DE1668482C - Procedure for splitting acetals or hemiacetals - Google Patents

Description

from about 8.7 to 10.8 weight percent used. According to the invention, it is of crucial importance

30 interpretation, with the shortest possible contact times

work because that way you get education

Avoids heavy by-products, which is not possible with a fixed catalyst.

The invention relates to a method of splitting Among the possible industrial applications of the

of acetals or hemiacetals by hydrolysis or the process of acetal hydrolysis according to the invention

Alcoholysis at elevated temperature using, in particular, the hydrolysis of methylal can

formation of a formaldehyde and methanol which is insoluble in the reaction medium and the hydrolysis of

Ion exchange resin with SO ₃ H groups as catalyst butyrals and isobutyrals of the crude butyl alcohols

sator. from the oxo synthesis. In case of

The principle of the application of acidic ions from 4 ° methylal can formaldehyde directly during the exchangers for the alcoholysis of acetals and the simple distillation stage of the reaction products licher reactions are known. Two can be removed. The formaldehyde is then in shape A distinction is made between groups of processes, namely its solution in water or water plus methanol Borrowed discontinuous processes in which the received, which the residue product in this heating of the reaction medium on the reflux condenser 45 represents distillation. In the case of butyrals and isos, or continuous processes in which the butyrals can be the butyraldehyde and the isobutyric pure Fixed, immobile exchange bed in a reac- aldehyde easily by distillation from the corresponding column is provided. the alcohols in the form of their binary aldehyde-water

The process of the invention does not correspond to any of these azeotropes being separated.

in the. Working methods. In contrast, the invention relates to 50 As mentioned above, the method according to

dung a method for splitting acetals or the invention also with similar advantages to the

Hemi-acetals by hydrolysis or alcoholysis in alcoholysis of acetals or hemi-acetals with alcohol

increased temperature using an in the reac- fetch with the formation of acetals,

tion medium insoluble ion exchange resin with which the alcohol residues from the starting alcohols

SO ₃ H groups as a catalyst, which are thereby marked differently. An industrial application of a

is characterized is that the resin is in the liquid homogeneous such reaction z. B. the reaction of metha-

The reaction mixture is kept in suspension and the umol with a solution of formaldehyde dibutyl acetal,

Settlement temperature is regulated to 60 to 140 ° C. dissolved in butanol or water-saturated butanol.

Maintaining a homogeneous reaction The process of the invention can be batchwise mediums is crucial. When running medium 60 or continuously. That’s continuous is heterogeneous, the suspended borrowed working method can, for. B. by passing it through Ion exchangers do not evenly distribute the liquid reactants within the liquid reactants. Rather, the temperature has been heated by a suspending endeavor, carried out at the interface of the liquid th catalyst containing reaction zone To accumulate phases, whereby its effectiveness becomes 65, whereby a pressure is applied which is substantial is weakened. In addition, there is sufficient space to keep the reaction mixture in the liquid state drive to hold too much of the ion exchanger. One can advantageously use a cone during Use the constant peeling of the reaction-shaped reactor with its tip pointing downwards

is directed, by soft the reaction mixture upwards flows and so the particulate catalyst in a suspended state in a fluidized state holds within the entire liquid phase. Such a reactor is in the German patent 1136 676 described.

The reactions according to the invention generally proceed with acetals of moderately high molecular weight away quickly. It is advantageous to this Perform reactions at relatively high temperatures in order to take advantage of the increase in temperature caused an increase in the reaction rate and to make the formation more complex To prevent compounds of undefined degree of polymerization resulting from hydrolysis released aldehyde at moderately high temperatures form Oas is z. B. the case with formaldehyde.

The preferred pressure range is between 5 and 8 atmospheres.

The preferred contact time is 1 to 3 hours depending on the type of acetal used.

Since acetals are insoluble or only slightly soluble in water, it is necessary to work in the presence of a solvent for the acetals which is also miscible with water under the working conditions. So that no foreign substance is introduced into the reaction, it is advantageous to use an alcohol as the solvent which is identical to that which is released by the hydration.

The amount of water to be used in this case, which apparently from the solubility of the alcohol or others introduced into the reaction medium Depending on solvents, can vary within fairly wide limits, preferably from 8.7 to 10.8%, based on the weight of the reaction mixture, depending on the working conditions used.

example 1

Some hydrolysis processes are carried out in the presence of a polystyrene resin with S0 ₃ H groups from butylbutyrals formed during an oxo synthesis from butyraldehydes (namely n-butyraldehyde and isobutyraldehyde). It is known that this synthesis gives rise to the formation of condensed compounds as by-products and leads to the fact that, inter alia, a butanol fraction (n-butanol and isobutanol) is obtained which contains important amounts of the various isomeric butyl and isobutyl butyrals and isobutyrals.

These butyrals and isobutyrals are according to the method of hydrolysis described above under the special working conditions, including the

as butanols (n-butanol and isobutanol) completely with Water are miscible and the role of solvents play for the latter is treated. There were the following procedures are carried out with these mixtures of butyrals and isobutyrals.

² attempt 4th 5 ¹ I. 8th 3 8th 8th 8th 2000 8th 2000 i 2000 2000 200 2000 200 , 200 200 400 200 400 i 400 400 130 400 130 I 130 130 3 130 2 I 1 3 2.56 3 2.57 1 2.5 2.45 2.46 2.56 2.40 : 2.3 2.31 96.1 2.45 93.3 ι 91 94.25 95.6

Absolute pressure (atmospheres)

Amount of acetal (ml)

Added water (ml)

Catalyst (ml)

Temperature ( ⁰ Q

Response time (h)

Starting butyraldehydes, bound in the form

of butyrals (moles per liter)

Butyraldehydes released (moles per liter)

Example 2

In a conical reactor of the type mentioned above with a total capacity of 0.71, 0.35 l of a polystyrene resin with SO ₃ H groups are introduced; 0.351 per hour of a mixture is then continuously introduced through the lower part of the reactor which is 85.54 percent by weight methylal (ie 11.25 mol / kg), 4.55 percent by weight methanol (1.42 mol / kg) and 9.91 percent by weight Contains water (5.5 mol / kg). The reactor is kept at a temperature of 96 ° C and under an absolute pressure of 7 atmospheres.

When the device operates at equilibrium, the content of formaldehyde is in the liquid at the outlet of the reactor 1.6 mol / kg, corresponding to a turnover of Methylais of 14.23 ° / _0th The concentration of the Fonnaldehyds in weight of the total amount of formaldehyde + water in the reaction products is relative to 40.5 ° / _0th

Example 3

In a reactor similar to that of Example 2, but to a greater extent, the alcoholysis is carried out of formaldehyde di-n-butyl acetal using methanol carried out for the production of methylal.

The following mixture is introduced continuously every hour through the lower part of the reactor into the reactor containing a polystyrene resin with SO _{3 H groups:}

Methanol 6000 g

Formaldehyde dibutyl acetal 1280 g

n-butanol 2216 g

Water 904 g

The reactor is at a temperature of 75 ° C and under an absolute pressure of 5 atmospheres held. The liquid mixture emerging from the reactor has the following composition each Lesson:

I 668 482'T

5

Methylal ..-. 38Og

Methanol 5680g

Formaldehyde dibutyl acetal 480 g

n-butanol 2956 g

Water 904 g

The molar conversion rate of the formaldehyde donated the unconverted starting acetal in German

butyl acetais is 62.5%. Reactor are recycled in such a way that one

Of course, in the case of those carried out continuously, a total conversion rate of essentially

Procedures after recovery of the reaction pro io 100% obtained.

Claims (5)

l 2 medium is removed from the apparatus instead of Claims: that the ion exchanger is evenly distributed in the Device remains, as is the case with the application of a J. Procedure for splitting acetals or homogeneous liquid phase is the case. Half-acetals by hydrolysis or alcoholysis at 5. The homogeneity of the reaction medium allows increased temperature to be regulated using an ion exchange time which is otherwise insoluble in the optimal contact reaction medium. Likewise, in the case of a homozes with SO ₃ H groups as a catalyst, the corresponding reaction medium, it is easy to maintain the temperature, which is the most favorable temperature for the reaction, always the same in the liquid homogeneous reaction mixture in the liquid, homogeneous reaction mixture. The suspension is held and the reaction temperature temperature is regulated to 60 to 140 ⁰ C. heat the reaction medium on the reflux condenser 2. The method according to claim 1, characterized in that the boiling point of the mixture works. This draws that the reaction medium is in liquid but by no means the optimal temperature for the This is maintained by alcoholysis or hydrolysis which can be considered at a pressure of 15 works between 5 and 8 atmospheres. In addition, the development of "steam 3. The method according to claim 1 or 2, characterized by blowing home boiling characterizes the homogeneity of the reaction, that the liquid mixture to be converted. liquid mixture continuously upwards through a The known processes are very generally in the catalyst-containing conical reac- ao carried out a column in which a fixed- gate, the tip of which is directed downwards. of the catalyst bed is located. The Kon 4. The method according to any one of claims 1 to 3, cycle time between the liquid uiid the catalyst characterized in that the con; time of the difficult to regulate. It depends primarily on the Reactant with the catalyst to 1 to viscosity and density of the liquid reaction mixture-3 Hours is regulated. 25 and the permeability of the catalyst 5. Procedure according to one of the preceding bettes, and precisely this last factor, the only one Claims, characterized in that it can be changed in the reaction, can hardly a water content in the mixture to be reacted can be varied within very large limits.