DE1956018A1 - Process for the production of isopropanol and acetone - Google Patents

Description

79-Saint-Leger ~ Les ~ -Melle (Beux-Sevrea) !France

Process for the production of isopropanol and asetone

For this registration the priorities of the French Registrations Mr. 500 / 39ux »Sevree from 25» Efovember 1968 and 6 922 666 of July 7, 1969 claimed

The present invention "relates to a process for the production of isopropanol and asetone from laobutyraldehyde by oxidation or oxidative decarbonylization of isobutyraldehyde in the liquid phase in the presence of a catalyst»

According to the! Invention isobutyraldehyde and a molecular oxygen-containing gas is brought together in the presence Onea catalyst into contact, which consists of one or more oxides, hydroxides or salts of metals of groups I _B II _SSF

III »,

_A , IV _A , Vj, vT _A j VII _a or VIII of the periodic systema

I _a

of the elements - within a liquid reaction medium. The reaction temperature is in the order of 100 to 170 °. The process can take place at atmospheric conditions or a different pressure, in particular above atmospheric pressure, for example up to one Pressure on the order of 5% of the catalyst content Bades, calculated as Metalloryd or Hetalloxyda, is in of the order of magnitude of 1 bio 10 wt.

009821/1956

BATH

else If the gas "which sä molakiilarea" oxygen enthe.lt _P Li2ft _f rmöoci · ^ u :? co »örfc." 4 <SEFC & r2 'Slnf © elih <3IT i * aims that this Angafcs; - to have a limiting character "In some cases, one or more of the following metals are used as a catalyst: silver, molybdenum, vanadium, chromium" tungsten, H.ickai _r Eita & f öer-, Eangan and cobalt, imd zv? Ar la.! Form of their oxides or hydroxy ds _? alone or in Hischiang "The solid catalyst is dispersed within the liquid healing process" medium which may contain a diluting or oiling agent "The diluting or solvent is *? the practical chemistry whether. inert under the ife & fctions ^ edingtmgea is * the agent can & an & n boiling point above 200 ° laesitsusn * i «a ssu termidesi ₅ , that a su erhebliohf: Mengs äieaea feräüaniangö- or ■ solvent files are exercised by the "Bad hinduröhgelsite""Sta Gasatrcm a

Regarding cUa: ve.iWöMbaran 'Tftrdünrxy ^ gs- or g

canoe a great saw! oi-gaaiachßs? Substances are called ^ which u ^ ter d-i5Si Es £ htionsbedingMGge; 3 are liquid * bite playö.weise OÄycTiitior.sbefrbänd ^ Estex * w: - ^ Earl3osy3.es; over with an ire: r ~ 3 ^f > vei.- stöki Kstto in iliraai Molekiilj the at least 12 KaKlenstoff

ethyl.psatyl-4-i: v3thyl-2 ethyl pentancate uM. dergl * or aii re-ii / ¥ 7ie al ίphatii; ^ arbansäiire ^ i with normal set te ^ which contain S to 12% hlonsto-ffa1; ü} ne, for example 3? e! argon .-- «K & pryl- and caprineaure, odsi · ixnuh aliphatic ■ or aromatic ■ would include it high boiling point, such as, 2, B, rd ~ {2 '- / i.thyl-he ^ yl) - "" - aiher mid - uiphanyl ether ^ or also alit> hatieo.he Sohloiiwaaserßtoi'faj, the 12 to 16 aoiil '.enetcffatcme contain * v / is s.Bc ε-Uo-fleoan and !! ■ "iEetra'teöanj or also silicone oils, or Biisohunge dissar 3toffe" - - _:. '

At 4θΐ · Burohfilhruxi;,; ü.03 "% rfi'.hi ^{! i} sne" karm also with Vbr'ieil

od ^ r Lüßmi.geirdfctel "yerwendot, become", the monotony ° baaitst * Αΐε so lohe β low iaieda

009821/1950 bad original

Boiling point below 200 ° baaitst * Αΐε so lohe β low

M * * J there »

Isobutyric acid is particularly suitable as a diluent or solvent. The interest in the use of isobutyric acid arises because this acid is one of the by-products of the oxy.dationa reaction of xsobutyraldehyde, so that when it is used as a diluent or solvent, no foreign substance is introduced into the reaction _or it simplifies the following separation processes of the products obtained α

As a precaution v / ir-d the process is carried out continuously, by adding streams of a molecular oxygen containing gas and liquid isobutyraldehyde to the heated reaction bath initiates which the catalyst is dispersed in State contains = At the beginning, the bath advantageously consists of one Suspension of the catalyst within the liquid - or solvent and is either stirred mechanically or by effectively dispersing the oxygen-containing Sas within the liquid * The Turbu-It; na There should be sufficient inside the bath to ensure that there is intimate contact between the gas and the liquid and uniform Distribution of the catalyst throughout the liquid Painting sites <>

The preventive working conditions are at one temperature from 110 to 3.50 °, a pressure of the order of magnitude swiecheß

and 5 atm and a catalyst content, calculated as oxide, as indicated on the bath calculated _f from 1 to 6 öav /.- ^. The choice of work pressure! depends on the sea door and the flow velocity of the oxygen contained ufiari ßas «3. UZV Dx'iiick is not supposed to. should be high, but should avoid the formation of isobutoric acid within the bath, aye -in XTel'iGiiprodulct der -öxyda.tiona reaction clarstallt., Yfean ar.'lorsrseit "o. cu dCv'3 Yf: v <iunnv: a% ii '. ~ ode - v LÖntingamlütel "by the the%' :. '"} vv>rl; ^ are iid "jra 0.1ns _{Eiitgenotfrniüft}:} rji as a result of imgc '. ». ügar · <lc ü

009821/1956

BATH

Pressure are too considerable, it is simple and expedient to Install a ventilation system behind the Heaktor © ine ssu ,, aie the low boiling point products including iao- "butyric acid separates and enables these connections to be removed, while all or part of the connections sent back to the reaction bath with high boiling points will·

If Xs.o butyric acid- which has a relatively low boiling point used as a thinning or solvent It is advisable to either use a sufficiently high pressure to work to prevent this acid from being entrained by the gases which leave the reaction bath at a Geßerenze ^ which is higher than the rate at which they are generated within the bath, or for the vapors leaving the bath to provide a dephlegmation device, which the condensation and the backflow of the entrained excess isobutter " acid sum bath allows to maintain a constant volume of bath. Am eolcheo essentially from one low-boiling diluents or solvents Incidentally, the bathroom will gradually be used in the course of the procedure replaced by a higher-boiling bath, which mainly consists of high-boiling by-products of the oxidation reaction.

In this case the pressure is preferably of the order of magnitude from 0.5 to 5 Ear, especially between about 1 and 4 Bai \ - As can be seen from the following examples 12 and 15, allows the use of an Esaktoro with a perforated Plate is provided to introduce the air, also haira Working under a pressure of only 1 bar a good conversion rate and a high yield.

The catalysts used also raind in dissolved form effective in the oaydation bath, and consequently rich very small amounts of "dee catalyst, for example IO or some “dozen!” parts per million fclä about 1,000 parts per

009821/1956

ORIGINAL

1958018

Million of catalytic * metal from “For example, 30 to 1,000 ropes per million molybdenum or 10 to 1,000 parts per million manganese can be used

If. under the specified preferred reaction conditions works, the rate of conversion of isobutyraldehyde up to $ 85 per round, generally $ 35 to $ 60, usually be around $ 50. Using those metalloids as catalysts which give the best results, g and which are indicated above as preferred are the practical ones molar yield for the three main products of the oxidation reaction

for isopropanol $ 30 to $ 40

for asetone $ 30 to $ 45 and for isobutyric acid $ 0 to

¥ on then impurities in the finished reaction mixture are present, isopropyl formate, isobutyrate " Acetic acid, propionic acid, methyl ethyl ketone, diasethyl, sisopropyl ether and diiaopropy! ketone »The gaseous by-products are mainly the following

Carbon monoxide 70 to 80 Liohlendioxid 10 to 20 vol. ~ # Propane 10 to 15 vol .- ^.

Also Waaser is formed in the fieaktion "The crude Seaktionaprodukt contains 5 to 10 Gfew. ~ # Water at the top is give ~ nsn preferred conversion Saver Keeps Nissen * Naturally, the water content depends on the exact Ulnwandlimgaverhältnis from"

The catalyst in the Röaktionabadö does the rest3 a partial destruction of the peroxides. The oxidation of isobutyraldehyde in a liquid bath can even be observed AbwöQnheit a catalyst can be carried out, but this · leads very quickly to dangerous and intolerable peroxygene

009821/1956 BADORiGlNAL

1958018

kept in the bath and especially in those obtained in the reaction Products containing 150 to 200 g per liter of peroxides, calculated as perisobutyric acid

The products formed are obtained in the usual way Way, especially through condensation »washing the excess Gases after ordinary distillation or extractive distillation.

The following examples explain various forms of execution jdjer_Br_findungj__. . "^ __ ™ ..-

example 1

The starting bath consists of a dispersion of 100 g of molybdenum _{oxide (MoO 3} ) in 2 liters of a mixture of equal volumes of 2-ethylhexyl-2-ethylhexanoate and 4-methyl-2-ethylpentyl-4-methyl-2-ethylpentanoato

The reactor containing the bath is made of stainless steel with a total capacity of 3 liters, which is equipped with a rotating stirrer, which rotates at 1,000 rpm * The oxygen-containing gas is introduced into the bath through a bore. A Kotarneter measures the feed rate of the gas. The isobutyraldehyde is obtained with the aid of a measuring pump fed. The gases and vapors that leave the reactor are passed through a device that controls the gas from the plus separates and has a capacity of 200 ecm. The separated liquid parts sweep from here through one Siphon back to the reactor. The gases leaving the separation vessel are passed through a condenser, which is cooled with water at room temperature, and further through a, with Water from 10 ° cooled condenser, and finally through condensers made with a mixture of Asse ton and solid carbon dioxide chilled bind "

009821/1956

From the liquid mixtures recovered in the various condensers and from the last condensers When leaving Gaeen, chromatographic analyzes are carried out. These gases contain significant amounts of isobutyraldehyde, acetone and isopropanol, the latter in small quantities. The gases are freed from these compounds by passing them through an aqueous solution of Hydroxylaiainhydrochlorid passes, whose alyee before and after the procedure a control of the chromatographic analysis which allows gases leaving the preceding capacitors. Finally, a gas meter measures the amount of effluent washed in this way

The working conditions are as follows (the gaevolume in this and in the following examples at mold temperature and original print converted):

The amount of isobutyraldehyde added 284 g per hour

¹¹ air 300 1 per hour

Bath temperature 130 °

Pressure 1 atm

The results are as follows:

Not converted isobutyraldehyde 154 g per hour

Xsopropanol recovered 38 g per hour

Acetone recovered 35 g per hour

Isobutter acid recovered 17 g per hour

The amount of gas blown off after washing is 329 liters per hour. It contains 3.3 liters of ffionlenedioxide, 3.6 liters of propane, 19.8 liters Coal monoxide and 34 l oxygen. The remainder is made up of nitrogen.

See the results given above

a conversion ratio of isobutyraldehyde

$ 45.8 per round

a molar yield of isoprai> anol of $ 35.1

009821/1956 _{BM) wmml}

a molar yield of aaetane. from 33? 5 $>

and one molar yield of isobutyric acid v. 10.7? £.

Hall 2 '.

Process is carried out in the apparatus of Example 1 * by using the same Ausgangsbadea _Λ The Work; aind following conditions

^; - Feed quantity qLöb Xsobrity! Aldehyde 186 g per hour

• 300 3 air supply rate per hour

Temperature of the bath. 130 °

Pressure 1 atti

The results are as follows:

Hlciitumgewanäelter uaobutyraldshyd 9? g per hour

Recovered laopropä'ciol. 27.5 g per hour

Aaetone recovered 26.6 g per hour

Recovered xeobric acid. 6 _S 3 g per hour

The amount of gas flowing off after washing is 310 1 p: co hour. It contains 3.1 1 carbon dioxide, 3.5 1 propane, 18.6 carbon dioxide and 30 _f 4 1 oxygen _o Bsr Heat consists of nitrogen,

The results reported above give a conversion ratio of isobutyraldehyde

Per-pass-. Of 47.8 %

sine iao-lare'.Isopro pano lousy prey of 3? _T $ 1

a molar asset loot of 37 »! $>

and an isobutyric acid molar yield of $ 5.8.

The process is carried out in the same device as in Example 1 and with the same starting bath. The working conditions are the following:

009821/1956

1958018

Feed rate of isobutyraldebyd 250 g per hour

Feed rate of air 450 1 per hour

^ temperature of the bath 120 °

Pressure 1 atm

E3 the following results are obtained:

High levels of isobutyraldehyde 131 »5 g per hour Isopropanol recovered 35 g per hour

sJewonnenes Aaeton 30 _f 8 g per hour

Xsobutyric acid recovered 9 »5 g per hour

Bas ·· -Vblumen de "- effluent after the washing gas is 47S 1 per hour" Ee contains 6.1 Kohlandioxydj 1, 2,7 propane 1 ,, 1 carbon XMO noxyd and 53 _y 5 1 oxygen "The Heat consists of Nitrogen,

See the results reported above

a conversion ratio of isobutyraldehyde

3 © passage from 4-7? $ 4

■ a molar yield of isopropanol of 35 »5 $

a molar Ακθton yield of 32.2 jo

a molar yield of isobutyric acid of 6 »6 Ji

Saß Verfshrert is the same in the device according to Example 1 Av.agangsbad carried out the Ai-Arbeitsbedingimgen are the following

The isobutyraldehyde feed rate is 250 g per hour

Feed rate of air 450 liters per hour

i'empsratur des .ftedes 120 °

Pressure 2 atm

The following results were obtained

View of converted isobutyraldohyd 112.5 g per hour

Göwonnenea isopropanol 34 »5 δ per hour,

Acetone recovered 47.1 g per hour

Laobutyric acid recovered 10.1 g per hour

0 0 9 8 21/19 5 6

1958018

~ ίο -

These results show

a conversion ratio of the isobutyraldehyde

^ e passage of 55 5 ^

a molar yield of isopropanol of 30.1 #

a molar yield of acetone of 42.5 #

a molar yield of isobutyric acid of .6 #

Example 5

The process is carried out in the device according to Example 1. The starting bath consists of a dispersion of 100 g Molybdenum oxide (MoO ^ ~ -l53r 2 Idtern a ^ s silicone oil-isit the handIs name "Fluide SI 550" from SISS (Societe industrial of silicone).

The working conditions are as follows

Amount of isobutyraldehyde added 273 g per hour

^{Infeed quantity of the} purchase 300 1 per hour

! temperature of the bath 130 g

Pressure 1 attt

The following results are obtained:

Unreacted ^ sobutyraldahyd 137 g per hour

Isobutyraldehyde recovered 33.3 g per hour

Aaetone recovered 36.3 g per hour

Isobutyric acid recovered 13.8 g per hour

The gas volume flowing off after washing was 303 l per Hour. It contained 2.4 liters of carbon dioxide, 1.6 liters of propane, and 21 liters Carbon monoxide and 26 1 oxygen, the rest consists of nitrogen,

The results reported above show a conversion ratio of isobutyraldehyde

Each passage of. 49.8 #

an isopropanol molar yield of $ 29.4

one molar yield of acetone of 33 »! i *

a molar yield of isobutyric acid of S.3 56

0 0 9 8 21/19 5 6

The procedure of this example is repeated with the change, This time the diluent was 2 liters of rimethylolpropane tripivalate be used. The results are substantial the same.

The process is carried out in the device according to Example 1. Bae starting bath consists of a dispersion of 40 g
Silver oxide in 2 l of the silicone oil according to Example 5 *

The process conditions are as follows:. |

Feed rate of isobutyraldehyde 230 g per hour

Feed rate of air 300 liters per hour

Bath temperature 130 °

Pressure atmospheric pressure

The following results θ are obtained j

Unreacted isobutyraldehyde 14-5 * 5 g per hour

IsopropanoX recovered 25 »5 g per hour

Acetone recovered 24.5 β per hour

Isobutyric acid recovered 14 _S 9 g per hour

Show Bieee Results? "

a conversion ratio of isobutyraldehyde t

^ e passage of 36.7 5ß

a molar yield of isopropanol of 36 _t 2 $
a molar yield of acetone of $ 36>

a molar yield of isobutyric acid of 14 »4- $>

The process is in the device of Example äex \ with
bath given in Example 6 * The processing conditions are as follows

Isobutyraldehyde feed rate 253 g per hour

Supply amount of air 300 liters per hour

iempei-atur dea bath 120 °

Atmospheric pressure

009821/1956 ^ _mQlHAL

* - 32 -

The following results are obtained: Power-set isobutyraldehyde: Isopropanol obtained
Recovered acetone
Isobutyric acid recovered

These results are evident

a Umwandlungsverhältnie of the isobutyraldehyde $ e passage of a molar yield of isopropanol from a molar yield of acetone from e-i'ne molar yield of isobutyric acid of

161.3 g per hour 24 g per hour 21 g per hour 14.2 g per hour 56.2 31.4 28.4 12.7 *

Example 8

The process is carried out in the device according to Example 1. The initial bath consists of a dispersion of 100 g of ohromoxide (Or ₂ O ^) in Tt 1 2 -ethylhaxyl-2-ethylhexanoate

.275 g per hour - 500 ~ T ~ p ¥ ö ~ hour 120 °

Atmospheric pressure

141 g per hour

24.5 g per hour

35.6 g per hour 25 * 2 g per hour

48.8 21.9 52.9

The working conditions are as follows:

Amount of isobutyraldehyde

Amount of air supplied, temperature of the bath
pressure

The following results are obtained:

Isobutyraldehyde is bloom. Isopropanol obtained
Aseton won
Isobutyric acid recovered

These results are evident

a conversion ratio of isobutyraldehyde per pass of -a molar yield of isopropanol of a molar yield of acetone of

a molar amount of isobutyric acid v. $ 15.4

009821/1956 SAD

The process of this example is repeated, using instead of chromium oxide, this time oxides dee nickel, vanadium, tungsten and titanium are used * The results obtained in these various processes are nioht substantially different from each other., Sub AEEN same conditions Oeroxyd are substantially the Same results, but with a lower catalyst content of the bath ", namely 1.25 wt. ~ # instead of 5 wt. ~ $"

Example 9

Initial reaction bath. consists of 1 liter of Isobuttereaure »which contains 3 Sew.-56 Holybdäaoxya (MoO-) and is housed in a stainless steel container» which has a capacity of 3 liters

585 g of isobutyraldehyde and 900 liters of isobutyraldehyde per hour are poured into the bath (measured under normal conditionseu) Air introduced. The working temperature is 130 °, cK & ^ pressure 3 »5 bar, and the stirring, happens with the help of an anchor blower, mechanical stirrer, which rotates at a speed of 1,000 Upsi »

The isobutyraldehyde is introduced with the aid of a measuring pump and the air with the help of a Bdtameter through a in the liquid protruding drilling supplied «The one from the bath through dis Gases entrained vapors are condensed, and the balance of the process is made taking into account the condensate and the non-condensed Gaae ingested "

The peroxide content of the bath, calculated as perisobutyric acid, is 7 g per liter «

The entire conversion of -Xsobutyraldehyde at one time Passage is 64.5 ^.

The molar yields are as follows:

BATH ORIGINAL

00 98 21/19 56

Acetone 33 .9 55 luopropanol 14th , 15 laopropyl formate 9 »4 Isopropyl isobutyrate 3 laobutyric acid 10

The conversion to acetone is 102 g per hour per liter of the bath

The procedure is carried out as in_ Example ^, but aaoh a filtration of the starting bath, which ^ the catalyst in the dispersed state contains to the only suspended To remove Xatalyaator and only the dissolved portion leave in the bath.

The dissolved amount of MoO .. is 1 g per liter «.

The results are as follows

Peroxide content of the bath Bg per liter

The isobutyraldehyde in total is converted with a single pass. $ 64

Molar Yield Test "-

Aseton 35 _S S ^

laopropanol $ 23.1> Isopropylforiaiat 7.15 "^ -

Isopropyl isobutyrate - 3 »! $

Isobutyric acid 14 5 ^

üja conversion in Aseton 109 g per hour © per liter

of the bathroom

ΒβίΒ, ρΙβΙ 11

The process is carried out in the same apparatus and with the same starting bath as iii Example 9, and under the following conditions:

009821 / 13SS

1953018

Overpressure 1 bar temperature 110 °

Under these conditions, it is necessary to maintain the conversion rate of isobutyraldehyde at about 65%, the feed rates of isobutyraldehyde and air
in comparison with example "3 considerably reduce au» it
were supplied:

Isobutyraldehyde 115 g per hour

Air - 150 normal liters * per hour |

Total conversion Ivuigameage dee
Isobutyraidehyas at one-time
Passage * 65.4 #

Molar yields:

Acetone 42.2 % Hour per
Bath Isopropanol 13.5 ■ # Isopropyl formate 14.1 # Isopropylisobu «-
tyrat 5.25 io Isobutyric acid 14.1 ^c / Yield of asetone 25.6 g per
Liters of

In this way of working, the image is enlarged Iaopropyl chloride and a decrease in isopropanol formation were observed.

The beactor consists of a vertical tube made of stainless steel
Steel of 4 m tubes and 57 mm inner diameter. The tube is γόη an ordinary coat at * temperature control while passing Kühlflüsaigkoit as Waaeer or heating fluid such as steam umgöben * Aeee At ground% HREA is Aich setting for fine distribution of air within the Flussig- ~? Äoit you bssteht from a perforated plate _t which is provided with 7 perforations Giiiem Burobiaeeser van 1,5 mm «

009821/1956 8AD ORIGINAL

1955018

Above the reactor there is arranged a distillation column of 2.5 m height "the isto filled with packing material, the gases and vapors leaving the top of the column are passed capacitor by a _t and a corresponding portion of the condensed liquid is sum the upper end of Column redirected back. The reflux is adjusted so that a constant level of liquid bath is maintained inside the reactor. Another purpose of the reflux is to prevent the isobutyric acid vapors from escaping from the obscure bath of the column.

The initial reaction bath consists of 4 liters of isobutyric acid, which in the dissolved state contains 100 parts per million manganese, which is used in 3Orsi of its asetate in the reaction,

The working conditions are as follows:

Temperature of the bath 123 °

overpressure 1 bar

Isobutyraldehydauführung 880 g per ^ö tunde

Air supply 2 200 normal liters

per hour

You total conversion rate of xsobutyraldehyde at one time Passage is $ 79 o

The moderate yields are as follows:

Aaeton 62 <£

Isopropanol 23 i>

Isopropyl formate 1.5 %

Isopropyliso-

butyrate 0.8 fo

■ Isobitteraic acid 4 »4 $

The amount of acetone obtained is 83.5 g ρΐΌ hour per liter dea bath fl *

009821/1956 ORIGINAL BATHROOM

19S3018

Example .1.3

The procedure is carried out in the same device as in example 12 carried out, with an output bath that consists of 2.9 Isobutyric acid consists, which in a dissolved state 15 parts per A million contains manganese which is in Bbrm of its acetate in the reaction is brought * The working conditions are as follows

Bath temperature 126 °

Overpressure 1 bar

laobutyraldehydauführungsmenge 1,440 g per ^ö tunde (j

Air supply volume 22G0 UoTsialliter

per hour

The total amount of isobutyraldehyde converted in one time Passage is 72 #.

The molar yields are as follows

Acetone 57 i> ^ sopropanol $ 26 ^ sopropyl formate $ 1.2

Isopropyliao-

butyrate $ 0.9>

Isobutyric acid 1.8 # ^

The amount of acetone obtained is 134 g per hour per liter of bath.

ORIGINAL INSPECTED

009821/1956

Claims (1)

Claims / loy process for the catalytic production of isopropahol and L- / Aaetone, characterized in that one laobutyraldehyde and an Sas containing molecular oxygen in the presence .; _ eXnae— ^ e ^ teEr-Ka ^ alyQatsrQr-iäer from one or more « Oxides, hydroxides or salts of metals of groups Ig, 1X _B , m _A , IT _A , V _A ,? I _A ,? II _A or VIII of the periodic table of elements consists, within a liquid reek tio name diuras at a temperature in of the order of 100 "to 170 ° _{brings together a} ■ ' 2 "The method according to claim 1, characterized in that the Temperature was in the range of 110 to 150 °, 3> _e method according to claims 1 or 2, characterized in that the jerk is within the order of magnitude of. 0.5 bar to 5 bar. -4. Method according to claim 3 »" characterized in that ^ uIaB - the Pressure is no more than 3 atmospheres » 5. The method according to any one of claims 1 to 4, characterized in that that the gas containing molecular oxygen Air is. 6 «Method according to one of claims 1 to 5, characterized in that that all catalysts are silver, molybdenum, vanadium, Ohröm, 'WoIf-ram »Nickel, ^ itan, Car, Eaagaa or Cobalt in 0 9 8 21/19 5 8 originally inspected '- 19 - lorm of their oxides or hydroxides alone or in a mixture with « each other ^ rwend-t be. eB. according to one of claims 1 "to 6 _? characterized in that the catalyst is dispersed in the liquid reactant or the misoimag. B, Ye rfahren according to any one of claims 1 to 7 »- characterized characterized ,, ö; ate 3 Hatalysatorgelia.lt of fieaktionsmediume or OCE · mixture in the Grb'ßeiiordirang 1-10 wt" - $ _f · berecluiet as oxide, lies" Ie7: - 'Ahren according to claim S ₁ , which means that the catalyst content of the reaction medium or the mixture generally has a size of 1 to 6 crews "-5S, calculated as A method according to any one of claims 1 to S ₁ characterized in that the liquid medical treatment or the mixture is incorporated. Yeredunn'oiigd - or solvent contains "that - represents a fill liquid or a liquid mixture - and, among other things, dsn. Procedure conditions. practically chemically inert and has a boiling point _{above ::: · 200 o} 11. Yev'falirßn according to claim 10 _ä thereby gekemiselohne: t that the 7erdünnungs- or Iiöaungsuiitt @ l is a carboxyl ester with a branched chain, which contains in its molecule at least 12 carbon: aa to ffatome, 12, The method of claim ll _s gekennaelehnst characterized in that it is in the JSater by 2 ~ Äthylh83; yl-2-äthylliexanoat, 4-Metiiyl> 2 - äthylpentyl - 4-methyl ~ 2 - or äthylpsjitanoat BATH ORIGINAL 009821/1956 b j 01 8 13 «Method according to claim 10, characterized in that the Diluent or solvent is an aliphatic carboxylic acid with a normal chain, which has 8 to 12 carbon atoms contains » 14. The method according to claim 13 * characterized in "that it calibrate to the acid around pelargonic acid, caprylic acid or Capric acid? acts «. 15 «Procedure according to Anapruch 10 ,. characterized in that it look at the solvent or diluent for one aliphatic or aromatic ether with a high boiling point acts * 16 »Method according to claim 15, characterized in that the Ether PA ~ (2A'thylhexyl) ~ ether or diphenyl ether is « 17 «ancestors xi according to claim 10» characterized in that the Diluent or solvent an aliphatic hydrocarbon which contains 12 to 16 carbon atoms " 18. The method according to claim 17 »characterized in» that the Hydrocarbon is n-dodecane or n ~ 2! Etradecane., 19. The method according to claim 10 _T, characterized in that the; Thinner or solvent is a silicone oil. 20 * Process according to claims 1 to 9 _f, characterized in that the diluent or solvent is practically inert under the process conditions and has a boiling point below 200 °. 21.1 Method according to claim 20, characterized in that the diluent or solvent is IsobuttersUurö ... 0 9 8 2 1/19 5 6 BAD ORIGINAL ~ 21 - 22 * Procedure after address. 21, characterized * that the Catalyst in the liquid reaction mixture or mixture is solved a 23 "" Method according to claim 22, characterized in that the Catalyst content of the reaction mode or of the mixture “Between 10 parts per million or a few dozen parts per million to about 1,000 parts per million ,, calculated on the catalytic metal, which carries » 2Ί. Method iiach one of claims I to 23? characterized, that © s is carried out continuously » 25. The method according to claim 24, characterized in that streams of a molecular oxygen-containing gas and liquid laobutyraldehyde are introduced into the heated reaction bath with stirring ₉ which contains the catalyst in dispersed suatand « 26, method according to claim 25 »characterized in that the Bath a suspension at the moment the procedure begins or dispersion of the catalyst in the liquid diluent or Solvent represented 009821/1966