BE535876A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 



   From aliphatic carboxylic acids of their esters, for example glycerides and / or anhydrides, natural or synthetic, it has already been proposed to prepare carbinols, using copper chromite as a catalyst, with hydrogen under high pressure and at elevated temperatures. The hydriding can be carried out in stages or continuously, with careful control of the reaction conditions allowing good carbinol yields to be obtained. Although now simplified, the preparation of copper chromite has remained costly. The manufacturing costs would be less heavy if the copper chromite used as catalyst had a longer life, corresponding for example to that of the grease hardening catalysts, or if, at least, the catalyst could be easily regenerated.

   In "Chemioal Engineering" of June 1951 (page 117), Richard F. WARREN indicates, for the operating workshops, a consumption of 1.5% of fresh catalyst, related to the alcohol present, but one consumed in addition an unknown quantity of copper chromite. According to WARREN's report, catalyst costs can reach up to half of the total operating costs. These costs can be reduced by using carefully distilled esters as the starting material for hydriding, but the operating efficiency is thus reduced by the cost of preparing the ester and a significant part is also lost. reaction space for the alcoholic ester components. For reasons of reaction kinetics, lower alcohols are undesirable for esterification.



   However, it has been found, which is surprisingly, that copper alone, without any addition of any activator, is an excellent catalyst for converting into corresponding carbinols, long-chain aliphatic carboxy compounds, with chains of C6 or more, of preferably in C11 and above. A prerequisite for this is in any case that the copper is in colloidal form during the hydriding. This is achieved by dissolving copper, in particular electrolytic copper or its compounds soluble in fatty acids, such as oxides, hydroxy carbonates or organic salts of copper, preferably hot between about 100 and 140 C, in fatty acids and by separating the copper in a particularly active colloidal form by heating the solutions, for example at 150 ° C. or above, in the presence of hydrogen.



   This colloidal state must be maintained during the hydriding by carrying out the said hydriding in the presence of protective colloids, such as sterides, phosphatides, albuminoids, muonins, and other substances accompanying natural oils, fats or fatty acids, of so as to prevent agglutination of the colloidal copper used as a catalyst. Also suitable as protective colloids are polymerisates or mixed polymerisates of styrols, vinyl compounds, for example vinyl esters, in particular with higher fatty acids or vinyl ethers of acrylic compounds , in particular esters of acrylic or metacrylic acids with higher fatty alcohols, caprolactam and other amides or ethylene oxide or ethylene imide,

   and artificial condensation resins, such as alkyd resins, phenoplasts, aminoplasts and polyurethane resins which are soluble in hot fatty acids, their esters or their anhydrides. It is for example particularly advantageous to use a mixed polymerizate of styrol and maleic acid anhydride, in a molecular ratio of 1: 1 and of an average molecular weight of 15,000 and 20,000. This mixed polymerizate can be an anhydride. poly-1,2-dicarboxy-4-phenylbutane, which is almost insoluble in fatty acids, and which, therefore, can advantageously esterify with alcohols resulting from the hydriding of fatty acids.

   In addition, substances acting as protective colloids must not

 <Desc / Clms Page number 2>

 adversely affect the smell or color characteristics of the alcohols that are formed; during the subsequent hydriding and distillation, they must not form volatile products which could contaminate the alcohols. The stabilizing effect is particularly great when the synthetic substances acting as protective colloids have as high a degree of polymerization as possible, which can rise to the limit of a remaining sufficient solubility in hot fatty acids.



   As raw materials for the process which is the subject of the present invention, mention may be made of fats or oils of vegetable or animal origin, unpurified, fatty acids obtained therefrom by hydrolysis, for example by alkaline saponification followed by precipitation acde from careful washing, distillers fatty acids or synthetic fatty acids.



   While it was common in the known processes to employ well-purified starting materials, for example carefully distilled ester, the process which is the object of the present invention has the essential advantage of allowing to successfully treat crude fatty acids, without having to subject them, before hydriding, to a purification by distillation or to an esterification. It is in particular possible to use, for the process which is the object of the present invention, the fatty acids resulting from the hydrolyzed separation - tick of fats and oils, the hydrolytic separation not having to be pushed very far, because it is possible to use as raw materials mixtures of fats, oils and other mail with -. Fatty acids.



   To fatty acids or esters, preferably glycerides and anhydride, which are poor in accompanying substances or which are totally or almost entirely free from them by distillation, such as for example fatty acids obtained from distillation, said accompanying substances can be added, for example the pitch-type residues from the distillation of fatty acids or preferably the clear waxy residues from the distillation of alcohols obtained by the present invention.



   Instead of these additions from natural oils or fatty acids, analogous materials from other sources or mixtures of oils and fatty acids can also be used.



   The amounts of additions of accompanying substances which are necessary to maintain good catalyst efficiency depend on the origin or nature of the raw materials and they vary for each vas. But they can easily be determined by preliminary tests, especially since as a rule excess of added accompanying substances are not troublesome. Synthetic protective colloids need only be added in extremely small amounts, for example between 0.1% and 1%. Higher additions are also possible.



   Another advantage of the present invention is apparent from the fact that, unlike hydriding with copper chromite, fatty acids containing iron, as formed by prolonged stay in steel tanks. or in iron pipes, which have taken up iron in an amount such that a layer of iron soap slurry has settled on the bottom, can be used for hydriding without any risk. In general, it is even indicated to add small amounts of iron or manganese, for example a few% of the copper content. These metals can for example be added in the form of pure iron powder or in the copper used.

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   The fine dispersion of copper in the carboxy compounds to be hydrated can be obtained advantageously by adding to them, before or during the reaction, copper acylates where, at temperatures above 1500 and in the presence of hydrogen, the copper separates under a particularly active colloidal dispersion. By adding, in accordance with the invention, accompanying substances or residues from the distillation of fatty acids or from the distillation of alcohols obtained by the process forming the subject of the present invention, the colloidal dispersion is obtained. copper, during hydriding, is maintained to a sufficient extent and thereby copper retains its catalyst properties.



   The resulting colloidal copper solution is colored black and consists for the most part of copper particles of 10-5 to
10-7 cm. copper only partially settles very slowly and cannot be separated by an ordinary hand. The solution passes through a double pleated filter.



   Copper acylates can be obtained for example by dissolving copper in fatty acids, advantageously with vigorous stirring and hot, for example at temperatures from 100 to 1400, in the presence of oxygen, more particularly in the presence of air. . The dissolution of copper can be accelerated by using for the production of copper acylate a finely divided powder of copper, for example - electrolytic copper, and passing through the liquid, effecting the dissolving process, of oxygen, for example air.



   For the production of the catalyst according to the present invention, it is also possible to use, instead of copper powder, precipitated compounds of copper soluble in fatty acid, such as copper hydroxides, copper oxides and copper compounds. copper carbonates. The so-called copper compounds are more easily soluble in fatty acids than copper. This is why they are used advantageously in those of fatty acids, in which the copper powder dissolves only very slowly.



  In order to prepare the catalyst which is the object of the present invention, it is also possible to use copper compounds other than those indicated, in particular basic copper salts. Starting for example with electrolytic copper dissolved in nitric acid, it is possible, by treatment with alkalis or by heat treatment, to obtain a copper salt which is perfectly suitable for hydriding.



   Copper compounds with a high content of SO4- or / and Cl ions, which are often found in commercial types, are of little or no use at all.



   Lead and bismuth can in particular act as contact poisons. It is therefore advisable to ensure that these elements or their compounds are not present during the hydriding and are not added with the copper used as a catalyst or its compounds or else that they are not used. contact with devices used for operations.



   Copper acylates are soluble in excess fatty acids at high temperature, for example greater than 50, on the other hand, as already indicated, they are not very stable above 1500. This fact can be taken into account various ways for the manufacture of the catalyst of the present invention. Thus, for example, a concentrated copper acetylate solution, which can be heated to about 150, is mixed, in the presence of hydrogen, with the starting materials contained in the reaction vessel.

   The carboxy compounds used as starting materials, to which can be added the accompanying substances ne-

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 necessary for maintaining the fine dispersion of the copper during the hydration, may, before mixing the copper acylate, be heated to the hydriding temperature or to another higher or lower temperature, and find the pressure under which must be carried out. hydriding. But it is also possible not to heat in the oven, at the temperature of hydriding and in the presence of hydrogen, until after its preparation, the mixture formed of a solution of copper acylate and carbon compounds. - boxy.



   In many cases, it has proved advantageous to heat to temperatures of about 250 to 300 the majority of the carboxy compounds to be subjected to hydriding, in known heating devices, under hydrogen pressure, and then place them in the reaction oven. After that, a smaller part of fatty acids which contains, in the form of copper acylate, the copper necessary for the catalyst, is introduced into the furnace at a maximum temperature of 150. The reaction then begins immediately and sharply.



   It is also possible to use the whole quantity of the carboxy compounds to be hydrated to dissolve the copper or the copper compounds necessary for the hydriding and then to introduce into the reaction furnace the solution containing the copper.



   In the process according to the present invention, it is advantageous to have, for the hydriding, a copper content of 1 to 4%, preferably of 2.0 to 2.2%, calculated on the basis of the mass to be hydrated.



  This copper concentration in the mass to be hydrated is obtained quickly by stirring the copper powder or the copper compounds while hot, if necessary by passing air, until the desired concentration is obtained. copper acylate, the dissolution for example of the copper powder being accelerated by its addition in excess up to 100%. Unconverted copper powder can be removed from solution by allowing it to stand or by using other analogous separation methods.



   When adding copper to the material to be treated, to produce the copper catalyst required for hydriding, a certain fatty acid content is required in the raw material. If free fatty acids, for example, are not present in the processing of fatty acid esters and glycerides, a sufficient quantity of suitable fatty acids can be added.



   For the preparation of the copper catalyst according to the present invention, it is also possible to introduce, into the carboxy compounds to be hydrated, the necessary copper in another very finely dispersed form, for example in that of a colloidal solution. ; care must then be taken to ensure that the necessary protective materials are already contained in the carboxy compounds or that they are added to them at the same time as the colloidal copper solution.



   During the hydriding of fatty acids, of their esters, in particular their glycerides and (or) their anhydrides, one obtains, by the process according to the present invention, alcohols having diacid numbers lower than. 1 and saponification indices less than 2, when, by applying methods known per se, the water formed during the hydriding is removed, for example by constantly withdrawing hydrogen from the reduction vessel, by cooling it to condense the water vapor it contains, and then returning it to the reduction vessel.



   The carbinols are purified by careful distillation with precaution and the yields obtained are of the order of approximately 95%. The

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 residue still has an OH number of 50 to 100 and a saponification number of 20 to 50. This residue can again be mixed with new material, for example new fatty acid, and resubmitted. during hydration. Up to nearly 100% of the fatty acid used can thus be passed into the 98 carbinol.



   This procedure according to the present invention has the advantage that, during the treatment of non-distilled fatty acids, there can hardly be a lack of accompanying substance important for the hydriding and that an addition such substances is unnecessary.



   For the economical implementation of the process, with the addition of synthetic protective colloids, it is essential that the latter can be easily isolated from the natural accompanying substances of the fats and oils used as raw materials, and can be reused subsequently. The mixed polymerizate of styrol and maleic acid anhydride, preferably used in its esterized form, converts upon hydriding into a diol although more slowly than the fatty acids convert into fatty alcohols. The ester and its hydriding products up to the diol remain in the residue during the distillation of the alcohols obtained and can be used again.

   The diol of the mixed polymerizate has the same stabilizing properties as the ester of the polymerizate itself, and is easily and completely dissolved in hot fatty acids. During the processing of undistilled fatty acids, the natural fatty acids which also remain in the distillation residue are enriched after a certain number of passes. The stabilizer can be released therefrom by thin film distillation or by extraction with selective solvents.



   As the heating means of the heating device of the reaction furnace, it is advantageously possible to use the hydrogen used for the hydration. The latter is first heated to a high temperature and then in a heater. For this purpose, a hydrogen circuit can be provided through the heating system and a heater, in which the hydrogen takes the heat necessary for working in the autoclave. On leaving the heating device, hydrogen is introduced into the carboxy compounds, which are in the autoclave, preferably so as to simultaneously cause mixing of the contents of the autoclave.



   The hydrogen can be switched on through the autoclave and a cooling device, in order to constantly drive the water of reaction out of the autoclave. Along with the water vapor, the carbinols condense in the cooling device, the latter being entrained by the hydrogen due to their partial pressure. They are in particular the alcohols with the lowest boiling point, so that, by this hydrogen circuit, a partial separation of the low boiling alcohols and the alcohols with a low boiling point is obtained at the same time. high boiling point.



   Once the hydriding is complete, the contents of the autoclave are relaxed in an extension or other similar device. Here the liquid carbinols contain in the form of copper acylate or colloidal copper, the quantity of copper introduced into the reaction. There is no separation of the metallic copper, which would be liable to disturb the operation of the furnace. On the contrary, the autoclave can remain in interrupted operating condition for several months.



   To allow economical implementation of the process of the present invention, it is essential to ensure good separation of the copper.

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 of the product of the hydriding. Obviously, the better the colloidal copper is stabilized and the more difficult it is to achieve separation, which can be achieved in different ways.



   For example, alcohols can be left to stand for 24 hours and even longer, at temperatures above the melting point, or they can be briefly subjected to the action of water and water vapor and centrifuged at high speed. dispersion broken thereby. The copper can also be filtered by filters made of sponges or foam asbestos or earths having a similar effect. The filter mass must not contain material prejudicial to hydriding, so that the copper can be reused.



  Finally, the copper dispersion can also be broken into flakes in an ultrasonic field of appropriate frequency, the copper then having to be filtered in the usual manner.



   The isolated copper which moves through the circuit like the stabilizer is dissolved again in the fatty acid. For dissolving the recovered copper, it is advisable to use horizontal mixers with a fast rotating horizontal eccentric shaft and equipped with beaters. Tests have shown that under these conditions, contrary to what happens with vertical shaft devices, heavy metal powders are more easily prevented from settling and the duration of the dissolution process is reduced to a fraction of what it is. would be otherwise.



   By using a sponge or foam filter to separate the copper, the insoluble elements of the filter are removed from the copper fatty acid by any suitable means, they are deacidified and optionally reused.



   The process is suitable for both batch, semi-continuous and continuous work. The batch operation is particularly simple, given that the progress and the end of the operation can be observed by the absorption of hydrogen. Working semi-continuously, the raw material is subjected to a high flow of hydrogen circulating under reaction temperature and pressure for a predetermined time while maintaining the pressure constant. and then we depend. By series coupling of several such units, which can be grouped into a whole by fully automatic coupling, continuity of operation can be achieved.

   Continuous operation can also be achieved by passing the reaction mass through a tower reactor and allowing it to flow downward in countercurrent with the upward hydrogen.



   The copper residues moistened or impregnated with fatty alcohols, which have been separated from the hydriding products, can be stored safely for some time. However, if this alcohol is removed from this copper slurry, for example by means of solvents, a highly pyrophoric copper is obtained, which ignites very easily on contact with air.



   Small amounts of copper, less than 1%, which could not be separated from the carbinols by centrifugation or otherwise, can easily be removed by mineral acids, preferably by dilute nitric acid. They can also be left in the products; they are then found, after distillation of the alcohols, in the distillation residues and can be subjected, at the same time as these residues, to a new hydriding.



   In the application of the process according to the present invention, the copper parts are extremely low and therefore the catalyst costs are practically not taken into account. Another advantage of said process lies in that, for all fatty acids dissolving in

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 high temperature finely dispersed copper, the installation and operation of a catalyst factory can be avoided and inexpensive commercial electrolytic copper can be used. In addition, with the temperatures and pressures applied in the process of the present invention, no hydrocarbons are formed or only in such small amounts that they can no longer be detected directly.



   The process according to the present invention is preferably carried out at temperatures of 200 to 335, advantageously of 265 to 3000, and at pressures of 300 to 700 atm.



   In batch operation, the reaction becomes very lively when a certain temperature is reached. A sudden rise in temperature of the order of 15 to 25 is then observed, accompanied by a strong absorption of hydrogen.



   The temperature at which the reaction begins depends on the average chain length of the carboxy compounds to be hydrated. For example, for fatty acids with short chains, it is higher than for fatty acids with medium or long chains. Furthermore, it depends on the pressure at which one is operating and, in a certain sense, also on the amount of the materials being reacted. On the scale of industrial control, the priming temperature is situated, in a pressure zone of 300 kg / cm2, between 250 and 265; in laboratory tests it is about 20 less.



   In a zone: with a pressure of about 300 kg / cm2, the hydriding lasts about 15 minutes. After this time, the absorption of hydrogen decreases sharply. The carbinols formed then have an average saponification index equal to 6, which after another 15 minutes of reaction time drops to 2 and down to 0.



   The reaction rate increases with increasing pressure and decreases to a few minutes for a pressure of 700 kg / cm2. This pressure zone is therefore particularly advantageous for continuous walking.



   As the catalyst arrives in dissolved form in the reaction vessel, the process according to the present invention avoids the highly reduced abrasive effect heretofore caused by copper chromite on pumping bodies, valves. and valves.



   It has furthermore been found that even the parts of the apparatus which, during and after expansion, come into contact with the manufacturing products containing metallic copper, are attacked only in the proportion of normal jet wear. Unlike copper chromite, copper does not exert a corrosive action.



   The invention is now explained in detail in the embodiments described below, without limitation.



  -EXAMPLE 1.-
An industrial fatty acid called top or first juice from coconut oil or palm oil acids having an acidity and saponification number of 333 was stirred with Cu powder at a temperature of 130. by passing air and in the presence of hydrogen, until the acid graàs has absorbed 2% of copper. This raw material was used for the following two series of tests: a) 800 g of the material were treated in an autoclave with a magnetic stirrer, with a capacity of 2.1, at a temperature of 300 to 3100 and under. a hydrogen pressure of 300 atm.

   No absorption has occurred.

 <Desc / Clms Page number 8>

 Sensitive hydrogen reaction and three other successive tests, under the same conditions, gave acid numbers of 310, 305 and 290. The added copper separated from the fatty acid by coarsely sticking to the bottom of the tank. container. b) In the second series of tests, 100 parts of said material were mixed with 5% of a residue from the distillation of coconut alcohols (obtained from fatty acids of coconut oil or non palm oil. previously distilled) and subjected to hydriding under the same conditions as those adopted for tests 1 ao. Already during the heating of the autoclave, there was a notable absorption of hydrogen;

   for a temperature of around 280, the absorption of hydrogen increases sharply and the temperature rises rapidly to 315 o Three tests carried out under the same conditions gave the following results:
 EMI8.1
 
<tb> <SEP> acidity index <SEP> <SEP> de-saponification index <SEP> <SEP> index OH
<tb>
<tb> 1.9 <SEP> 2.3 <SEP> 360
<tb>
<tb> 0 <SEP> 2,3 <SEP> 362
<tb>
<tb> 0 <SEP> 1, <SEP> 8 <SEP> 359
<tb>
 Example 2.-
An industrial fatty acid from the oxidation of paraffin with essentially C7 - C9 molecules and an acid number of 386, was treated under the same conditions as those adopted for example le a) In three tests carried out without addition of At the distillation residue, the substantially unchanged fatty acid with an acid number of 380 was removed from the autoclave.

   In this case too the added copper is almost completely removed in coarse form. b) In three other tests, carried out after addition of 5% of the residue of alcohols obtained by applying the process according to the present invention, it was obtained, under a temperature ranging up to 320 and under a hydrogen pressure of 300 at 340 atm, a product corresponding to the following indices:

   
 EMI8.2
 
<tb> <SEP> acidity index <SEP> <SEP> index of <SEP> saponification <SEP> <SEP> index OH
<tb>
<tb>
<tb>
<tb> 0 <SEP> 2.5 <SEP> 423
<tb>
<tb>
<tb> 1.8 <SEP> 5.6 <SEP> 418
<tb>
<tb>
<tb> 0.5 <SEP> 3.5 <SEP> 421
<tb>
 
Part of the copper is dispersed in such a fine way in the products that it passes through a double pleated filter and that, during centrifugation in a laboratory centrifuge, it is not completely sedimented. This copper can be extracted carbinols obtained according to the invention, using dilute mineral acid, for example nitric acid.



  Example 3.-
A distilled coconut oil fatty acid, with an acid number of 263 and an iodine number of 14, was brewed until dissolved with 3% Cu (OH) 2. By precipitation from a dilute copper nitrate solution, the hydroxide was prepared cold with a 20% caustic soda solution to a pH equal to 10 and, after filtering with NUTSCHE and decanting, more. Several times it was almost freed of nitrate by simplified dialysis. After drying in a stream of hot air at 40, a blue powder with a Cu content of 65% was obtained after careful grinding.

   

 <Desc / Clms Page number 9>

 a) In an autoclave with a magnetic stirrer with a capacity of 2 liters, 5 portions or batches of each 700 g of the fatty acid containing copper salts were subjected to hydriding, at a temperature between 280 and 290 under an average pressure of 300 kg / cm2. The following results were obtained:
 EMI9.1
 
<tb> Portions <SEP> <SEP> index of acidity <SEP> <SEP> index of <SEP> saponification
<tb>
<tb>
<tb> 1 <SEP> 4 <SEP> 40
<tb> 2 <SEP> 8 <SEP> 69
<tb>
<tb> 3 <SEP> 19 <SEP> 98
<tb>
<tb> 4 <SEP> 21 <SEP> 98
<tb>
<tb> 5 <SEP> 18 <SEP> 95
<tb>
 b) The test was repeated under the same conditions with a fatty acid based on peanuts, not distilled, obtained by aqueous hydrolysis with water, with the same content of copper salts.

   The result was:
 EMI9.2
 
<tb> Portions <SEP> <SEP> index of acidity <SEP> <SEP> index of <SEP> saponification
<tb>
<tb>
<tb> 1 <SEP> 1 <SEP> 2,3
<tb>
<tb> 2 <SEP> 0 <SEP> 5, <SEP> 6 <SEP>
<tb>
<tb> 3 <SEP> 0 <SEP> 6.3
<tb>
<tb> 4 <SEP> 0 <SEP> 3 <SEP>
<tb>
<tb> 5 <SEP> 0 <SEP> 2.8
<tb>
<tb> 6 <SEP> 0 <SEP> 0 <SEP>
<tb>
 Example 4.-
In stearic acid, with an acidity number of 176 and a saponification number of 196, 3% of Cu (OH) 2 at 130 Ce solution were dissolved, according to the process indicated in Example 3, divided into five portions of 700 g. each was hydrided in an autoclave with magnetic stirring or stirring with a capacity of 2 l, under a temperature of approximately 280 and a hydrogen pressure of 300 kg / cm20 The results obtained were as follows:

   
 EMI9.3
 
<tb> Portions <SEP> <SEP> index of acidity <SEP> <SEP> index of <SEP> saponification
<tb> 1 <SEP> 0 <SEP> 0 <SEP>
<tb>
<tb> 2 <SEP> 1 <SEP> 4 <SEP>
<tb>
<tb> 3 <SEP> 1 <SEP> 2.5
<tb>
<tb> 4 <SEP> 0 <SEP> 2 <SEP>
<tb>
<tb> 5 <SEP> 1 <SEP> 3 <SEP>
<tb>
<tb>
<tb> Average iodine <SEP> index <SEP>: .less <SEP> of <SEP> 2
<tb>
<tb> Average <SEP> OH <SEP> index <SEP> 203
<tb>
 Example 5.-
A spermaceti oil was resolved at a temperature of 250 by aqueous hydrolysis and it then showed an acid number of 83.

   It was treated, at 130, with 3% copper hydroxide and hydrided in 6 portions of 700 g in the autoclave with magnetic stirring of 2 1, at a temperature of 270 285 and under an average pressure of 300 kg / om2. the results were as follows:

   
 EMI9.4
 
<tb> Portions <SEP> Acidity <SEP> index <SEP> Saponification <SEP> index <SEP>
<tb>
<tb>
<tb> 1 <SEP> 0 <SEP> 4
<tb>
<tb>
<tb>
<tb>
<tb> 2 <SEP> 0 <SEP> 5 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 1 <SEP> 3
<tb>
<tb>
<tb>
<tb>
<tb> 4 <SEP> 0 <SEP> 4
<tb>
<tb>
<tb>
<tb>
<tb> 5 <SEP> 0 <SEP> 5 <SEP>
<tb>
<tb>
<tb>
<tb> 6 <SEP> 0 <SEP> 6 <SEP>
<tb>
 

 <Desc / Clms Page number 10>

 Example 6.-
4 kg of a whale oil fatty acid, composed mainly of highly unsaturated C18, C20, and C22 acids (with the following analytical indices - acidity 177, saponification 182, index of iodine 181), according to the method indicated in Example 3, for 2 hours at 1150 with Cu (OH) 2. Their copper content was then equal to 2.2%.



   During the first hydriding test, there was hardly any hydrogen absorption. The Cu separated and agglutinated at the bottom. The smell and the color made any analysis unnecessary. To the remainder of 3.5 kg were added 140 g of coconut alcohol distillation residues obtained by the process of the present invention, and the whole, divided into five portions of 700 g were subjected to hydriding o After separation of the copper from the reduced mass and the regrouping of the different portions, it remained
3,300 g of crude alcohol with an acid number 2, a saponification number 3, an iodine number 7 and an OH number 1890 Example 7.-
Fatty acids were obtained by alkaline saponification of castor oil.

   Non-distilled fatty acids have the following analytical indices:
Acidity index 190 Saponification index 192
Iodine number 89 OH number 175
After stirring for two hours at a temperature of 100 ° C. with copper hydroxide, the fatty acid absorbed 2.2% Cuo. The hydration, in five portions of 700 g each, was carried out in the 2 le magnetically stirred autoclave at an average temperature of 285 and an average pressure of 300 kg / cm 2 The reaction time was approximately 30 minutes.



   After separation of the copper, the 6 combined portions were obtained:
 EMI10.1
 
<tb> 3280 <SEP> g <SEP> of crude <SEP> alcohol <SEP> with <SEP> a <SEP> index <SEP> of acidity <SEP> 1
<tb>
<tb>
<tb> a <SEP> index, <SEP> of <SEP> saponification <SEP> 3.5
<tb>
<tb>
<tb>
<tb> a <SEP> index <SEP> of iodine <SEP> 4
<tb>
<tb>
<tb>
<tb> and <SEP> a <SEP> index <SEP> OH <SEP> 345
<tb>
 Example 8.-
10 t of coconut oil fatty acid, - crude from separation, having an acid number of 235, a saponification number of 265 and: an iodine number of 14, were reduced, after having been divided into numerous batches, in a heated oven, as described to hydrogen by a hydrogen circuit passing through the autoclave and provided with a cooler.

   The fatty acid had been brought to an average content of 2.2% copper, derived exclusively from copper decomposed several times. The reaction started briskly at 265, the highest temperature was 285, the average reaction time 30 minutes, the pressure 300 kg / cm2.



   The product obtained had an average acid number of 0.5
An average saponification number of 1.4 and an average OH number of 280.



   From the gas circuit, 7% lower alcohols separated in the separator of the cooler after extraction of 1 water), with an OH index of 3900

 <Desc / Clms Page number 11>

 example 9.-
After having distributed them into a large number of batches or portions, 20 tonnes of a mixture of crude fatty acids from separation containing 60% of oil fatty acids were hydrided in an oven of the model indicated above. coconut and 40% fatty acids from beef tallow, having an acid number of 202, saponification number of 233 and an iodine number of 25 (copper content 2.1%).



   The reaction started vigorously at about 260, the highest temperature was 280, the average reaction time 30 minutes and the pressure 300 kg / cm 2.



   The product featured:
 EMI11.1
 
<tb> a <SEP> index <SEP> of acidity <SEP> average <SEP> of <SEP> 0
<tb>
<tb>
<tb> a <SEP> index <SEP> of <SEP> saponification <SEP> average <SEP> of <SEP> 1
<tb>
<tb>
<tb> a <SEP> index <SEP> of iodine <SEP> mean <SEP> of <SEP> 1
<tb>
<tb>
<tb>
<tb> and <SEP> an <SEP> index <SEP> OH <SEP> average <SEP> of <SEP> 242.
<tb>
 



     6% lower alcohols) with an OH number of 345, were retained in the cooler separator.



  Example 10.-
From raw beef tallow of mediocre quality giving off an unpleasant odor and very dark in color, having the indices: acidity 64.5, saponification 194 and iodine 54.4 were obtained by doubling with water at 275 and under pressure a fatty acid with the following indices:
Acidity 64.5 saponfication 200 iodine 55.7 appearance: from very dark to black.



   The 130 fatty acid was treated in a horizontal stirrer for several hours with copper powder. During this time, it absorbed 2.5% of its weight in copper. Then, as a 20% solution in excess tallow alcohol, 0.5% of the diester of the mixed polymerization of styrol and maleic acid anhydride was added to alcohols of; 3uif. . In a V2A steel magnetically stirred autoclave with a capacity of 2 liters, 700 g of the reaction liquid were hydrated each time at an average temperature of 290 to 300 and an average pressure of 31 atm. . Hydrogen uptake was completed in 20-30 minutes.



  The tallow alcohols obtained act normally and, after passing through a fine filter, they have a color so light that in a thin layer they appear absolutely colorless. There is no copper separation in the autoclave, the dark black reaction liquid passes residue-free through a simple pleated laboratory filter.

   The alcohols obtained presented the following analytical indices:
 EMI11.2
 
<tb> <SEP> acidity index <SEP> <SEP> index of <SEP> saponification
<tb>
<tb>
<tb> 1.7 <SEP> 3, <SEP> 5 <SEP>
<tb>
<tb> O <SEP> 4, <SEP> 5 <SEP>
<tb>
<tb> 1 <SEP> 2, <SEP> 5 <SEP>
<tb>
<tb> 2 <SEP> 5
<tb>
<tb> 1.5 <SEP> 5
<tb>
<tb> 0 <SEP> 4.5
<tb>
<tb> 0.5 <SEP> 2.5
<tb>
<tb> 2 <SEP> 4.5
<tb>
<tb> 1, <SEP> 5 <SEP> 3
<tb> 2 <SEP> 3
<tb>
 

 <Desc / Clms Page number 12>

 
Between the different batches or portions to be treated, the autoclave was emptied in an inclined position and no cleaning was carried out. The controlled OR indices only differed by one unit from the theoretical figure calculated.



  Test loads from the same batch, subjected to hydriding without addition of stabilizer, attached to saponification indices between 20 and 60; in no case did the copper dispersion remain intact, in part there was even total precipitation.



  Example 11.-
A fatty acid - defined by the supplier as a fatty acid originating from the refining of palm oil, having the following indices: acidity 228 saponification 252 iodine 15.2 very dark shade up to black, contained due to a stay in a container with walls lined with lead sheets 10 mg of Pb for 1 kg of fatty acid The following tests were carried out in the 2 L autoclave made of V2A steel with magnetic stirrer, at a temperature of 295 0, an average pressure of 310 atm and for a batch of 700 g. The operation was first carried out with an Ou-Or-0 catalyst carefully prepared according to the Org. Synthesis 19/33. With a catalyst at 7%, a reaction time of 20 minutes was obtained,

   an alcohol having an acid number of zero and a saponification number equal to 1. The fatty acid from refining, containing lead, gave in 80 minutes, with the same quantity of catalyst under slow absorption of hydrogen, a alcohol having an acid number equal to 7 and a saponification number equal to 40, although once the reaction is complete, it is still left to run for two and a half hours under pressure and temperature with a magnetic stirrer working rapidly.



   The fatty acid was then brought, by means of copper powder, to an Ou content of 2.2% and then it was subjected to hydriding without addition of stabilizer. The results were as follows:
 EMI12.1
 
<tb> Portions <SEP> <SEP> index of acidity <SEP> <SEP> index of <SEP> saponification
<tb>
<tb> 1 <SEP> 12 <SEP> 65
<tb>
<tb> 2 <SEP> 10 <SEP> 66
<tb> 3 <SEP> 10 <SEP> 71
<tb>
<tb> 4 <SEP> 15 <SEP> 73
<tb>
<tb> 5 <SEP> 9, <SEP> 5 <SEP> 71
<tb>
<tb> 6 <SEP> 9, <SEP> 5 <SEP> 72
<tb>
<tb> 7 <SEP> 139 <SEP> 220
<tb>
 For all batches, copper was eliminated; for batch n. 7 the intoxication of the oven had become such that the hydriding stopped prematurely.



   Even with an amount of copper increased to 3%, no better results were obtained:
 EMI12.2
 
<tb> Portions <SEP> <SEP> index of acidity <SEP> <SEP> index of <SEP> saponification
<tb>
<tb>
<tb> 1 <SEP> 9, <SEP> 5 <SEP> 59
<tb>
<tb>
<tb>
<tb> 2 <SEP> 9 <SEP> 68
<tb>
<tb>
<tb>
<tb> 3 <SEP> 10 <SEP> 72
<tb>
<tb>
<tb>
<tb> 4 <SEP> 12 <SEP> 70
<tb>
 
Industrial tests with batches of 400 kg. In autoclaves of 1000 liters, under the same conditions, with a stream of hydrogen which beaded and simultaneous elimination of the water of reaction, gave better results, but they have nevertheless shows a weakening of the reaction.

   Upon opening the furnace, after processing 10 batches, the entire liquid filled portion of the furnace was found to be packed with red copper powder, either solid or powdery.
 EMI12.3
 
<tb>



  <SEP> indices of <SEP> this <SEP> produced:
<tb>
<tb>
<tb> <SEP> acidity index <SEP> <SEP> index of <SEP> saponification
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> '<SEP> 4
<tb>
<tb>
<tb>
<tb> 2 <SEP> 10
<tb>
<tb>
<tb>
<tb> 3 <SEP> 12
<tb>
<tb>
<tb>
<tb>
<tb> 5 <SEP> 20
<tb>
<tb>
<tb>
<tb> 4 <SEP> 15
<tb>
<tb>
<tb>
<tb> 3 <SEP> 12
<tb>
<tb>
<tb>
<tb> 8 <SEP> 40
<tb>
<tb>
<tb>
<tb> 6 <SEP> 45
<tb>
<tb>
<tb>
<tb>
<tb> 10 <SEP> 105
<tb>
 

 <Desc / Clms Page number 13>

 
Almost all of the added copper had deposited in the autoclave. From the fourth batch, the hydriding times increased and finally exceeded 5 hours.



   In contrast to these tests, the fatty acid containing 2.4% copper was mixed with the 0.5% coconut alcohol diester of a mixed polymerizate of styrol and maleic acid anhydride and it was added. hydrided under the same conditions in the 2-liter autoclave.



   During the 40 tests carried out, there was no removal of copper, either in the autoclave or in the piping.



  Example 12.-
A fatty acid from cottonseed oil refining containing 2.5% Cu, very dark in color, with the indices: acidity 116.5 of saponification 195.6 and iodine 96 was mixed with a diol obtained from distillation residues, acting as a stabilizer, and subjected to hydriding under known conditions. As the average value for 6 treated batches, an acid number of 1 and a saponification number of 2.5 were determined. All lots were stained dark black by the colloidal copper, and no removal occurred. By filtering through fine filters, the very dark fatty acid gave a crude alcohol which, even without distillation, only had a light yellow tint under fairly thick layers.



  Example 13.-
The fatty acid used in Example 10 was hydrided under the conditions of Example 10. Instead of the stabilizer used in Example 10, 1/2% of polyoctadecyl vinyl ether was added. as a waxy mass. The reaction proceeded normally in the autoclave and without removal of copper.



  The alcohols thus obtained gave the following indices:
 EMI13.1
 
<tb> Acidity <SEP> Saponification
<tb>
<tb>
<tb> 2 <SEP> 4.2
<tb>
<tb> 0.8 <SEP> 3.5
<tb>
<tb> 0.6 <SEP> 2.2
<tb>
<tb> 1.5 <SEP> 1.8
<tb>
<tb> 0.7 <SEP> 5.6
<tb>
<tb> 1.0 <SEP> 2.6
<tb>
 Example 14. -
The procedure was as for Example 10, but using as stabilizer an ester of polyvinyl alcohol, polyvinyl palmitate, in the proportion of 1/2%. In this case too, the reaction proceeded normally without removing the copper.



   The alcohols obtained presented the following indices:
 EMI13.2
 
<tb> Acidity <SEP> Saponification
<tb>
<tb> 0.6 <SEP> 6
<tb>
<tb>
<tb> 0.5 <SEP> 2.4
<tb>
<tb> 0.7 <SEP> 1.8
<tb>
<tb> 1.2 <SEP> 3.1
<tb>
<tb> 1.0 <SEP> 1.0
<tb>
<tb> 0 <SEP> 2.0
<tb>
 

 <Desc / Clms Page number 14>

 Example 5.-
The starting materials, process and apparatus were the same as for Example 10. As stabilizer, a mixed polymerizate composed of α-Methylstyrol and blown linseed oil was used. After filtering off the copper-containing fatty acid and treating with the stabilizer, 0.6% polymerizate in the fatty acid was found. The reaction proceeded normally and without removal of copper.



   The indices of the alcohols obtained were as follows:
 EMI14.1
 
<tb> Acidity <SEP> Saponification
<tb>
<tb>
<tb> 2.1 <SEP> 2.3
<tb>
<tb> 0 <SEP> 4
<tb>
<tb> 0.5 <SEP> 1.5
<tb>
<tb> l <SEP> 1.8
<tb>
<tb> 0 <SEP> 0.5
<tb>
<tb> 1.5 <SEP> 4.5
<tb>
 Example 16.-
The starting materials and working conditions were the same as in Example 10. 0.6% polyketyl acrylate was added as stabilizer. A small amount of insoluble fatty acid was removed. by filtration. The reaction, as in the previous examples, proceeded normally, without removing the copper.

   Here are the clues obtained:
 EMI14.2
 
<tb> Acidity <SEP> Saponification
<tb>
<tb>
<tb>
<tb>
<tb> 0.5 <SEP> 3, <SEP> 3 <SEP>
<tb>
<tb>
<tb>
<tb> 0 <SEP> 2.8
<tb>
<tb>
<tb>
<tb> 0.5 <SEP> 4.2
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> 1.5
<tb>
<tb>
<tb>
<tb> 0 <SEP> 0.5
<tb>
<tb>
<tb>
<tb> 1.5 <SEP> 5.2
<tb>



    

Claims (1)

ABSTRACT. The subject of the invention is: 1) A process for the manufacture of carbinols with chains at C6 or more, preferably at C11 and above, by catalytic hydriding, suitable di-fatty acids, their esters, in particular glycerides and (or) anhydrides, using copper acylates , said process consisting essentially of using colloidal copper as a catalyst and hydriding in the presence of protective colloids, so as to prevent clumping of the colloidal copper during the reaction. 2) In such a process, the following additional characteristics taken in isolation and in all their technically possible combinations: a) during hydriding, the copper content is from 1 to 4%, preferably from 2.0 to 2, 2, relative to the quantity of substances to be hydrated; b) copper, in particular electrolytic copper, or its compounds soluble in fatty acid, such as oxides, hydroxides, carbonates or organic copper salts, are dissolved, preferably hot, for example at a temperature of 100 at 14000, in fatty acids and separated in a particularly active colloidal form by heating the solutions, for example at 150 or more, in the presence of hydrogen; <Desc / Clms Page number 15> c) during the dissolution of copper or its compounds, gases containing oxygen, for example air, are passed through the liquid; d) preferably only a small part, in fatty acid form, of the substance to be hydrated is used as the solvent for copper; said solution then being mixed with the rest of the substance to be hydrated and the whole of the mixture being finally subjected to hydriding; e) the copper acylate solution is brought to a temperature at which no separation of the copper has yet taken place and is mixed in the reaction vessel with the remainder of the substance to be hydrated, preferably in such a manner that the copper acylate solution is introduced into the substance already heated to a higher temperature, for example to the reaction temperature; f) as protective colloids, synthetic polymerization and / or condensation resins of a high molecular weight are used ,. which are soluble in hot acids; g) as protective colloid, a mixed polymerizate of styrol and of maleic acid anydride is used, preferably in esterified form; h) the protective colloids are used in the proportion of 0.1 to 1% relative to the mass of the substance to be hydrated; i) as protective colloids, sterides, phosphatides, albuminoids, mucins and other substances accompanying natural oils, fats or fatty acids are used; j) unpurified fats or oils of vegetable or animal origin are used as starting material, as well as fatty acids, distillation fatty acids and synthetic fatty acids which are extracted therefrom by hydrolysis, for example alkaline saponification followed by acid precipitation and careful washing; k) fatty acids contaminated with iron are used as raw material; 1) in addition to copper, small amounts of iron or manganese are added to the base material to be hydrated; m) to fatty acids poor in accompanying substances or deprived of said substances by distillation, such accompanying substances or residues from the distillation of fatty acids or distilled alcohols obtained according to the invention are added; n) during the reaction the presence of metals acting as a catalyst, such as lead or bismuth, is avoided; p) the presence of sulfate ions or chlorine ions is avoided during the reaction; q) hydriding takes place at temperatures from 200 to 335, preferably 265 to 3000; r) the hydriding is carried out under pressures of 200 to 700 atm; s) the first superheated hydrogen is directed through a heating system provided in the hydradration furnace and it is only then introduced into the substance subjected to hydriding; t) the hydrogen is passed several times through the heating system and an outside heater, before <Desc / Clms Page number 16> bring it into the substance; u) the catalyst is separated, for example by centrifugation, from the material subjected to the hydriding, and is then reused; v) during the distillation, the copper residues remaining in the alcohols are removed by passing part of the distillation residue, continuously or periodically through a centrifuge to then return it to the distillation; w) after standing for some time or after undergoing treatment with water or steam, copper is separated from the product by high speed centrifugation of the broken dispersion; x) copper is removed from the product by filtration through a sponge filter made of asbestos or the like; y) copper is removed from the product by treating the dispersion in an ultrasonic field and subsequent filtration; z) the dissolution of the new or recovered copper takes place in agitators with a horizontal shaft, preferably rotating rapidly and eccentrically and comprising beaters.