SE176355C1 - - Google Patents

Description

Uppfinnare: G Natta och P Pino Prioritet begtird frail den 29 mars 1955 och den februari 1956 (Schweiz) Foreliggande uppfinning avser ett satt att framstalla foreningar med den allmanna for-mein: CH— COOH 112— CH— COOH, van i R, resp. R, betyda vale eller en alkyl-, aryl- eller alkylarylradikal. Inventors: G Natta and P Pino Priority set for March 29, 1955 and February 1956 (Switzerland). . R 1 represents vale or an alkyl, aryl or alkylaryl radical.

For framstallning av foreningar av denna typ utgar man ifran monoacetylenforeningar med den allmanna formeln: van i substituenterna 111 och R2 ha ovan angivna betydelse. Genom omsattning med koloxid och vatten bildas under de nedan angivna betingelserna barnstenssyra eller substituerade barnstenssyror, vilka i det foljande kort benamnas barnstenssyror. For the preparation of compounds of this type, monoacetylene compounds of the general formula used in the substituents 111 and R2 have the meaning given above. By reaction with carbon monoxide and water, succinic acid or substituted succinic acids are formed under the conditions given below, which in the following card are called succinic acids.

F8r framstallning av substituerade barnstenssyror anvandas substituerade derivat av acetylen (monoacetylenforeningar, sasom etylacetylen, fenylacetylen, difenylacetylen. For the preparation of substituted succinic acids, substituted derivatives of acetylene (monoacetylene compounds, such as ethyl acetylene, phenylacetylene, diphenylacetylene) are used.

Reaktionen kan askadliggoras genorn f51- jande reaktionsschema: R1— C + 2 CH + 2112 0 --->" - CH — C001-1 I R2R2 CH — CO OR. The reaction can be sequestered by the following reaction scheme: R1 - C + 2 CH + 2112 0 ---> "- CH - C001-1 I R2R2 CH - CO OR.

Del har visat sig, att omsattningen med acetylen eller acetylens substituerade derivat kan genomforas med gott resultat for framstallning av barnstenssyra rasp. barnstenssysans derivat vid arbete i neutralt till surt medium, om man genomfor reaktionen vid temperaturer fran 80-280° C och vid tryck mellan 30 och 500 atm i narvaro av organiska losningsmedel, vilka kunna lOsa acetylen eller acetylenforeningen, vatten och katalysatorn, och i narvaro av karbonylfareningar som katalysatorer med de metaller tillhOrande pe- riodiska systemets attonde grupp, vilka kunna bilda karbonylforeningar av typen Me„,(C0)„, i vilka m an stOrre an I. It has been found that the reaction with acetylene or the substituted derivatives of acetylene can be carried out with good results for the production of succinic acid rasp. derivatives of the amber sysene when working in neutral to acidic medium, if the reaction is carried out at temperatures from 80-280 ° C and at pressures between 30 and 500 atm in the presence of organic solvents, which can dissolve the acetylene or acetylene compound, water and the catalyst, and in the presence of carbonyl compounds as catalysts with the metals belonging to the eighteenth group of the periodic table, which can form carbonyl compounds of the type Me „, (CO)„, in which m is larger than I.

Enligt den tyska patentskriften 888 009 är det kant att framstalla dikarbonsyror av ace- tylenkolvaten och koloxid i narvaro av cyan- eller rodanforeningar av nickel, kobolt eller jam i alkaliskt medium. Detta forfarande ge- nomfores i Hera steg, varvid man t. ex enligt exempel 2, utgaende fran acetylen och GO, f8rst erhaller en reaktionsvatska, frail vilken man avskiljer en blandning av vatten och cyklopentanon och sedan avdestillerar cyklopentanon Iran det byre skiktet av kvarblivande kondensationsprodukt och slutligen hydrerar den darvid kvarblivande delen med vale, surgor med svavelsyra och darpa upp i propionsyra och barnstenssyra. 1 motsats till detta satt arbetar man enligt uppfinningen fOr det forsta med andra katalysatorer, vilka besta av karbonylforeningar av bestamda metaller bland vilka nickel joke inraknas, for det andra genomfores reaktionen i ett steg i neutralt till surt medium och for det tredje arbetar man -vid hogre tryck, foretradesvis vid 200-500 atmosfarer, gentemot 30-40 atmosfarer enligt ovan angivna patentskrift. Man erhaller darvid en produkt, som innehaller starre mangder barnstenssyra eller, am man anvander substituerad acetylen, substituerade barnstenssyror. Gentemot den angivna patentskriften erhaller man salunda enligt uppfinningen pa ett enklare satt produkter, som innehalla st8rre kvantiteter barnstenssyra, varigenom for forsta gangen ett tekniskt forfarand.e fOreligger for framstallning av denna syra pa ett enkelt och billigt satt. Forst darigenom blir det mojligt att anvanda den som en viktig utgangsprodukt for organisk syntes. According to German Pat. No. 888,009, it is possible to produce dicarboxylic acids from the acetylene carbonates and carbon monoxide in the presence of cyan or rodane compounds of nickel, cobalt or jam in alkaline medium. This process is carried out in step Hera, in which, for example, according to Example 2, starting from acetylene and GO, first a reaction vessel is obtained, from which a mixture of water and cyclopentanone is separated off and then cyclopentanone is distilled off from Iran by the remaining layer of condensation product. and finally the remaining part hydrates with vale, acids with sulfuric acid and drips into propionic acid and succinic acid. In contrast, the invention is carried out firstly with other catalysts, which consist of carbonyl compounds of certain metals among which nickel joke is included, secondly the reaction is carried out in one step in neutral to acidic medium and thirdly, higher pressures, preferably at 200-500 atmospheres, versus 30-40 atmospheres according to the above patent. A product is obtained which contains larger amounts of succinic acid or, when substituted acetylene is used, substituted succinic acids. In contrast to the stated patent specification, according to the invention, a simpler set of products is obtained which contain larger quantities of succinic acid, whereby for the first time a technical procedure is available for the production of this acid in a simple and inexpensive manner. Only in this way will it be possible to use it as an important starting product for organic synthesis.

De eventuellt substituerade barns tensyror;la firma industriell anvandning bland annat 2— — for framstallning av Mjukningsmedel och som mellanprodukter for fargamnen och lakemedel. The tensoric acids of the optionally substituted children have industrial use, inter alia, for the production of plasticizers and as intermediates for dyes and pharmaceuticals.

Nedan 6.1erges i tabellform exempel ph de metaller tillhorande attonde gruppen, vilka kunna bilda karbonylforeningar av typen Mem(C0)„ i vilka in Or stone I. The following is a tabular example of the metals belonging to the eighteenth group, which may form carbonyl compounds of the Mem (C0) type in which in Or stone I.

Metall m = 1M = 2M=3M = 4 Fe Fe(C0) Fe2(C0)9 Fe3(C0)12 — Co — Co(CO)8 — Co4(C0)12 Ru Ru(C0) Ru2(C0)9 Ru,(C0)12— Os Os(C0) 0s2(C0)9 — Ir — 1r2(CO)8 — Sadana karbonylforeningar, i vilka in Or storre 1, kunna antingen inforas i reaktionen eller ocksh kunna de bildas under reaktionen av enkla karbonylforeningar (m = 1). Det Or emellertid Oven mojligt att infora metallforeningar med metaller, tillhorande attonde gruppen, t. ex. koboltsuccinat i reaktionen. I narvaro av t. ex. koloxid ocb. Tate bildas sedan en katalytiskt verksam karbonylforening, i vilken in Or stone 1. Metal m = 1M = 2M = 3M = 4 Fe Fe (C0) Fe2 (C0) 9 Fe3 (C0) 12 - Co - Co (CO) 8 - Co4 (C0) 12 Ru Ru (C0) Ru2 (C0) 9 Ru , (C0) 12— Os Os (C0) Os2 (C0) 9 - Ir - 1r2 (CO) 8 - Such carbonyl compounds, in which in Or larger 1, can either be introduced into the reaction or they can also be formed during the reaction of simple carbonyl compounds (m = 1). However, it is also possible to introduce metal compounds with metals belonging to the eighteenth group, e.g. cobalt succinate in the reaction. In the presence of e.g. carbon monoxide ocb. Tate then forms a catalytically active carbonyl compound, in which in Or stone 1.

Av attonde gruppens metaller kunna forutom kobolt och jam n Oven adelmetallerna komma i fraga som katalysatorns metalliska komponent. Pa grund av sitt htSga pris komma de emellertid i andra hand efter metallerna i den fjarde perioden, namligen kobolt och jarn. Koboltkarbonylforeningar Oro sarskilt lampliga, men ¥ jarnkarbonylforeningar ge goda resultat. Of the eighth group metals, in addition to cobalt and jam, the noble metals may also be considered as the metallic component of the catalyst. However, due to their high price, they come second to the metals in the fourth period, namely cobalt and iron. Cobalt carbonyl compounds are particularly suitable, but iron carbonyl compounds give good results.

Dessa metallers karbonylforeningar med hogre molvikt dro mycket verksamma katalysatorer for syntesen av barnstenssyror, om man utgar fran acetylen eller acetylens substitutions derivat. The higher molecular weight carbonyl compounds of these metals were very effective catalysts for the synthesis of succinic acids, starting from acetylene or acetylene substitution derivatives.

Nickel, vilken som kant icke kan bilda nagra karbonylforeningar med hogre molvikt och hos vilken alltse. in = 1, Or icke lamplig som katalysatorer for omsattning enligt uppfinningen trots sin likhet med kobolt. Fors& har visat, att de hittills for det mesta anvanda nickelkatalysatorerna inte Oro lampliga for anlagring av koloxid till acetylenforeningar vid en syntes av sarskilt stora mangder barnstenssyror i ett neutralt till surt medium. Sasom framgar av det nedanstaende utforingsexemplet 6, erhaller man i ett neutralt till surt medium anlagringsprodukter med en nickelkatalysator, utan att det darvid bildas barnstenssyra. Daremot overfores en stor del av koloxiden i koldioxid. Nickel, which as an edge cannot form any higher molecular weight carbonyl compounds and in which all. in = 1, Or not suitable as catalysts for reaction according to the invention despite its resemblance to cobalt. Fors & has shown that the nickel catalysts used for the most part so far are not suitable for the storage of carbon monoxide in acetylene compounds in a synthesis of particularly large amounts of succinic acids in a neutral to acidic medium. As can be seen from the following embodiment 6, in a neutral to acidic medium, storage products with a nickel catalyst are obtained, without the formation of succinic acid. On the other hand, a large part of the carbon monoxide is converted into carbon dioxide.

Med losningsmedel fOrstas shdana organiska vatskor, vilka 0 ena sidan Oro blandbara med vatten och i vilka A andra sidan acetylen Or loslig. Rent allmant kommer alifatiska och alicykliska ketoner, sasom t. ex. aceton, metyletylketon, cyklopentanon, eller etrar, sasom t. ex. etylenglykoldimetyleter och di-oxen i fraga. By solvents are meant those organic liquids which on one side are miscible with water and in which on the other side acetylene is soluble. In general, aliphatic and alicyclic ketones, such as e.g. acetone, methyl ethyl ketone, cyclopentanone, or ethers, such as e.g. ethylene glycol dimethyl ether and dioxene in question.

Reaktionen mellan acetylen eller en ace tylenforening och vatten och koloxid Carlo-per i narvaro av en karbonylforening enligt uppfinningen utan tillsats av ovan angivna losningmedel med brukbar hastighet blott vid temperaturer fran och med ungefar 140° C. Det bildas emellertid samtidigt en ringa mangd av andra produkter (karbonylforeningar) och dessutom overfores en del av koloxiden i koldioxid. Utbytet av barnstenssyra blir dOligt. Dessutom sonderdelas t. ex. koboltkarbonylen eller hydrokarbonylen snabbt, varvid den katalytiska effekten gar forlorad. The reaction between acetylene or an acetylene compound and water and carbon monoxide Carloper in the presence of a carbonyl compound according to the invention without the addition of the above solvents at a usable rate only at temperatures from about 140 ° C. However, a small amount of other products (carbonyl compounds) and in addition some of the carbon monoxide is converted into carbon dioxide. The exchange of succinic acid becomes poor. In addition, special parts e.g. cobalt carbonylene or hydrocarbonylene rapidly, the catalytic effect being lost.

Onskar man enligt uppfinningen omsfitta cii acetylenforening med koloxid och vatten en neutralt till surt medium i narvaro av en karbonylkatalysator med hogre molvikt och I narvaro av ett organiskt losningsmedel, Or det lampligt att anvanda ett overskott av vat-ten raknat ph den erforderliga teoretiska mangden. Exempelvis kunna 2,5 mol vatten per mol acetylen anvandas. Vidare Or det att valja ett viktsmassigt Overskott av organiska losningsmedel rdknat ph det anvanda vattnet. Utbytena bli sarskilt hoga, om 2 till 15-f aldig viktmangd losningsmedel raknat pa vatten anvandes. If it is desired according to the invention to react in acetylene compound with carbon monoxide and water a neutral to acidic medium in the presence of a higher molecular weight carbonyl catalyst and in the presence of an organic solvent, it is convenient to use an excess of water at the required theoretical level. For example, 2.5 moles of water per mole of acetylene can be used. Furthermore, the choice of a weight-bearing excess of organic solvents is calculated by the water used. The yields will be particularly high if 2 to 15 times the amount of solvent dissolved in water is used.

Med dessa betingelser Or det mojligt, att lata reaktionen aga rum redan vid en sh lag temperatur som 80° C. Viii temperaturer mellan 100-120° C forloper reaktionen sedan med tillfredsstallande hastighet. With these conditions, it is possible to allow the reaction to proceed even at a temperature as low as 80 ° C. At temperatures between 100-120 ° C, the reaction then proceeds at a satisfactory rate.

Anvandningen av ett losningsmedel, i vilket acetylen Or lattlosligt, tillater sarskilt om ett stort viktmassigt overskott av losningsmedel gentemot vatten foreligger, att man arbetar med en Mg acetylenkoncentration i vatskefasen, varvid forhallandevis lOga partialtryck [Or acetylen upptrada. Detsamma galler Oven acetylens derivat. Dessutom mojliggor det forhallandet, att dikoboltoktakarbonyl Or losligt i organiska losningsmedel, att man kan genomfora reaktionen I flytande, homogen [as, med bdtingelser, vid vilka katalysatorn bibehaller sin aktivitet 15.nge. Losligheten av dikoboltoktakarbonyl Or just denna katalysator sarskilt lamplig. The use of a solvent in which acetylene is readily soluble, especially if a large weight excess of solvent relative to water is present, allows one to work with a Mg acetylene concentration in the liquid phase, with relatively low partial pressures [or acetylene occurring. The same grid Oven acetylene derivatives. In addition, the condition that dicobalt octacarbonyl is soluble in organic solvents allows the reaction to be carried out in liquid, homogeneous conditions, with conditions in which the catalyst retains its activity. The solubility of dicobalt octacarbonyl Is this particular catalyst particularly suitable?

Reaktionstiden Jigger alit efter den anvanda acetylenfOreningen och alit efter temperaturen och trycket mellan nagra minuter och nagra timmar. T. ex. genomfores framst511- ningen av vanlig barnstenssyra av acetylen, vatten och koloxid i narvaro av dikoboltoktakarbonyl vid en temperatur av ungefar 110° och vid ett tryck av 200 atm redan Mom 30 min med 60 % utbyte av det teoretiska, raknat pi den anvanda acetylenen. Reaction time Jigger alit according to the acetylene compound used and alit according to the temperature and pressure between a few minutes and a few hours. Eg. the production of ordinary succinic acid from acetylene, water and carbon monoxide is carried out in the presence of dicobalt octacarbonyl at a temperature of about 110 ° and at a pressure of 200 atm already Mom 30 min with 60% yield of the theoretical, shaved in the acetylene used.

Tekniskt viktigt Or ocksa det fOrhallandet, att reaktionen kan genomforas med gott resultat vid temperaturer under 120°, t. ex. mellan 100 och 120°, varvid reaktionen dger rum mom ett sh stort temperaturintervall som fran 80-250°. Viii sadana temperaturer overgar namligen koloxid blott ytterst langsamt i koldioxid, Dessutom stravar man efter — —3 att inskranka de erhallna syrornas korroderande verkan pa reaktionsapparaturens me-taller. AV dessa skal arbetar man helt naturligt hellre vid mojligast laga temperaturer. Technically important Is also the fact that the reaction can be carried out with good results at temperatures below 120 °, e.g. between 100 and 120 °, the reaction taking place in a temperature range ranging from 80-250 °. Namely, at such temperatures, carbon monoxide passes only extremely slowly into carbon dioxide. In addition, efforts are made to limit the corrosive effect of the acids obtained on the metals of the reaction apparatus. Of these shells, it is quite natural to work at the lowest possible temperatures.

Det har visat sig, att man kan erhalla barnstenssyra i ett enda reaktionssteg med over 60 % utbyte, raknat pa acetylen, om man genomtor reaktionen mellan acetylen, koloxid och vatten enligt de ovan angivna reaktionsbe tingelserna sarskilt med koboltkarbonylforeningar och da speciellt dikoboltoktakarbonyl. Reaktionen medger mojligheten av att framstalla barnstenssyra pa ett enkelt och billigt satt. Barnstenssyran är en viktig utgangsprodukt for organisk syntes. It has been found that succinic acid can be obtained in a single reaction step with a yield of more than 60%, calculated on acetylene, if the reaction between acetylene, carbon monoxide and water is carried out according to the above reaction conditions, especially with cobalt carbonyl compounds and especially dicobalt octacarbonyl. The reaction allows the possibility of producing succinic acid in a simple and inexpensive manner. The succinic acid is an important starting product for organic synthesis.

De hittills kanda satten att framstalla barnstenssyra, omfatta minst tva reaktionssteg enligt foljande schema. To date, they have been able to produce succinic acid, comprising at least two reaction steps according to the following scheme.

CH -_--- CH + 2C0 -I- 2C1-120H (C0)± CH300C — CH,C1-12— 000CH2 H+ ) HOOC — CH2 — — CH2— COOH + 2CH2OH + 21430 Ni(COM(2HC1) CH '-... CH + 200 + 2NaOH [K2; Na00C — CH2— CH2— COONa__>. HOOC — — CH2— CH2— COOH + 2NaCl. CH -_--- CH + 2CO -I- 2C1-120H (C0) ± CH300C - CH, C1-12— 000CH2 H +) HOOC - CH2 - - CH2— COOH + 2CH2OH + 21430 Ni (COM (2HC1) CH ' -... CH + 200 + 2NaOH [K2; NaOOC - CH2— CH2— COONa __>. HOOC - - CH2— CH2— COOH + 2NaCl.

Vid dessa omsattningar aro utbytena, raknade pa acetylen, i allmanhet mycket laga till foljd av bildning av talrika biprodukter. Vid det enligt formeln 1) askadliggjorda sattet ligger acetylenutbytet vid 35 %. Utbytet raknat pa metanol ar ocksa sarskilt lagt 3540 %, vid detta satt. Vid det enligt den andra formeln askadliggjorda sattet har man blott laga utbyten raknat pa kohnonoxid, som till stor del over& i koldioxid. In these reactions, the yields, calculated on acetylene, are generally very suitable as a result of the formation of numerous by-products. In the case of the ash-oxidized process according to formula 1), the acetylene yield is 35%. The yield calculated on methanol is also especially 3535%, in this way. In the method which has been neutralized according to the second formula, only low yields have been calculated based on carbon monoxide, which is largely converted to carbon dioxide.

Reaktionen genomfores lampligen i en autoklav, i vilken reaktionsmediet och katalysatorn befinna sig och i vilken man sd smaningom inleder acetylen och koloxid, tills ett hOgre partialtryck for koloxid och ett acetylentryck under explosionsgransen uppnatts. Exempelvis kan man arbeta med partialtryck for koloxid pa 30 atm och mer. Lampligen skakas autoklaven eller far en rorelse pa liknande satt. The reaction is conveniently carried out in an autoclave in which the reaction medium and the catalyst are located and in which acetylene and carbon monoxide are gradually introduced, until a higher partial pressure of carbon monoxide and an acetylene pressure below the explosion limit are reached. For example, one can work with partial pressures for carbon monoxide of 30 atm and more. The autoclave is shaken or shaken in a similar way.

Reaktionen fOr framstallning av barnstenssyror genomfores lampligen i en enda homogen, flytande fas, som innehaller katalysatorn, lOsningsniedlet, vattnet oak acetylenforeningen. The reaction for the production of succinic acids is suitably carried out in a single homogeneous, liquid phase, which contains the catalyst, the solvent, the water and the acetylene compound.

Sattet enligt uppfinningen kan genomforas diskontinuerligt eller kontinuerligt. For en lopande produktion är det lampligt att genomfora reaktionen kontinuerligt och avskilja reaktionsprodukten Iran reaktionsmediet. Moderlutarna, vilka innehalla losningsmedlet, katalysatorn och eventuellt fortfarande en del av barns'tenssyrorna, aterforas atminstone delvis till reaktionskarlet, varvid losningsmedelsforluster kunna ersattas, sedan de blivit f6rsatta med koloxid och en acetylenforening. The set according to the invention can be carried out batchwise or continuously. For a continuous production, it is appropriate to carry out the reaction continuously and to separate the reaction product Iran reaction medium. The mother liquors, which contain the solvent, the catalyst and possibly still some of the succinic acids, are returned at least in part to the reaction vessel, whereby solvent losses can be replaced after they have been provided with carbon monoxide and an acetylene compound.

For att avskilja de bildade barnstenssyrorna, kan man ocksa avdestillera det flyktiga lOsningsmedlet Fran den uttagna omloppsvatskan oeh lata den sâ erhallna vattenhaltiga losningen kristallisera. Man erhaller pa detta satt forhallandevis rena barnstenssyror, som kunna anvandas f8r andra andamal utan vi-dare upparbetning. In order to separate the succinic acids formed, it is also possible to distill off the volatile solvent from the withdrawn circulating water and allow the aqueous solution thus obtained to crystallize. In this way, relatively pure succinic acids are obtained, which can be used for other purposes without further processing.

Det har vidare visat sig, att det ar lampligt att genomfora alla operationer i en COatmosfar i frAnvaro av syrgas, for att uppratthalla katalysatorns effekt, dvs. separe ringen av barnstenssyrorna, tillsattningen av acetylen eller en acetylenforening till moderluten resp. den fornyade mattningen med acetylen samt aterforingen am losningen. Koloxidens partialtryck maste darvid vara hogre an sonderdelningstrycket for den i losningen befintliga katalytiskt verksamma metallkarbonylforeningen. Detta ãr beroende pa den temperatur, vid vilken de olika operationerna aga rum. Det racker med tryck av ungefar en atm vid 0° C, medan h8gre tryck erfordras vid hogre temperaturer, t. ex. tryck pa 3-10 atm yid 10-30° C och tryck pa 2030 atm vid 50-80° C. Onskar man forsatta moderlutarna med acetylen eller monoacetylenforeningar, g8r man lampligen sa, att man tillfogar den erforderliga mangden acetylen eller monoacetylenforeningar till moderluten i franvaro av syre och lampligen i narvaro av koloxid, till dess ett partialtryck for acetylen pa 2-20 atm uppnatts. It has further been found that it is convenient to carry out all operations in a CO atmosphere in the absence of oxygen, in order to maintain the effect of the catalyst, i.e. the separation of the succinic acids, the addition of acetylene or an acetylene compound to the mother liquor resp. the renewed matting with acetylene as well as the feeding back to the solution. The partial pressure of the carbon monoxide must then be higher than the probe separation pressure for the catalytically active metal carbonyl compound present in the solution. This depends on the temperature at which the various operations take place. It racks with pressures of approximately one atm at 0 ° C, while higher pressures are required at higher temperatures, e.g. pressure at 3-10 atm yid 10-30 ° C and pressure at 2030 atm at 50-80 ° C. If you want to continue the mother liquors with acetylene or monoacetylene compounds, you should do so by adding the required amount of acetylene or monoacetylene compounds to the mother liquor in absence of oxygen and preferably in the presence of carbon monoxide, until a partial pressure of acetylene of 2-20 atm is reached.

Det har vidare visat sig att katalysatorns aktivitet raskt avtar vid utforande av sattetenligt uppfinningen, om barnstenssyrornas koncentration i reaktionslosningen blir relativt hog. Detta ãr for barnstenssyra fallet vid en halt av mer an 30-35 viktprocent. Det ãr darfor lampligt att arbeta med lagre koncentrationer, vilket kan foretagas genom att I overensstammelse darmed regelbundet bortfora reaktionsprodukterna frail reaktionskarlet, sarskilt vid kontinuerligt arbetssatt. It has further been found that the activity of the catalyst decreases rapidly in the practice of the invention, if the concentration of succinic acids in the reaction solution becomes relatively high. This is the case for succinic acid at a content of more than 30-35% by weight. It is therefore convenient to work with lower concentrations, which can be done by accordingly regularly removing the reaction products from the reaction vessel, especially at continuous operation.

Aven om man onskar skona katalysatorerna genom att halla en lag koncentration av barnstenssyra i reaktionslOsningen, kan katalysatorns aktivitet avta langsamt. Denna utveckling kan man motverka darigenom, att reaktionslosningen tillfores fly katalysator. Man kan emellertid efter barnstenssyrans franseparering overfOra barnstenssyrans i vatskan befintliga metallsalt, t. ex. koboltsuccinat eller jarnsuccinat, i motsvarande metallkarbonylforening, alltsa t. ex. i koboltkarbonyl eller i jarnkarbonyl, med koloydd och vale vid en temperatur av 120-200° C och aterfora vatskan, innehallande den senare in i reaktionsapparaturen. Although it is desired to spare the catalysts by maintaining a low concentration of succinic acid in the reaction solution, the activity of the catalyst may decrease slowly. This development can be counteracted by feeding the reaction solution to escape catalyst. However, after the separation of the succinic acid, the metal salt of the succinic acid in the liquid can be transferred, e.g. cobalt succinate or ferrous succinate, in the corresponding metal carbonyl compound, i.e. e.g. in cobalt carbonyl or in iron carbonyl, with colloid and vale at a temperature of 120-200 ° C and the athera liquid, containing the latter into the reaction apparatus.

Pa samma satt ãr det mojligt, om barn- 4— 176 stenssyrans salter sta till fOrfogande som sa.- dana, att uppslamma dessa i de losningsmedel, som skola tillsattas, och overfora dem i karbonylforeningar med koloxid och vate. In the same way, it is possible, if the salts of succinic acid are available as such, to suspend them in the solvents which are to be added, and to transfer them into carbonyl compounds with carbon monoxide and hydrogen.

Vid den kontinuerliga bo.rnstenssyresyntesen liar det visat sig lampligt att anvanda cyklopentanon som. losningsmedel. Den se- nare bildas som biprodukt vid reaktionen och behover joke darfor forvarvas genom Up. In the continuous succinic acid synthesis, it has been found appropriate to use cyclopentanone as. solvents. The latter is formed as a by-product of the reaction and needs a joke, so it is distorted through Up.

Den kannetecknas av en hog kokpunkt, sa att fOrangningsforlusterna bliva mycket sma. De trots detta upptradande losningsmedelsfarlusterna kunna utjamnas genom bildning av cyklopentanon som biprodukt. It can be characterized by a high boiling point, so that the disposal losses become very small. The solvent losses occurring despite this can be compensated for by the formation of cyclopentanone as a by-product.

I beskrivningen, utforingsexemplen och patentanspraken aro samtliga temperaturuppgifter angivna i celciusgrader. Uttrycket Ni betyder normalliter. In the description, the exemplary embodiments and the patent claims, all temperature data are given in degrees Celsius. The term Ni means normal liters.

Uppfinningen forklaras narmare i efterfoljande utforingsexempel. The invention is explained in more detail in the following exemplary embodiments.

Exempel 1 ãr ett jamforelseexempel, vangenom visas att ett genomforande av reaktioner utan narvaro av lOsningsmedel for till oekonomiska utbyten. Example 1 is a comparative example, showing that carrying out reactions without the presence of solvents leads to uneconomical yields.

Exempel 6 visar som jamfbrelse, att arbete med foreskrifter enligt uppfinningen men med anvandning av en nickelkatalysator 'eke erbjuder flagon mojlighet att framstalla barnstenssyra. Example 6 shows as a comparison that work with regulations according to the invention but with the use of a nickel catalyst does not offer flake the possibility of producing succinic acid.

I exempel 8 beskrives med hanvisning till den bifogade ritningen ett utforingsexempel for kontinuerlig framstallning av barnstenssyra. In Example 8, with reference to the accompanying drawing, an exemplary embodiment for the continuous production of succinic acid is described.

Exempel 1 (jamforelseexempel utan losningmedel). Example 1 (comparative example without solvent).

I en autoklav med 300 ml volym infores 100 g vatten, som innehaller 10 g dikoboltoktakarbonyl i vattensuspension. Darefter inledes 2,5 Ni acetylen och successivt kolmonoxid till dess ett totalt tryck av 200 atm erUnits. Man uppvarmer autoklaven till 40° C och hojer temperaturen sa smaningom till 140° C. Efter ungefar 6 timmar kyler man autoklaven till rumstemperatur, avgasar den och analyserar gasen. Ungefar 4,6 % av CO har Overgatt i CO ° medan 10 % av CO reagerat med acetylen. In a 300 ml volume autoclave, 100 g of water containing 10 g of dicobalt octacarbonyl in aqueous suspension are introduced. Then 2.5 N of acetylene and successively carbon monoxide are introduced until a total pressure of 200 atm is reached. The autoclave is heated to 40 ° C and the temperature is gradually raised to 140 ° C. After about 6 hours, the autoclave is cooled to room temperature, degassed and the gas analyzed. About 4.6% of CO has converted to CO ° while 10% of CO has reacted with acetylene.

De flytande produkterna destilleras. Ater- stoden efter destillationen upptages med vat-ten och fran denna erhalles genom kristallisation 2 g barnstenssyra, sedan kobolt avlagsnats. Utbytet utgiir 16,5 % raknat pa acetylen. The liquid products are distilled. The residue after distillation is taken up with the water and from this 2 g of succinic acid are obtained by crystallization, after cobalt has been removed. The yield is 16.5% calculated on acetylene.

Exempel 2. Example 2.

I en autoklav med 1710 ml volym infores 216 g aceton, 72 g vatten och 10 g dikoboltoktakarbonyl. Darefter inledes 14 Ni acetylen och sit smaningom kolmonoxid, till dess ett tryck av 200 atm uppnatts. Man uppvarmer autoklaven till 110° C och hailer denna temperatur under 3 timmar, varefter man nedkyler och avgasar. Gasanalysen visar aft 6,2 % har overgatt i CO2. Into an autoclave with 1710 ml volume are introduced 216 g of acetone, 72 g of water and 10 g of dicobalt octacarbonyl. Then 14 N of acetylene and its carbon monoxide are introduced, until a pressure of 200 atm is reached. The autoclave is heated to 110 ° C and this temperature is maintained for 3 hours, after which it is cooled and degassed. The gas analysis shows that 6.2% have converted to CO2.

Exempel 3. Example 3.

I en autoklav med 310 ml volym infores 36 g vatten, 90 g dioxan och 4 g dikoboltoktakarbonyl. Darefter inledes 9,5 NI acetylen och sedan kolmonoxid sit lunge, att ett tryck av 200 atm uppnas. Man upphettar autoklaven under 5 timmar till 110° C, varefter man nedkyler och avgasar den gasformiga produkten. De flytande produkterna destilleras. Destillatet innehaller 1,59 g karbonylforeningar, raknade som cyklopentanon och 4 g av en blandning av akrylsyra och propionsyra med Over 60 % akrylsyra. Into an autoclave with 310 ml volume are introduced 36 g of water, 90 g of dioxane and 4 g of dicobalt octacarbonyl. Then 9.5 NI of acetylene and then carbon monoxide are introduced into the lungs to reach a pressure of 200 atm. The autoclave is heated for 5 hours to 110 ° C, after which the gaseous product is cooled and degassed. The liquid products are distilled. The distillate contains 1.59 g of carbonyl compounds, shaved as cyclopentanone and 4 g of a mixture of acrylic acid and propionic acid with Over 60% acrylic acid.

Destillationsaterstoden bestar ndstan uteslutande av barnstenssyra. Genom aterupplosning och kristallisering erhalles ddrvid 32,5 g. Utbytet for barnstenssyra dr 65 % raknat pa acetylen. The distillation residue consists almost exclusively of succinic acid. Through redissolution and crystallization, 32.5 g are obtained. The yield of succinic acid is 65% calculated on acetylene.

Exempel 4. Example 4.

I en skakautoklav med 1710 ml volym infores 10 g dikoboltoktakarbonyl, 90 g vatten, 198 g aceton och 1,294 mol fenylacetylen. Sedan luften utdrivits genom upprepad genomblasning med koloxid, intryckes koloxid, sit att trycket blir 200 atm, och autokIaven uppvarmes till 140° C under fortgaende skakning. Sedan denna temperatur uppnatts, konstateras att trycket under loppet av ungefar 4 timmar nainskas. Darefter far autoklaven svalna till ungefar 20° C. Gaserna avgasas och reaktionsprodukterna uttagas ur autoklaven. De flytande produkterna (ungefar 332 g), vilka uppvisa en sur reaktion, destilleras vid vanligt tryck vid temperaturer Indian ungefar 55 och 100° C. Destillationsaterstoden behandlas med alkali och surgOres sedan, varvid man erhaller 0,071 mol racemisk fenylbarnstenssyra med en smaltpunkt av 166° C. Utbytet av fenylbarnstenssyra utgor raknat pa anvand fenylacetylen ungefar % och raknat pa den anvdnda koloxiden ungefdr 57%. In a shake autoclave with a volume of 1710 ml, 10 g of dicobalt octacarbonyl, 90 g of water, 198 g of acetone and 1.294 mol of phenylacetylene are introduced. After the air has been expelled by repeated blowing with carbon monoxide, carbon monoxide is forced in, the pressure becomes 200 atm, and the autoclave is heated to 140 ° C with continuous shaking. After this temperature has been reached, it is found that the pressure increases over the course of about 4 hours. The autoclave is then allowed to cool to approximately 20 ° C. The gases are degassed and the reaction products are removed from the autoclave. The liquid products (about 332 g), which show an acidic reaction, are distilled at ordinary pressure at temperatures of about 55 DEG and 100 DEG C. The distillation residue is then treated with alkali and acidified to give 0.071 mol of racemic phenyl succinic acid, m.p. 166 DEG. C. The yield of phenylsuccinic acid is about 9% on the use of phenylacetylene and about 57% on the basis of the carbon monoxide used.

Exempel 5. Example 5.

I en skakautoklav med 1710 ml volym infores 10 g Fe(C0), 90 g vatten, 198 g ace-ton. Efter blasning med koloxid infores 0,762 mol acetylen och koloxid patryckes, sit att ett tryck av 200 atm erhalles. Darefter uppvarmes den i rorelse befintliga autoklaven till 180° C. Man konstaterar en sankning av trycket, vilken upphor efter ungefar 1 timmar. Man later autoklaven svalna till omkring 20° C. Gaserna fa avga och reaktionsprodukterna uttagas ur autoklaven. De senare (ungefar 3g) uppge sur reaktion och uppdestilleras vid vanligt tryck vid tempera.turer mellan 55-100° C. Destillatet innehaller 4,082 g (0,0552 mol) monokarbonsyra (propionsyra och akrylsyra), motsvarande 19,5 % av omsatt acetylen. Vidare erhalles 3 g (0,0337 mol) cyklopentanon, motsvarande 14,2 % av omsatt acetylen. I destillationsaterstoden finnes 20,3 g (0,1732 mol) barnstenssyra, mot- — 176 svarande 24 % av omsatt acetylen. Analys visar, att 34 % av acetylenen inte liar reagerat och att reaktionsprodukterna innehalla ungefar 74 % barnstenssyra, Exempel 6 (jamforelseexempel med nickelkatalysator) I en liknande autoklav som i exempel 2 med 1710 ml volym infores 10 g Ni(C0)4, 90 g vatten. och 198 g aceton. Efter genomblasning med koloxid infores 0,961 mol acetylen. Sedan patry&es koloxid till ett tryck av 200 atm. Man uppvirmer autoklaven, som är i rorelse och konstaterar, att en koloxidabsorbtion forst intraffar over 200° C. Man hailer autoklaven i rorelse ungefar 4,5 timmar vid temperaturer mellan 200 och 217° C. Sedan nedkyles autoklaven till ungefar 20° G. De avgaende gaserna innehalla 15,4 % acetylen, som icke har reagerat. Vatskan har sur reaktion och innehaller 0,737 mol monokarbonsyra och 0,033 mol monokarbonylforeningar. De narvarande syrorna isoleras som natriumsalter. Fran dessa erhalles genom surgoring oth extraktion med eter efter efterfoljande destillation 50 g av en blandning av akrylsyra och propionsyra, motsvarande ungefar 0,6 mol monokarbonsyra. En del av akrylsyran polymeriseras under denna be-handling. Del är darfOr late mojligt att Atervinna denna. Fran dessa produkter kunde icke nagon barnstenssyra isoleras. In a shake autoclave with a volume of 1710 ml, 10 g of Fe (CO), 90 g of water, 198 g of acetone are introduced. After blowing with carbon monoxide, 0.762 moles of acetylene are introduced and carbon monoxide is reprinted, until a pressure of 200 atm is obtained. The moving autoclave is then heated to 180 ° C. A decrease in pressure is observed, which ceases after about 1 hour. The autoclave is allowed to cool to about 20 ° C. The gases are allowed to escape and the reaction products are removed from the autoclave. The latter (approximately 3 g) give an acid reaction and are distilled off at ordinary pressure at temperatures between 55-100 ° C. The distillate contains 4.082 g (0.0552 mol) of monocarboxylic acid (propionic acid and acrylic acid), corresponding to 19.5% of the acetylene reacted. . Furthermore, 3 g (0.0337 mol) of cyclopentanone are obtained, corresponding to 14.2% of the acetylene reacted. The distillation residue contains 20.3 g (0.1732 mol) of succinic acid, corresponding to 24% of the acetylene reacted. Analysis shows that 34% of the acetylene does not react and that the reaction products contain about 74% succinic acid. Example 6 (comparative example with nickel catalyst) In a similar autoclave as in Example 2 with 1710 ml volume, 10 g of Ni (CO) 4, 90 g are introduced. water. and 198 g of acetone. After blowing with carbon monoxide, 0.961 mol of acetylene is introduced. Then patry & es carbon monoxide to a pressure of 200 atm. The moving autoclave is heated and it is found that a carbon monoxide absorption first occurs above 200 ° C. The autoclave is stirred for about 4.5 hours at temperatures between 200 and 217 ° C. The autoclave is then cooled to about 20 ° C. the exhaust gases contain 15.4% of unreacted acetylene. The liquid has an acidic reaction and contains 0.737 moles of monocarboxylic acid and 0.033 moles of monocarbonyl compounds. The acids present are isolated as sodium salts. From these, 50 g of a mixture of acrylic acid and propionic acid, corresponding to about 0.6 mol of monocarboxylic acid, are obtained by acidification and extraction with ether after subsequent distillation. Some of the acrylic acid is polymerized during this treatment. Part is darfOr late possible to Recycle this. No succinic acid could be isolated from these products.

Exempel 7. Example 7.

I en skakautoklav med 1710 ml volym infores 7,13 g koboltsuccinat, 251 g aceton, 45 g vatten och 0,270 mol acetylen. Darefter infores en blandning av CO och H2 i forhallandet 4:1 med ett tryck av 250 atm i autokla: ven och denna skakas fortghende ocb. uppvarmes. Vid 170° C borjar absorbtionen, vilken ar avslutad efter ungefar 5 timmar. Efter nedkylning till rumstemperatur fa gaserna avga. Ax gasanalys framgdr, att all acetylen har reagerat. Fran autoklaven uttages 820 g av en vatska, som innehaller ungefar 18,1 g (0,1535 mol) nybildad barnstenssyra. Utbytet är 45,5 % raknat ph den inforda acetylenen efter avrdkning av den i borjan av forsoket som koboltsuccinat tillsatt barnstenssyra. Vidare innehaller vatskan jamte spar av karbonylforeningar ytterligare 3,01 g (0,406 mol) propionsyra och akrylsyra. Detta motsvarar ett utbyte av 14 % av den inforda acetylenen. Reaktionsprodukterna utOra tillsammans ungefar 22 g. Darav är 18,1 g barnstenssyra i ett utbyte av Over 80 %. In a shake autoclave with a volume of 1710 ml, 7.13 g of cobalt succinate, 251 g of acetone, 45 g of water and 0.270 mol of acetylene are introduced. Then a mixture of CO and H2 is introduced into the 4: 1 ratio with a pressure of 250 atm in the autoclave and this is shaken continuously and so on. heated. At 170 ° C the absorption begins, which is completed after about 5 hours. After cooling to room temperature, allow the gases to escape. Ax gas analysis shows that all acetylene has reacted. From the autoclave, 820 g are taken out of a liquid, which contains approximately 18.1 g (0.1535 mol) of newly formed succinic acid. The yield is 45.5% shaved on the introduced acetylene after stripping it of succinic acid added at the beginning of the experiment as cobalt succinate. Furthermore, the liquid together with traces of carbonyl compounds contain an additional 3.01 g (0.406 mol) of propionic acid and acrylic acid. This corresponds to a yield of 14% of the introduced acetylene. The reaction products together yield about 22 g. Of this, 18.1 g is succinic acid in a yield of over 80%.

Exempel 8 (exempel pa kontinuerligt arbets- satt, j amf or med den bifogade ritningen). Example 8 (example of continuous work, cf. with the accompanying drawing).

En blandning med en halt av 90 % acetylen, 5 % koloxid och Vo andra gaser, daribland 1\12,CH4,112, komprimeras med hjalp av kompressorn 2 till ungefar 8 ate' och infores underifran i absorbtionskolonnen 3. In i absorbtionskolonnen infOres ovanifran en frau separeringsanlaggningen 9 kommande omloppslOsning, som forutom vatten, cyklopentanon, barnstenssyra och en liten mangd propionsyra samt akrylsyra innehaller koboltkarbonylforeningar. Sedan omloppslosningen upptagit acetylen, runner den ut ur absorbtionskolonnens nedre ande, komprimeras av kompressorn 4 till ungefdr 300 ato och infOres i reaktionskolonnen 5, som dr forsedd med en varmemantel. Den for reaktionen nodvandiga koloxiden komprimeras aven genom kompressorn 1 till ungefar 300 ato och inf8res i reaktionskolonnen. Den senare ar sa dimensionerad, att reaktionsvatskan kvarbliver dari ungefar en timme. Reaktionskolonnea halles vid temperaturer mellan ungefar 110 och 120° C medelst en varmemantel, som genomstrommas av en vatska, som inkommer i varmemanteln vid 15 och lamnar den- na vidVid reaktionskolonnens ovre del avgar icke reagerad koloxid och aterfores me-deist pumpen 7 till reaktionskarlet, sedan den passerat kylaren 12. Den vid kylningen avskilda omloppslosningen samlar sig i behallaren 6 och Ewes harifran till reaktionskolonnen. A mixture with a content of 90% acetylene, 5% carbon monoxide and Vo other gases, including 1 \ 12, CH4,112, is compressed by means of the compressor 2 to approximately 8 ate 'and introduced from below into the absorption column 3. Into the absorption column is introduced from above a frau solution from the separation plant 9, which in addition to water, cyclopentanone, succinic acid and a small amount of propionic acid as well as acrylic acid contains cobalt carbonyl compounds. After the bypass solution has taken up acetylene, it runs out of the lower spirit of the absorption column, is compressed by the compressor 4 to about 300 atm and is introduced into the reaction column 5, which is provided with a heating jacket. The carbon monoxide required for the reaction is also compressed by the compressor 1 to about 300 atm and introduced into the reaction column. The latter is so dimensioned that the reaction liquid remains there for about an hour. The reaction column is maintained at temperatures between about 110 and 120 ° C by means of a heating mantle which is passed through by a liquid which enters the heating mantle at 15 and leaves it at the upper part of the reaction column emits unreacted carbon monoxide and is returned to the reaction vessel by pump 7. after it has passed the cooler 12. The bypass solution separated during cooling collects in the container 6 and Ewes from here to the reaction column.

Reaktionsvatska uttages vid reaktionskolonnens 8vre del genom ledningen 16 till expansionskarlet 8 och far expandera till ett tryck inom omradet av ungefar 20-30 ato. Harvid Mlles reaktionsvatskan sa varm, att ingen kristallisering kan intraff a. Darefter avgar reaktionsvatskan till filtrena 9, forsedda med kylmantlar, varvid de hallas vid 0° C genom i kylmantlarna bcfintliga flytande NH8. Den harvid utkylda barnstenssyran uttages omvaxlande frau de bada filtrena och tvattas med aceton. Moderluten Aterfores medelst pumpen 11 genom ledningen 17 till absorptionskolonnen 3. De for reaktionen erforderliga mangder vatten, Risningsmedel och katalysator, vilka skola ersatta forlusterna, tillforas den moderlut, som skall aterforas i karlet 10, genom Oppningen 18. Karlet 10 ar kopplat efter filtrena 9 och anordnat fore pumpen 11. Reaction liquid is taken out at the upper part of the reaction column through the line 16 to the expansion vessel 8 and is allowed to expand to a pressure in the range of approximately 20-30 atm. The Mlles reaction liquid is so hot that no crystallization can occur. The reaction liquid then emits to the filters 9, provided with cooling jackets, whereby they are kept at 0 ° C by liquid NH8 present in the cooling jackets. The succinic acid which has thus cooled is removed alternately from the two filters and washed with acetone. The mother liquor is recirculated by means of the pump 11 through the line 17 to the absorption column 3. The quantities of water, risers and catalyst required for the reaction, which are to compensate for the losses, are fed to the mother liquor to be recirculated in the vessel 10 through the opening 18. The vessel 10 is connected after the filters 9 and arranged for the pump 11.

For att undvika anrikning av inert gas (1. ex. NH3, H.) och biprodukter (t. ex. propionsyra, akrylsyra, cyklopentanon) i appraturen, avlagsnas en del av gaserna genom avloppet 14 och en del av vatskan genom avloppet 13 ut ur systemet. Apparaterna 8, 9 och 10 hfillas hela tiden under CO-atmosfar, i det att man UM& dem koloxid Over en led-fling 19 fran gasbehallaren 20. To avoid enrichment of inert gas (1. eg NH3, H.) and by-products (eg propionic acid, acrylic acid, cyclopentanone) in the apparatus, part of the gases are deposited through the drain 14 and part of the liquid through the drain 13 out out of the system. Appliances 8, 9 and 10 are constantly filled under CO atmosphere, in that carbon monoxide is passed over a joint flake 19 from the gas tank 20.

Ritningen visar vid rorledningarna riktningen f8r vatskor och gaser, som foras genom apparaturen. Dessutom innehalla rorledningarna ytterligare ett antal avstangRings- resp. regleringsventiler, vilka icke aro angivna med siffror. The drawing shows at the pipelines the direction of water shoes and gases, which are passed through the apparatus. In addition, the pipelines contain a further number of shut-off or control valves, which are not indicated by numbers.

Enligt en sarskild utforingsform for det 6— — kontinuerliga sattet kan, sedan atminstone en del av barnstenssyran avseparerats, det metallsalt regenereras, som bildats i moderluten genom katalysatorns sonderdelning, i det att man OverfOr den metallsalthaltiga moderluten till en metallkarbonylforening eller en metallhydrokarbonylfiirening med koloxid och vale vid temperaturer Mom omradet 1202000 C, dvs. ovanfor den driftstemperatur, vid vilken den kontinuerliga reaktionen enligt exemplet genomf ores °eh Led& vats-ken, innehallande den regenererande katalysatorn, till kretsloppet. According to a special embodiment of the 6-continuous process, after at least a part of the succinic acid has been separated off, the metal salt formed in the mother liquor can be regenerated by separating the catalyst liquor by transferring the metal salt-containing mother liquor to a metal carbonyl compound or a metal hydrocarbon fiber. vale at temperatures Mom range 1202000 C, ie. above the operating temperature at which the continuous reaction according to the example is carried out the Led & water, containing the regenerating catalyst, to the cycle.

Claims (22)

Patentansprak:Patent claim: 1. Salt att framstalla eventuellt substituerade barnstenssyror med den allmanna formeln: R1 — CH — CO OH B2 — CH — COOH, vari R1 resp. R. betyda vale eller en alkyl-, aryl- resp. alkylarylradikal, kannetecknat darav, att monoacetylenforeningar med den allmanna formeln: i vilken R1 och R. ha ovan angiven betydelse, vid temperaturer mellan 80 och 250° G och tryck mellan 30 och 500 atm, omsattas i neutralt till surt medium med koloxid och vatten i narvaro av katalytiskt verksamma karbonylforeningar med sadana metaller, tillhOrande periodiska systemets attonde grupp, vilka kunna bilda karbonylf5reningarna av typen Mem(G0)., i vilka in dr stone an 1, och i narvaro av organiska lOsningsmedel, vilka kunna losa acetylenforeningarna, vatten och katalysatorerna.Salt to produce optionally substituted succinic acids of the general formula: R1 - CH - CO OH B2 - CH - COOH, wherein R1 resp. R. mean vale or an alkyl, aryl or alkylaryl radical, characterized in that monoacetylene compounds of the general formula: in which R1 and R. have the meaning given above, at temperatures between 80 and 250 ° C and pressures between 30 and 500 atm, are reacted in neutral to acidic medium with carbon monoxide and water in in the presence of catalytically active carbonyl compounds with such metals, belonging to the eighth group of the Periodic Table, which may form the carbonyl compounds of the Mem (G0) type, in which in stone 1, and in the presence of organic solvents, which may dissolve the acetylene compounds, water and catalysts . 2. Salt enligt patentanspraket 1, kannetecknat darav, att reaktionen genomfores i narvaro av koboltkarbonylforeningar eller jarnkarbonylforeningar.Salt according to claim 1, characterized in that the reaction is carried out in the presence of cobalt carbonyl compounds or iron carbonyl compounds. 3. Salt enligt patentanspraket 1, Urineteeknat darav, att dikoboltoktakarbonyl anvandes som katalysator.Salt according to claim 1, Urine derived from the use of dicobalt octacarbonyl as catalyst. 4. Satt enligt patentanspraket 1, kannetecknat &ray, att karbonylforenigar med hogre molvikt bildas av enkla karbonylforeningar i reaktionsrummet.4. According to claim 1, it is claimed that higher molecular weight carbonyl compounds are formed by simple carbonyl compounds in the reaction chamber. 5. Satt enligt patentanspraket 1, kannetecknat darav, att metallkarbonylforeningen bildas i reaktionsrummet av ett salt med denna metal5. A kit according to claim 1, characterized in that the metal carbonyl compound is formed in the reaction chamber of a salt with this metal 6. Salt enligt patentanspraket 5, Untietecknat darav, att en barnstenssyra innehallande losning, t. ex. ett redan anvant reaktionsmedium, anvandes som reaktionsvatska och att koboltsaltet overfores i dikoboltoktakarbonyl vid temperaturer mellan 120-200° C och tryck over 20 atm.Salt according to patent claim 5, Unsubscribed from the fact that a succinic acid containing solution, e.g. an already used reaction medium, was used as a reaction liquid and the cobalt salt was transferred to dicobalt octacarbonyl at temperatures between 120-200 ° C and a pressure above 20 atm. 7. Satt enligt patentanspraket 1, kanne tecknat darav, att man arbetar med ett molekylart overskott av vatten raknat pa den teoretiska mangden.7. Set according to patent claim 1, can be characterized by working with a molecular excess of water calculated on the theoretical amount. 8. Satt enligt patentanspraket 1, kannetecknat darav, att alifatiska eller alicykIiska ketoner, sasom aceton, metyIetylketon, cyklopentanon, anvandas som organiskt losningsmedel. a. Salt enligt patentanspraket 1, kannetecknat darav, att etrar, sasom etylenglykoldimetyleter, dioxan, anvandes som losningsmedel.8. A kit according to claim 1, characterized in that aliphatic or alicyclic ketones, such as acetone, methyl ethyl ketone, cyclopentanone, are used as the organic solvent. a. Salt according to claim 1, characterized in that ethers, such as ethylene glycol dimethyl ether, dioxane, are used as solvents. 9. Satt enligt patentanspraket 1, kannetecknat darav, att man arbetar med ett viktmassigt overskott av organiskt lOsningsmedel gentemot den anvanda mangden vatten.9. A kit according to claim 1, characterized in that a weight-bearing excess of organic solvent is used in relation to the amount of water used. 10. Satt enligt patentanspra'ket 1, kannetecknat darav, att barnstenssyra framstalles genom omsattning av acetylen, koloxid och vatten i narvaro av jarnkarbonylf5reningar.10. A kit according to claim 1, characterized in that succinic acid is produced by reacting acetylene, carbon monoxide and water in the presence of iron carbonyl compounds. 11. Satt enligt patentansprfiket 1, kannetecknat darav, att fenylbarnstenssyra framstalles genom omsattning av fenylacetylen, koloxid och vatten i narvaro av koboltkarbonylf6reningar.11. A kit according to claim 1, characterized in that phenylsuccinic acid is prepared by reacting phenylacetylene, carbon monoxide and water in the presence of cobalt carbonyl compounds. 12. Salt enligt patentanspraket 1, kannetecknat darav, att reaktionen med koloxid genomfores i en enda homogen flytande fas, vilken innehaller losningsmedlet, vattnet, acetylenforeningen och katalysatorn.Salt according to claim 1, characterized in that the reaction with carbon monoxide is carried out in a single homogeneous liquid phase, which contains the solvent, the water, the acetylene compound and the catalyst. 13. Salt att kontinuerligt genomfOra sattet enligt patentanspraket 1, kannetecknat darav, att reaktionsprodukten atminstone delvis skiljes fran reaktionslOsningen och att den kvarvarande vatskan (moderluten), vilken innehaller losningsmedlet, katalysatorn och eventuellt en del av reaktionsprodukten jamte vatten, aterfores in i reaktionsrummet tillsammans med nya tillfogade ramaterial.Salt to continuously carry out the process according to claim 1, characterized in that the reaction product is at least partially separated from the reaction solution and that the remaining liquid (mother liquor), which contains the solvent, the catalyst and possibly a part of the reaction product and water, is returned into the reaction space new added raw materials. 14. Satt enligt patentanspraket 4, kannetecknat darav, att losningsmedelsforluster ers5.ttas.14. Set according to patent claim 4, characterized in that solvent losses are compensated. 15. Satt enligt patentanspraket 14, kannetecknat darav, att reaktionen med koloxid genomfores i en enda homogen flytande fas, som innehaller losningsmedlet, vattnet, acetylenforeningen och katalysatorn.15. A kit according to claim 14, characterized in that the reaction with carbon monoxide is carried out in a single homogeneous liquid phase, which contains the solvent, the water, the acetylene compound and the catalyst. 16. Satt enligt patentanspraket 14, kannetecknat darav, att avskiljningen av reaktionsprodukterna och aterforingen av moderluten foretages i narvaro av koloxid och i franvaro av syre.16. A kit according to claim 14, characterized in that the separation of the reaction products and the recycling of the mother liquor is carried out in the presence of carbon monoxide and in the absence of oxygen. 17. Satt enligt patentanspraket 17, kannetecknat darav, att reaktionslosningen och moderluten Mlles vid temperaturer mellan 50 och 80° C under ett CO-tryck mellan 20 och 30 atm.17. A kit according to claim 17, characterized in that the reaction solution and the mother liquor are milled at temperatures between 50 and 80 ° C under a CO pressure between 20 and 30 atm. 18. Salt enligt patentanspraket 14, kannetecknat darav, att moderluten efter avskiljning av reaktionsprodukterna forsattes med en sadan mangd acetylen, att acetylenens partialtryck utgor 2-20 ato.Salt according to claim 14, characterized in that the mother liquor, after separation of the reaction products, is continued with such an amount of acetylene that the partial pressure of the acetylene is 2-20 atm. 19. Salt enligt patentansprfiket 14, 'alinetecknat darav, att halten barnstenssyrar hat- — —7 les sa lag i reaktionsvatskan, att barnstenssyrornas koncentration icke overskrider 35 viktprocent.19. A salt according to patent claim 14, characterized in that the content of succinic acids is so low in the reaction liquid that the concentration of succinic acids does not exceed 35% by weight. 20. Satt enligt patentanspraket 14, kannetecknat darav, att, efter avskiljning av en del av barnstenssyran, det i moderluten befintliga metallsaltet med barnstenssyrorna overfores i en metallkarbonylf5rening eller en metallhydrokarbonylforening med koloxid och vate vid en temperatur av 120-200° C och att den sa utvunna pa katalysator anrikade vatskan aterfores i kretsloppet.20. A kit according to claim 14, characterized in that, after separation of a part of the succinic acid, the metal salt present in the mother liquor with the succinic acids is transferred into a metal carbonyl compound or a metal hydrocarbonyl compound with carbon monoxide and water at a temperature of 120-200 ° C and that it so the catalyst enriched in catalyst is recycled to the cycle. 21. Satt enligt patentanspraket 14, kannetecknat darav, att moderluten innehallande koboltsuccinat behandlas med koloxid och vale vid temperaturer i omradet frail 120-200° C och vid tryck over 20 at och att den harvid utvunna koboltkatalysatorn aterfores i kretsloppet.21. The kit according to claim 14, characterized in that the mother liquor containing cobalt succinate is treated with carbon monoxide and vale at temperatures in the range from 120-200 ° C and at pressures above 20 atm and that the cobalt catalyst thus recovered is recycled into the cycle. 22. Satt enligt patentanspraket 1 eller 14, kannetecknat darav, att reaktionslosningarna Wallas under ett koloxidpartialtryck, soul ãr hogre an sonderdelningstrycket for den i losningen befintliga katalytiskt verksamma metallkarbonylforeningen. Anfiirda publikationer: Patentskrif ter f rein Tyskland 888 099. Stockholm 1961. Kong]. Boktr. P. A. Norstedt Stiner. 610089 FIG.J GENERALSTABENS22. According to claim 1 or 14, characterized in that the reaction solutions are walled under a carbon monoxide partial pressure, soul is higher than the probing pressure of the catalytically active metal carbonyl compound present in the solution. Cited publications: Patentskrift ter f rein Tyskland 888 099. Stockholm 1961. Kong]. Boktr. P. A. Norstedt Stiner. 610089 FIG.J GENERAL STABENS