 parts of whale oil are mixed in an autoclave with 3 parts of the product thus prepared (about two per cent. of metal contents) the autoclave closed and the mixture being well stirred and heated While hydrogen is passed through, to about 180 to centigrade, the outlet of the hydrogen being so regulated that-the pressure in the autoclave is about 140 lbs. After half an hour the oil after cooling is quite hard, the iodin number being reduced from 128.8 to 36.1.

Example 7.

Emample VI,

Asbestos is impregnated with a solution containing equal parts of nickel nitrate (crystals), and copper nitrate (crystals) in such strength that the metal contents of asbestos and oxids, after their production amount to twenty per cent. of the combine lea weight of the same. The impregnated asbestos is dried and heated to convert the nitrates into oxids. Seventy five parts of cot tonseed oil are mixed in an autoclave with 5.5 parts of the asbestos thus prepared (the metal contents amounting to about one per cent. of the ,oil) the autoclave is closed and the mixture is heated while being-well stirred and'hydrogen being passed through at about 180 to 190' centigrade and the outlet of the hydrogen is so regulated that the pressure in the .autoclave is about 140 lbs. After half an hour the oil after cooling is quite hard and practically converted into a saturated compound the 'iodin value being reduced from 113 to 2.7.

According to all the above examples the catalyst is separated from the oil at the end of the operation by filtration and can be used over again or reconverted by well,

known methods. In case some traces of the catalyst'shouild remain in the oil the same can be removed in a manner well known toil-chemists.

-- In the foregoing examples we have described the use of the oxide in quantities the metal contents of which amount to about one or twp'per cent. of the weight of oil treated. We do not limit ourselves to these proportions as they maybe considerably varied eitherlowered or increased.

We find that of the above mentioned mixed catalysts the one produced from nickelv and copper compounds is the most economic.

It is well known that certain substances poisons to a catalyst and care hastherefore to be taken that the hydrogen is act as pure and the oils to be hydrogenated are in a sufiicient state'of purit y in order to avoid the. destruction of the catalyst on this account. p

We have found that electrolytic hydrogen is always of suificient purity for the purpose of this-invention.

There are sometimes certain substances in some oils capable of coagulation which are very detrimental to the process of hydrogenation and have therefore to e removed in the well known way.

' For the purpose of the present invention I we desire to exclude the use of oxygen come pounds of iron mixed with other catalytic or non-catalytic metals or oxids thereof.

For simplicity and convenience,.we designa'te' the metals of group A above, viz., nickel, cobalt and copper, as heavy metal catalysts viz., palladium, platinum and silver, as no ble metal catalysts. It will be observed that the invention contemplates the preparaof a mixture of compounds 0 lytic metals, one'at least of which is a heavy and the'metals of group B,

a plurality of the of'one or more of these heavy metal catalysts in associationwith a noble metal catalyst. Whatever its components may be,

the mixed catalyst may beused by itself, or

; applied to a porous support. The term;

metal of the nickel groupi is-used to include nickel and cobalta H a What we claim is: 1. For use in the hydrogenation of fats and oils, a mixture of compounds of diflerent catalytic metals, one at least of which is a heavy metal catalyst, said mixture reducible by hydrogen in .t-he hydrogenation process.

2. For use in the hydrogenation of fats and oils, a mixture of compounds of'difl'erent catalytic metals, one at least of which is a heavy metal catalyst, said mixture retion of catalysts consisting either of" heavymetal'catalysts, or

so i

ducible by hydrogen in the hydrogenation process at temperatures not exceeding 200 C.

3. The method of preparing a-mix'ed catalyzer and hydrogenatingr fats 0r oils in one operation, which consists in treating the heated fat or oil with hydro en in presence 'diflerent catametal catalyst.

4. The method of preparingiamixed catalyzer and hydrogenating fats or oils in one operation, which consists in treatin the fat or oil with hydrogen in presence 0 a mix ture of compounds of difi'erent'catalytic metals, one at least of which is a heavy metal catalybst, at a temperature not exceeding 200' 5. For use in the hydrogenation of fats and oils, a mixture of compounds of different catalytic metals, one" at least of which] belongs to the nickel group,. said' mixture re ducible by hydrogen in thej'hydr'ogenation process 1 6. For use in the hydrogenation of fats