SE202871C1

SE202871C1 -

Info

Publication number: SE202871C1
Authority: SE
Publication date: 1965-01-01

Description

Uppfinnare: L Merle oeh T Gubeddu Prioritet begeird Iran den 30 november 1956 (Ndien) Derma uppfinning hänför sig till det kanda forfarandet for framstallning av vatesuperoxid genom alternerande hydrering och oxidering av alkylantrakinoner resp motsvarande hydrokinoner losta i lampliga lOsningsmedel. Inventor: L Merle oeh T Gubeddu Priority Asked Iran 30 November 1956 (Ndien) This invention relates to the known process for the preparation of hydrogen peroxide by alternating hydrogenation and oxidation of alkylanthraquinones or corresponding hydroquinones dissolved in suitable solvents.

Flera patent hanfora sig till framstaliningen av vatesuperoxid genom denna process, 1 vilken en alkylantrakinon, lost i ett losningsmedel eller en blandning av losningsmedel, hydreras i narvaro av en katalysator samt att hydrokinonen efter avskiljning av den for hydreringen anvanda katalysatorn oxideras med luft eller syre, varigenom vatesuperoxid bildas, som avskiljes genom vattenextrahering. Salunda kan antrakinonlosningen.'Atercirkuleras. Several patents relate to the production of hydrogen peroxide by this process, in which an alkyl anthraquinone, dissolved in a solvent or a mixture of solvents, is hydrogenated in the presence of a catalyst and the hydroquinone, after separation of the catalyst used for the hydrogenation, is oxidized with air or oxygen. thereby forming hydrogen superoxide, which is separated by water extraction. Thus, the anthraquinone solution can be recycled.

I ovannamnda process kunna mango_ losningsmedel anvandas och manga patent hanfora sig till dessa. Enligt det amerikanska patentet 2 668 753 och det brittiska patentet 686 567 anvandas som lOsningsmedel for de tvâ stegen, omfattande hydrering och oxide-ring, en blandning av en primar och sekundar nonylalkohol och en monometyl- eller dimetylnaftalen och fOretradesvis diisobutylketon i blandning med alfa-metylnaftalen. In the above process, mango solvents can be used and many patents can be applied to them. According to U.S. Patent 2,668,753 and British Patent 686,567 are used as solvents for the two steps, comprising hydrogenation and oxidation, a mixture of a primary and secondary nonyl alcohol and a monomethyl or dimethylnaphthalene, and preferably diisobutyl ketone in admixture with alpha- methylnaphthalene.

Det liar visatt sig att processen med goda resultat kan genomforas med anvandning som losningsmedel av diklormetan eller dikloretan i blandning med diisobutylkarbinol. It has been found that the process with good results can be carried out using as a solvent of dichloromethane or dichloroethane in admixture with diisobutylcarbinol.

N grund av den speeifika 18sningsfiirmagan has dessa blandningar aro de lampliga bade for hydreringssteget oth for oxidationssteget. Due to the specific solubility, these mixtures are suitable for both the hydrogenation stage and the oxidation stage.

Blandningen innekaller foretradesvis minst volymprocent av diklormetanen eller dikloretanen eller en blandning av dessa kolvaten och minst 60 volymprocent av diisobutylkarbinolen. The mixture preferably recalls at least 1% by volume of the dichloromethane or dichloroethane or a mixture of these carbohydrates and at least 60% by volume of the diisobutylcarbinol.

Genom anvandningen av diklormetan säkerstalles ej endast den lOslighet som erfordras for den oxiderade forrnen, utan det blir Oven majligt att avsevart hoja flampunkten for andra losningsmedel, som skola anvan.das vid framstallningen av vatesuperoxid, varigenom de bit mindre riskabla och mera lampliga for ett tillverkningsforfarande. The use of dichloromethane not only ensures the solubility required for the oxidized furnace, but also makes it possible to considerably raise the flash point of other solvents to be used in the production of hydrogen superoxide, making the pieces less risky and more suitable for a manufacturing process. .

Av denna orsak kan aven en foredragen blandning best& av 30-35 % av en blandning erhallen av 30 volymdelar diklormetan och 70 volymdelar dikloretan samt 70-65 volymprocent diisobutylkarbinol. Med dessa losningsmedel kunna manga alkylantrakinoner anvandas, men det fOredrages att anvanda etylantrakinon, foretradesvis i en mangd av 140 g/1 pa grund av dess stOrre loslighet och lattillganglighet. For this reason, even a preferred mixture may consist of 30-35% of a mixture obtained by 30 parts by volume of dichloromethane and 70 parts by volume of dichloroethane and 70-65% by volume of diisobutylcarbinol. Many alkyl anthraquinones can be used with these solvents, but it is preferred to use ethyl anthraquinone, preferably in an amount of 140 g / l due to its greater solubility and readiness.

Med ovannamnda blandning kan en arbetslosning innehallande 150 g/1 etylantrakinon framstallas och efter hydrering kan en lOsning innehallande 90-95 g/1 etylantrahydrokinon erhallas utan att flagon utfallning av denna produkt iakttages. With the above mixture a working solution containing 150 g / l of ethyl anthraquinone can be prepared and after hydrogenation a solution containing 90-95 g / l of ethyl anthrahydroquinone can be obtained without observing the precipitation of this product.

Utan att uppn& total omvandling av etylantrakinon till etylantrahydrokinon (eftersom denna omvandling sasom bekant beframjar bildningen av den mindre l5sliga tetrahydrokinonen) men med begransning av hydrerin.gen till 60-6Vo av den narvarande etylantrakinonen kan pa detta satt en koncentration 2 av 90-95 g/1 etylantrakinon dven uppnhs, vilken koneentration dr erforderlig for att man efter oxidation skall uppna den hOga halten 10-12 g/1 vdtesuperoxid i arbetslosningen. Without achieving total conversion of ethyl anthraquinone to ethyl anthrahydroquinone (since this conversion is known to promote the formation of the less soluble tetrahydroquinone) but with limitation of the hydrogen to 60-6Vo of the present ethyl anthraquinone, a concentration of 90-95 g can be set. / 1 ethyl anthraquinone is also obtained, which concentration is required in order to achieve the high content of 10-12 g / l of hydrogen peroxide in the working solution after oxidation.

Pet liar visat sig aft ,anvdndningen av en losningsmedelsblandning innehallande diklormetan och/eller dikloretan gör det mojligt att genorafora antingen hydreringen eller oxideringen inom en tidrymd, vilken är atminstone 2/3 kortare an den som ,erfordras med andra losningsmedelsblandningar. It has been found that the use of a solvent mixture containing dichloromethane and / or dichloroethane makes it possible to reverse either the hydrogenation or the oxidation within a period of time which is at least 2/3 shorter than that required with other solvent mixtures.

Detta hErgre vateabsorptionsforhallande medfor ej endast en uppenbar praktisk fordel med avseende ph anlaggningarnas storlek, utan bidrager dven avsevart till minskning av majligheten till bildning av produkter med hogre hydreringsgrad an den hos etylantrakinon, vilka dro mindre losliga .och ha en mycket redficerad hydrerings- och oxidationshastighet, sasom exem.pelvis är fallet med tetrahydroantrakinon. This higher water absorption ratio not only has an obvious practical advantage with regard to the size of the plants, but also contributes significantly to reducing the possibility of forming products with a higher degree of hydrogenation than that of ethylanthraquinone, which have less soluble and have a highly modified hydrogenation and oxidation rate. , as is the case, for example, with tetrahydroanthraquinone.

Foljande speciella exempel avse endast att belysa uppfinningen men icke att begransa derma. The following special examples are intended only to illustrate the invention but not to limit it.

Exempel 1. En blandning av 30 volymdelar diklormetan och 70 volymprocent dikloretan bereddes. 15 g etylantrakinon 18stes hastigt i 30 ml lay denna blandning och 70 ml diisobntylkarbinol tillsattes. Den sh erhallna arbetslosningen hydrerades i narvaro• av Raney-nickel som katalysator, varvid 830 nil vale, raknart vid. 0°C och 760 mm Hg infordes mom 3 minuter utan att flagon utfallning av etylantrahydrokinon iakttogs. Example 1. A mixture of 30 parts by volume of dichloromethane and 70% by volume of dichloroethane was prepared. 15 g of ethyl anthraquinone were rapidly added to 30 ml of this mixture and 70 ml of diisobutylcarbinol were added. The resulting working solution was hydrogenated in the presence of Raney nickel as a catalyst, leaving 830 nil vale, straight at. 0 ° C and 760 mm Hg were introduced for 3 minutes without observing the precipitation of ethyl anthrahydroquinone.

Efter avskiljning av katalysatorn, liar man arbetade med syre, visade sig losningen vara fullstdndigt oxiderad efter 2 minuter, och den erhallna vdtesuperoxiden extraherades med vatten. After separation of the catalyst, while working with oxygen, the solution was found to be completely oxidized after 2 minutes, and the resulting hydrogen peroxide was extracted with water.

Den sh. erhallna vatesuperoxiden utgjorde 1,2 g, dvs. 94,85 % av det teoretiska utbytet, raknat ph mangden anvant irate. Koncentrationen av den bildade valesuperoxiden i axbetslosningen fore extraheringen med vatten var 11 g/l. The sh. the hydrogen peroxide obtained amounted to 1.2 g, i.e. 94.85% of the theoretical yield, shaved ph amount used irate. The concentration of the valence superoxide formed in the pickling solution before extraction with water was 11 g / l.

Exempel 2. 14 g etylantrakinon loses i en blandning besthende av 30 ml diklormetan och 70 ml diisobutylkarbinol. Example 2. 14 g of ethyl anthraquinone are dissolved in a mixture consisting of 30 ml of dichloromethane and 70 ml of diisobutylcarbinol.

Denna lOsning underkastas hydrering i ndrvaro av Raney-nickel och darefter oxidation med syre. This solution is subjected to hydrogenation in the presence of Raney nickel and then oxidation with oxygen.

Den bildade vatesuperoxiden extraheras med vatten och ett utbyte av 11202 av 91 % erhalles, raknat ph det inf6rda vatet. The hydrogen peroxide formed is extracted with water and a yield of 91% of 91% is obtained, shaved off the introduced water.

Exempel 3. 14 g etylantrakinon loses i en blandning av 25 volymprocent diklormetan ocb 75 volymprocent diisobutylkarbinol. Denna losning underkastas hydrering i narvaro av en katalysator och darefter oxidation med syrgas. Example 3. 14 g of ethyl anthraquinone are dissolved in a mixture of 25% by volume of dichloromethane and 75% by volume of diisobutylcarbinol. This solution is subjected to hydrogenation in the presence of a catalyst and then oxidation with oxygen.

Behandlingstiderna motsvara de i exempel 1 ,angivna. The treatment times correspond to those given in Example 1.

Den erhallna vfitesuperoxiden extraheras med vatten och ett utbyte av 11202 av 93 % erhdlles, rdknat ph vdtet. The resulting white superoxide is extracted with water and a yield of 11202 of 93% is obtained, calculated from the weight.

Claims

Patent claim:

1. In the preparation of hydrogen superoxide according to the alkyl anthraquinone process, characterized in that dichloromethane or dichloroethane in admixture with diisobutylcarbinol was used as solvent for the anthraquinones and the corresponding hydroquinones in the hydrogenation and oxidation steps.

2. A process according to claim 1, Unsubscribed claim, that the mixture of solvents consists of at least 20% by volume of the dichloromethane or dichloroethane or of a mixture of these pistons and at least 60% by volume of the diisobutylcarbinol.

3. A process according to claim 1 or 2, characterized in that a mixture consisting of 30-35% by volume of dichloromethane and 70-66% by volume of diisobutylcarbinol, containing above 1 g / l of ethyl anthraquinone, is used.

4. A process according to claims 1 and 2, characterized in that a mixture consists of 30-36% of a mixture of 30 parts by volume of dichloromethane and 70 parts by volume of dichloroethane and 70-05% by volume of diisobutylcarbinol, Above containing 1 g / l of ethyl anthraquinone, any6.ndes. Cited publications: Patents from France 1,128,844; United Kingdom 449 360.