DE2057521A1 - Reppe-type catalytic carbonylation process - Google Patents

Description

SHELL INTERNATIONAL "RESEARCH MAATSCHAPPIJ N.V., The Hague, Netherlands

"Reppe-type catalytic carbonylation process" Priority: November 25, 1969, The Netherlands, No. 6917764

The invention relates to an improved carbonylation process, ie a process for the preparation of carbonyl compounds by reacting an unsaturated compound with carbon monoxide and a compound having a reactive hydrogen atom, ie a hydrogen atom bonded to an oxygen, sulfur or nitrogen atom. The unsaturated compound is optionally replaced by its precursor, ie a compound which is easily decomposed under the reaction conditions of the carbonylation process to form the unsaturated compound in question. Pre-products for olefins are, for example, in particular the alcohols or ethers, which can be regarded as addition products of water or alcohols to the ethylenically unsaturated bonds of the olefins.

Examples of suitable compounds with reactive Y / as Beretofffen are 'water, alcohols, ammonia, non-tertiary amines, Mercaptans and carboxylic acids. If the compounds of this class

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assigned the general formula HY is used in the carbonylation reaction a radical of the general formula I on a carbon atom of the unsaturated compound

-? r ^Y (D

bonded, while the hydrogen atom of the compound of the general formula HY is bonded to another carbon atom of the unsaturated compound. If the compound of the formula HY Y / ater iot (Y = OH) ₁ , the product obtained is accordingly a carboxylic acid. Esters or amides or amides or thioesters or carboxylic acid anhydrides substituted by hydrocarbon radicals are obtained when the compound of the formula HY is an alcohol or ammonia or a non-tertiary amine or a mercaptan or a carboxylic acid.

Provide some precursors for the unsaturated compounds in addition to the unsaturated compounds concerned, compounds with reactive Waaeeretoffatomen. An alcohol can for example form an olefinically unsaturated compound together with water, so that in principle there is no further to form a carboxylic acid Waeser is needed. Ethers are also examples of preliminary products for unsaturated compounds which can react with a reactive hydrogen atom without adding a compound. £ b form "" loh carboxylic acid esters, although in principle no other Alcohol content needs to be added.

Alcohols can thus react both in their property as precursors for olefinically unsaturated compounds and in their property as compounds with reactive hydrogen atoms. Of course, you can also use the carboxylic acids that are used in.

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a carbonylation reaction carried out in the presence of water arise, due to their reactive hydrogen atoms, further convert carboxylic acid anhyarides. If monocarboxylic acids are to be prepared from olefins, such as unbranched 0C-01efins, and carbon monoxide and water, at least 1 mol of water should accordingly be used per mole of the olefin (s), while generally the use of a molar excess of water, in particular an excess ^ from 0.5 to 1.5 moles of Hp ^ per equivalent of the olefinically unsaturated compound or its precursor, is preferable. , |

It can be seen that carboxylic acids and their salts can optionally also be prepared from compounds which have a radical of the general formula I in which Y is not a hydroxyl group. For example, esters can be saponified. In general, however, it is more economical to carry out the reaction in such a way that carboxylic acids are formed immediately. Furthermore, olefins and not their precursors are preferably used as a starting point.

It can be seen that the acids obtained in the abovementioned reaction always have a number of carbon atoms which is 1 greater than that of the olefins from which they are produced.

The aim of the invention relates in particular to improved carbonylation processes of the so-called "Reppe type", ie to carbonylation processes in which certain heavy metals and / or their compounds are used as catalysts (compare, for example, the book by Jürgen Falbe "Syntheses with carbon monoxide ¹¹ , Springer Verlag , Berl in, Heidelberg, New Yqrkj

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Pages 73 to 119) · Of the metals contained in the catalysts suitable for the Reppe process, the metals of Group VIII of the Periodic Table are preferred. On page 7β of the aforementioned book it is stated that iron, cobalt, nickel, ruthenium, rhodium and palladium can be added in the form of carbonyls, metals, salts, complex salts or oxides, depending on the type of reaction concerned. It is also stated there that the type of anions is unimportant when salts are used, especially in the case of nickel. The catalytic effectiveness of nickel halides increases with the atomic weight of the halogen in question. Fluorides show the lowest, iodides the highest activity.

Catalysts of the aforementioned type, in particular nickel iodide, are also used with preference for the purposes of the invention.

The invention relates to a catalytic carbonylation process of the Reppe type, which is characterized in that the reaction takes place in a gas phase or, preferably, a liquid Phase is carried out, which is in contact with a solid metal alloy, the

A) at least 40 percent by weight of nickel and chromium, the weight ratio being Nickel / chromium is 0.1: 1 to 10: 1, and optionally

B) iron, if appropriate

C) molybdenum and / or tungsten and optionally

I)) silicon and / or silver and / or copper and / or vanadium

and / or manganese and / or rhenium and / or cobalt contains.

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The metal alloy used as cocatalyst in the process of the invention preferably has an iron content of at most 50 percent by weight, in particular at most 10 percent by weight. The combined nickel and chromium content of the alloys used according to the invention is preferably at least 60 percent by weight, while the nickel / chromium weight ratio is preferably 0.2: 1 to 5 s 1, in particular 0.5: 1 to 2: ^Λ . Molybdenum and / or tungsten are preferred as components of the alloys used according to the invention over iron. λ The molybdenum content of such alloys it is preferably 10 to 30 weight percent, the tungsten content is preferably 1 to 10 weight percent.

The alloys used according to the invention preferably contain a total of no more than 10 percent by weight of the aforementioned metals other than nickel, chromium, molybdenum, tungsten and iron (D).

Good results are achieved with alloys which are 90 to 100 percent by weight, in particular 95 to 100 percent by weight Contains nickel and chromium taken together, especially when these two components are in at least approximately equal weights available.

According to the invention, however, it is particularly preferred to use Le- ' Alloys with a nickel content of 40 to 60 percent by weight, a chromium content of 10 to 25 percent by weight, a molybdenum content from 10 to 30 percent by weight, a V / OIfran content of 1 to 6 percent by weight and a proportion of at most 10 percent by weight, preferably less than 5 percent by weight, in particular

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especially less than 2.5 percent by weight of other components. Very satisfactory results will be obtained with a commercially available one Nickel alloy (nickel alloy C) achieved. This nickel alloy generally contains 4 to 8 percent by weight iron, 14 to 19 percent by weight molybdenum, 3 to 5.5 percent by weight tungsten, 12 to 16 percent by weight chromium, small amounts of silicon and manganese, traces of carbon and the balance nickel. The average composition of this alloy is: 51 percent by weight Ni, 17 percent by weight Cr, 17 percent by weight Mo, 6 percent by weight Fe, 1 percent by weight Si, 1 percent by weight Mn, 4.5 percent by weight W and at most 0.12 percent by weight C.

Although no special theoretical explanation is to be given for the co-catalytic effect of the nickel / chromium alloy used according to the invention, it should be noted that this is at least not due exclusively to phenomena on the surface of the solid alloy, but that part of the alloy in the reaction medium, at least if it is liquid, must solve in order for the co-catalytic V / MPACT in \ a maximum degree in phenomenon occurs. However, if it does, gradual corrosion of the alloy is inevitable. However, this corrosion can be too severe when using alloys

be used with an unfavorable composition. Such a undesirable effect is caused, for example, by a high iron content, while molybdenum and volcanic oil tend to limit corrosion.

Because of the inevitable corrosion, it is generally not very convenient to use a reactor, some of which is made up of one

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_ ₇ _ 2017 121

Alloy consists or is lined on the inside with such an alloy which, according to the method of the invention, is intended to be in contact with the reaction medium as a co-catalyst. According to a preferred embodiment of the method according to the invention, the alloy used as co-catalyst is within. of the reactor in the form of separate solid pieces, for example as chips, spirals, pipes, plates, tapes, fabrics, granules and / or powder. The contact of such alloy pieces with the reaction mixture can be improved by stirring. Following a modified method, one or more similar reactors, through which flows the reaction mixture, are charged with the aforementioned pieces. Chips and spirals are very well suited for this type of application. However, the alloy can also be applied to a suitable carrier, which can, for example, be in particle form. Pieces made of the alloy in question are particularly advantageous which are firmly attached in the reactor or can be easily removed again and if necessary or, if necessary, can be replaced. Such parts of \ the aforementioned alloy can have a functional purpose ER \ fill and for example as a stirrer, baffles serve OAER partitions. To make it easier to take them out, these objects can be attached to one or more strips, for example, or with help in front of them. Screws, bolts or pins to be connected. According to a modified method, the baffle plates and partition walls can be welded to the V / and of the reactor. The alloys can also be applied as a coating to the aforementioned functional parts.

For the reasons explained above, the reactor wall should

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preferably either itself from a corrosion-resistant material

al exist or lined with such a material inside be. Suitable materials which are sufficiently stable under the reaction conditions prevailing in the process of the invention are known. Examples are ^ etrafluoroethylene and various Alloys. Very suitable alloys are, for example, the various types of steel with low corrosion resistance and in particular nickel alloys, which consist of at least 40 percent by weight nickel and, as other components, e.g. molybdenum, Contains iron, chromium, manganese, copper, silicon, titanium and / or aluminum. Of these nickel alloys, those preferred, which consist mainly of nickel and molybdenum and their total proportion of other components, if such components are present at all, at most 20 percent by weight, in particular at most 10 percent by weight, and their chromium content

0 to 3.5 percent by weight, in particular 0 to 2 percent by weight. Very good results are achieved with alloys, which contain 45 to 75 percent by weight nickel, 20 to 50 percent by weight molybdenum and 0 to 2 percent by weight chromium. A An example of alloys of this class is a commercially available nickel alloy ("Nickel Alloy B"), which in general 24 to 32 percent by weight molybdenum, 3 to 7 percent by weight Contains iron, small amounts of silicon and manganese, traces of carbon and the remainder nickel. The average composition such an alloy is 60 percent by weight Ni, 28 percent by weight Mo, 6 percent by weight Fe, 1 percent by weight Si,

1 percent by weight Mn and at most 0.12 percent by weight C.

The one used as a cocatalyst in the process of the invention

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Nipkel / chromium alloy preferably has a specific surface of at least 10 cm / g. Such alloys are very useful! which has a total surface of at least 2 cm

ρ
and in particular at least 4 cm per ml of reaction medium, if this is liquid.

The proportion of the metal compound of the VIII group of the periodic

Reppe

Systems which in the process of the invention as (Haupt H & taly sat or is used is preferably from 0.002 to 0.2 gram atom of the metal in question per equivalent of the olefinically unsaturated. ^ - th compound or its precursor, which (s) carbonylert shall be. As a rule, the use of a higher amount of catalyst does not adversely affect the reaction, but it does because of the need to separate large amounts of catalyst from the reaction product, certain difficulties arise. Prevented proportions of 0.001 to 0.1 gram atom of the metal concerned per mole of the compound are used in the process of the invention with (a) reactive hydrogen atom (s), in particular Water. The proportion of nickel halides, especially the one used as a catalyst most preferred nickel iodide which are Halides ™ either used as such or formed in situ is preferably from 0.005 to 0.05 mol per mol of water or another compound with (a) reactive hydrogen * - atojn (en).

In one proposal, an improved Reppe method is described, according to which nickel iodide or a nickel iodide and pyridine containing system is used as the main catalyst. According to the above proposal, the catalyst system contains additional

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Lich hydriodic acid ', the molar ratio pyridine / iodine- " hydroic acid 8:10 to 10: 8, preferably 9:10 to 10: 9, in particular 9.5: 10 to 10: 9.5, the ratio of gram atom nickel / mol pyridine 1: 0.25 to 1:10, preferably 1: 1 to 1: 3 and the amount of nickel fed into the reactor 0.1 to 3 percent by weight, preferably 0.3 to 1.5 percent by weight, based on the total materials used, but

be,
without the carbon dioxide - / ^ in catalyst of this type can weraen also used as the main catalyst in the process of the invention.

In the Reppe process in general and also in dn. according to the invention Method carried out Reppe process, a liquid reaction mixture can be used, which is inert solution and / or contains diluents. In general, a gas mixture of carbon monoxide with at least a gas which is inert towards the reaction components and reaction products, such as nitrogen or a gaseous Aükai, can be used. The carbon monoxide concentration in such a gas mixture should, however, preferably be at least 50 percent by volume and substantially pure carbon monoxide is particularly preferred. The carbon monoxide partial pressure is generally not particularly critical. It can be over 200 atmospheres, but such high pressures make high demands the construction of aes reactor. The carbon monoxide partial pressure is thus preferably 30 to 200 atmospheres, in particular 70 to 150 atmospheres. The reaction generally takes place at such pressures in the liquid phase, the reaction components being reaction products and catalyst components do not evaporate to such an extent that the vapors concerned make up the total.

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vapor pressure in "the gas phase above the" liquid reaction medium

a share
diums essential / contributed. If pure carbon monoxide is fed in, its partial pressure can thus in general be equated with the total pressure. A proportion of carbon monoxide absorbed during the conversion can be replaced and the original pressure can thus be "maintained continuously or at regular intervals.

would result from the introduction of more carbon monoxide into the reactor to be restored.

The applied in the Reppe process reaction temperatures can depending are of the type of Reaktionskomponenten.innerhalb a "wide range. In general, sind'jedoch temperatures 140-250 ⁰ C suitable. In the production of carboxylic acids from unbranched ct-olefins or their precursors Temperatures within the abovementioned range are preferably used, in particular temperatures from 170 to 220 ^° C. One advantage of the special catalyst system used in the process of the invention is that the carbonylation takes place at a sufficiently high rate even at relatively low temperatures because unwanted side reactions like wanted it to take place in a much lower degree than at higher temperatures.

The effect of the aforementioned nickel / chromium alloy as a cocatalyst in the process of the invention can be increased by pretreating the catalyst under the conditions of the reaction. Such pretreatment is carried out for example at 200 ⁰ C and a carbon monoxide partial pressure of 140 atmospheres (gauge pressure) with an aqueous Nickeljodidlösung which to-

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-12-may also contain a small amount of hydrogen iodide.

The process of the invention can either be discontinuous, be carried out semi-continuously or continuously.

From the reaction mixture obtained according to the invention, the Products can be separated off by any suitable known method, for example by phase separation. Before product separation you can dilute the reaction mixture, e.g. with Pent ^ an. It can also be expedient to then apply the mixture to distill. The catalyst phase can be used again, if necessary after the addition of water. The alloy used as a co-catalyst can be used, for example, by decanting or filtration isolated and then used again.

The method of the invention, as the method described in the above-mentioned proposal, for the production of C ₁₀ _2 ₅ - "" ^ ^ ^{onocar ons} ^ ^{acids aua unverzwe} iil "t ^ ^en q_2A ~ ^f preferably> preferably C-C 2_2O ₁ .. .

As already explained in the above proposal, alkali salts, especially sodium salts, of the aforementioned monocarboxylic acids surface-active compounds with good detergent action, which are also suitable for use with "hard" water. Such alkali salts are also easily biodegradable, i.e. they are easily decomposed by microorganisms if they are washed up in e.g. rivers, lakes and canals after use

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will. The alkali salts »especially the sodium salts, the Carboxylic acids prepared by the process of the invention can be used as such or together with small amounts of conventional Additives for Toilettfceifen are used. However, the aforementioned salts can also be incorporated into mixtures which, for example, contain at least one solvent and / or diluent and / or contain at least one of the other components that are conventionally used in manufacture by counterfeit detergents for various purposes will.

The examples illustrate the invention.

example 1

A 250 ml autoclave made of nickel alloy B ^M with a diameter of 5.5 cm and a height of 11 cm, which is equipped with a magnetically driven propeller stirrer made of polytetrafluoroethylene, is filled with 1.36 g -

(4.34 mmol) nickel (II) iodide, 41.7 g (186 mmol) hexadecene-1, \ 6.95 ml (386 ml mol) water and 17.7 g spirals made of "nickel alloy C "is charged with a specific surface area of about 20 cm / g.

The autoclave is closed and rinsed twice with hydrogen-containing carbon monoxide (98 ",> CO + 2 # H ₂ ) by pressurizing it to a pressure of 20 atmospheres (overpressure) and then releasing the pressure. The CO partial pressure is then increased increased to 90 atmospheres (overpressure), after which the temperature is also increased to 200 ^° C. with stirring,

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The pressure rises to 140 atmospheres (overpressure). By regularly adding pressurized carbon monoxide the CO absorbed in the course of the reaction is replaced, and the pressure is maintained at about 140 atmospheres (gauge). There is no further pressure drop after 2.5 hours and the autoclave is cooled to room temperature. After releasing the pressure, the reaction mixture absorbed in pentane by decanting from the metal spirals separated, washed successively with water, 4 η hydrochloric acid and wieaer water and finally over waseerfreiera Dried sodium sulfate.

The residue obtained after evaporation of dea pentane contains 169 milliaquivalents of carboxyl groups, which corresponds to a yield of 91 percent, based on the hexadecene-1.

It is noted, DAT 33 mole percent of the entstanuenen carboxylic acids having a straight carbon chain 56 mole percent of a methyl group in- <i. abutment condition to the carboxyl group \ possess, 9 llolprozent an ethyl group in this ° C ~ position comprise and 2 mole percent in the 06-position have a propyl group or a longer hydrocarbon radical.

Example 2

The experiment of Example 1 is repeated, but with an-3tell'e Eg spirals made of "Liickelle alloyC" and made of this alloy existing cylinder with an outer diameter of 5 cm, a height of 9 cm and a wall thickness of 0.1 cm is placed in the autoclave. It is found that

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the reaction product has 58 milliequivalents of carboxyl groups after a reaction time of 5.5 hours, which is a Yield of 31 percent, based on the hexadecene-1, corresponds.

Example 3

The experiment of Example 1 is repeated for comparison purposes, but no spirals made of "nickel alloy C ^M are used. The reaction product obtained after a reaction time of 7 hours contains <32 milliequivalents of carboxyl groups, which corresponds to a yield of 17 mol percent based on the hexadecene. 1, corresponds to.

• Example 4

The experiment of Example 1 is repeated, but instead of spirals made of "nickel alloy C" 2.0 g of an alloy of 51 percent by weight nickel and 49 percent by weight chromium are used in a spiral shape. The reaction is also carried out in this case at 18O ⁰ C and while maintaining a pressure of about 120 atmospheres (gauge pressure). The temperature and pressure are thus lower than in the experiments in the aforementioned examples, so that the reaction proceeds at a comparable rate in the presence of this much more active alloy.

After a reaction time of 3.5 hours, the worked-up contains Crosslinking product 162 milliequivalents of carboxyl groups, which corresponds to a yield of 87 mol percent, based on the hexadecene-1.

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-16- Example 5

The experiment of Example 4 is repeated for comparison purposes, but instead of the spirals from the nickel / chromium -Alloy 1 g kickel powder is added. After a reaction time of 6 hours contains the reaction product 67 molar equivalents of carboxyl groups, which corresponds to a yield of 36 mol percent, based on the IIexadecen-1.

Example 6

The experiment of Example 4 is repeated for comparison purposes, but instead of the spirals from the nickel / chromium -Alloy 1 g of chromium powder is added.

After a reaction time of 6.5 hours, the reaction product contains 11 milliequivalents of carboxyl groups what a yield of 6 mol percent, based on the hexadecene-1, is equivalent to.

Example 7

The experiment of Example 4 is repeated for comparison purposes, but instead of the nickel / chromium alloy Mixture of 1 g nickel powder and 1 g chrome powder added will.

After a reaction time of 6 hours, the reaction product contains 37 roughly equivalent carboxyl groups, which corresponds to a yield of 20 mol percent, based on the 1-hexadecene.

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-17- Example 8

The experiment of Example 4 is repeated for comparison purposes, but no alloy is added as a cocatalyst will.

After a reaction time of 6 hours, the reaction product contains 0.8 milliequivalents of carboxyl groups, which is a yield of less than 0.5 mole percent, based on the hexadecene-1, corresponds.

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Claims (25)

Claims e \ Catalytic carbonylation process aea Reppe type 3, characterized in that the reaction is carried out in a gas phase or preferably a liquid phase which is in contact with a solid metal alloy A) at least 40 percent by weight nickel and chromium, where the nickel / chromium weight ratio 0.1: 1 to 10: 1 as well as, if applicable B) iron, if appropriate C) molybdenum and / or tungsten and optionally D) silicon and / or silver and / or copper and / or vanadium and / or manganese and / or rhenium and / or cobalt contains. 2. The method according to claim 1, characterized in that the alloy has an iron content of at most 50 percent by weight, preferably at most 10 percent by weight 3. The method according to claim 1 or 2, characterized in that the ^ common content of the alloy of nickel and Chromium is at least 60 percent by weight. 4. The method according to claim 3 »characterized in that the nickel / chron weight ratio 0.2: 1 to 5: 1, preferably 0.5: 1 to 2: 1. 5. Ve'rfahren according to claim 1 to 4, characterized in that that the alloy is 10 to 30 percent by weight of molybdenum contains. 109826/1990 6. The method according to claim 1 to 5, characterized in that the alloy contains 1 to 10 percent by weight of tungsten. 7. The method according to claim 1 to 6, characterized in that the total proportion of nickel, chromium, iron, molybdenum and tungsten various components at most 10 percent by weight amounts to. 8. The method according to claim 1 to 7, characterized in that that the alloy is 40 to 60 percent by weight nickel, 10 to 25 percent by weight chromium, 10 to 30 percent by weight molybdenum, 1 to 6 percent by weight tungsten and a maximum of 10 percent by weight, preventive less than 5 percent by weight, in particular contains less than 2.5 percent by weight of other components. 9. The method according to claim 1 to 7 »characterized in that a certain, commercially available nickel alloy (4 to 8 percent by weight iron, 24 to 32 percent by weight molybdenum, 3 to 5.5 percent by weight tungsten, 12 to 16 percent by weight chromium, small amounts of silicon and manganese, trace % carbon, balance nickel; "Nickel Alloy C"). 10. The method according to claim 1 to 9 »characterized in that that the co-catalytically active alloy within the reactor is in the form of separate, solid pieces, the reactor itself being made up of another, less susceptible to corrosion Material consists or is lined with such a material on the inside. 11. The method according to claim 10, characterized in that 109826/1990 2057S21 the co-catalytically effective alloy in the form of chips, Spirals, tubes, plates, tapes, Gev / even, granules and / or powders is present. 12. The method according to claim 10, characterized in that the co-catalytically active alloy within the Reactor is present in the form of parts, which are firmly attached or easily removed again and necessary- or can be replaced if necessary. 13 · Method according to claim 12, 'dadurcjh. marked, that stirrers, baffles and / or partitions are present in the reactor, which are aue of the co-catalytically active alloy exist and / or are coated with this. 14. The method according to claim 1 to 13 »characterized in that that the co-catalytically active alloy has a specific surface area of at least 10 cm / g. 15. The method according to claim 1 to 14 »characterized in that that the specific surface of the co-catalytically effective 2 seeds alloy in reactor at least 2 cm, preferably is at least 4 cm per ml of the reaction medium present in the liquid state. 16. The method according to claim 10 to 15 »characterized in that that the reactor wall consists of at least 40 percent by weight Nickel-containing alloy consists or is coated with such an alloy. 17. The method according to claim 16, characterized in that 109826/1990 2057SI1 that the alloy is 45 to 75 weight percent nickel, 20 to and
50 percent by weight molybdenum, 0 to 2 percent by weight chromium contains. 18. The method according to claim 17 »characterized in that the reactor wall made of a certain nickel alloy available in Hanael (24 to 32 percent by weight molybdenum, 3 to 7 percent by weight iron, small amounts of silicon and manganese, traces of carbon, the rest of nickel}" nickel alloy B " ) consists or is coated with such an alloy. Ä 19. Process according to Claims 1 to 18, characterized in that a compound of a metal is used as the Reppe catalyst of the VIII. Group of the Periodic Systems, preferably a cobalt or Hickel compound, is used. 20. The method according to claim 19t, characterized in that that as a catalyst a salt, preferably a halide, in particular an iodide, a metal of Group VIII of the Periodic Table, especially nickel (II) iodide, is used. 21. The method according to claim 19 or 20, characterized in that that an amount of Reppe catalyst is used such that per mole of the compound with (an) active Hydrogen atom (s), in particular V / water, 0.001 to 0.1 Gram atom of metal of Group VIII of the Periodic Table is present. 22.. The method of claim 1 bj ^ s 21, characterized in that the ReaktionsteDiperatur 140 to 250 ⁰ C, preferably 170 to 220 ⁰ C, beträft. 109826/1990 23. The method according to claim 1 to 22, characterized by, that the reaction is carried out at a pressure of 70 to 150 atmospheres (Overpressure) is carried out. 24. A method for the division of ^ü io-25 ~ ^{f vorzu} ßs ^w eise ^C 12-20 ~ ^ ^{onocartonic acids} *> ^einäü claim 1 to 23, characterized in that the starting materials are unbranched Cq_p ₄ - »preferably C ₁ ^^ - a -Oleefins or olefin mixtures used which contain a greater proportion, ie at least 75 mol percent, preferably at least 90 mol percent, of such olefins. 25. Use of at least one of those prepared according to claim 24 Carboxylic acids in the form of at least one of their alkali salts in detergent mixtures. 109826/1990