DE1956018B - Process for the catalytic production of isopropanol and acetone - Google Patents

Description

3 4

If solvents are used, it is advisable to either quickly switch to dangerous or intolerable Ferunter a high enough pressure to work to reduce the oxide content in the bath and especially in the entrainment of this acid by the gases to prevent reaction products containing 150 to those who are in the reaction bath at a rate of 200 g per liter of peroxide, calculated as per leaving, which is higher than its rate of formation isobutyric acid.

inside the bath, or for which the bath is used vapors leaving a dephlegmation device in the usual way, in particular by condensation, watch the condensation and reflux washing of excess gases after ordinary the entrained excess isobutyric acid for distillation or extraction distillation. Bath allows so as to maintain a constant volume of the io. The following examples illustrate various AusBaths. Such an essentially guiding form of the invention, from a low-boiling diluent or

Incidentally, the starting bath consisting of a solvent is Example 1

in the course of the process gradually through a higher- The starting bath consists of a dispersion of

Replaced a boiling bath, which mainly consists of high is 100 g of molybdenum oxide (MoO ₃ ) in a mixture of 21

boiling by-products of the oxidation reaction equal volumes of 2-ethylhexyl-2-ethylhexanoate and

consists. ^ Methyl ^ -ethylpentyl- ^ methyl ^ -ethylpentanoate.

In this case, the pressure is preferably of the order of magnitude of the reactor containing the bath from 0.5 to 5 bar. in particular free steel with a total capacity of between about 1 and 4 bar. As from the following 20 3 1, which is equipped with a rotating stirrer Beisp the 12 and 13 can be seen, which is made possible, which rotates at 1000 rpm. The oxygen Use of a reactor which is filled with a gas that is pierced through a pipe into the bath Plate zi> m introducing the air is provided, conducts. A rotamete measures the feed rate when working under a pressure of only 1 bar speed of the gas. The isobutyraldehyde is using a good conversion rate and a high 25 supplied to a metering pump. The gases and vapors Yield. which leave the reactor are

The catalysts used, which separate the gas from the liquid, are also activated dissolved state effective in the oxidation phase, and has a capacity of 200 ecm. The consequent very small amounts of the catalyzed liquid parts sweep from here through one sators, for example 10 or a few cleaning parts per 30 siphon back to the reactor. The verMillion Up to about 1000 parts per million of the catalytic gases are passed through a condenser look like metal. For example, you can pass 30 to that with water at room temperature ge-1000 Parts per million molybdenum, or 10 to 1000 parts, is cooled, and is continued by a water-containing per million manganese are used. 10 "chilled condenser and finally through

If one of the stated preferred 35 capacitors, which with a mixture of acetone

Reaction conditions works, the conversion and solid carbon dioxide can be cooled,

rate of the isobutyraldehyde per passage of the in the various condensers

up to 85%, generally 35 to 60%, usually recovered liquid mixtures and of

be about 50%. Using those gases leaving the last condensers

Metal oxides as catalysts, which are the best Er- 40 Chromatographic analyzes are carried out,

deliver results and those indicated above as preferred. These gases contain not yet negligible

are the practical molar yields for amounts of isobutyraldehyde, acetone and isopropanol,

the three main products of the oxidation reaction, the latter in small quantities. The gases are from

for isopropanol 30 to 40% «These compounds can be freed by using them

for acetone 30 to 45 ° / ⁴⁵ by an aqueous solution of hydroxylamine hydro-

and for isobutyric acid '.'. '.'. . '.'. '. Υ.'. '. 0 to 15% f ^Ιθή $ passes their analysis before and after

a control of the chromatographic

From the impurities that can be seen in the finished analysis of the previous capacitors

Reaction mixture are present, iso-leaving gases should be mentioned. Finally measure one

propyl formate, isobutyrate, acetic acid, propionic acid, 5 ° gas meter the amount of the so washed effluent methyl ethyl ketone, Diazethyl, diisopropyl ether and the gases.

Diisopropyl block. The gaseous by-products The working conditions are as follows (thereby

are mainly the following: the gas volume in this and in the following two

Carbon monoxide 70 to 80 volume percent ^{everal s} P, ^{na "f} normal temperature and normal pressure environmentally

Carbon dioxide 10 to z0 percent by volume ⁵⁵ g ^erecnne V ^:

Propane 10 to 15 percent by volume _ ....,

Feed rate of the

Water is also formed in the reaction. The isobutyraldehyde 284 g per hour

The crude reaction product contains 5 to 10% by weight of the amount of air supplied ... 300 liters per hour

Percent water at the preferred 60 temperature of the bath given above 130 °

Conversion ratios. Naturally, the pressure depends on 1 atm

Water content of the exact conversion ratio- _{The £} ^ _{are de} . ms from.

The catalyst present in the reaction bath is unreacted

Incidentally, it partially destroys the peroxides. 65 isobutyraldehyde 154 g per hour

In itself, the oxidation of isobutyraldehyde in recovered isopropanol could be 38 g per hour

buckets of liquid bath even in the absence of a recovered acetone 35 g per hour

Catalyst, but this results in Isobutyric Acid Recovered 17 g per hour

1

The amount of gas blown off after washing is 3291 per hour. It contains 3.31 carbon dioxide, 3.61 propane, 19.81 carbon monoxide and 341 oxygen. The ResL consists of nitrogen.

5 Show the results reported above

a conversion ratio of the

Isobutyraldehyde per pass of .. 45.8% a molar yield of

35.1% isopropanol

a molar yield of acetone of ... 33.5% and a molar yield of

Isobutyric acid of 10.7%

B e i s ρ i e 1 2

The process is carried out in the apparatus of Example 1, using the same starting bath. The working conditions are as follows: _ao

Feed rate of the

Isobutylaldehyde 186 g per hour

Air intake rate ... 3001 per hour

Bath temperature 130 °

Pressure 1 atm

The results are as follows:

Unconverted

Isobutyraldehyde 97 g per hour

Isopropanol recovered ... 27.5 g per hour

Acetone recovered 26.6 g per hour

Isobutyric acid recovered ... 6.3 g per hour

The amount of gas flowing off after washing is 310 'per hour. It contains 3.11 carbon dioxide, 3.5 1 propane, 18.6 1 carbon monoxide and 30.41 oxygen. The rest consists of nitrogen.

The results reported above result

a conversion ratio of the

Isobutyraldehyde per pass of ... 47.8 ° / ₀ a molar isopropanol yield of ... 37.1%

a molar acetone yield of 37.1%

and a molar isobutyric acid yield of 5.8%

45 Example 3

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

Feed rate of the

Isobutyraldehyde 250 g per hour

Air intake rate ... 4501 per hour

Bath temperature 120 °

Pressure 1 atm

The following results are obtained:

Unconverted

Isobutyraldehyde 131.5 g per hour

Isopropanol recovered .. 35 g per hour

Acetone recovered 30.8 g per hour

Isobutter obtained. ^ Iure .. 9.5 g per hour

The volume of the gas flowing off after washing is 476 liters per hour. It contains 6.11 carbon dioxide, 2.71 propane, 211 carbon monoxide and 53.5 Oxygen. The rest consists of nitrogen.

018 /

Show the results reported above
a conversion ratio of the

Isobutyraldehyde per pass of .. 47.4 ° / ₀ a molar yield of isopropanol

from 35,.,%

a molar acetone yield of 32.2%

a molar yield of isobutter

acid from "» "'0

Example4

The process is carried out in the device according to Example 1 with the same starting bath. the Working conditions are as follows:

Addition amount of the

Isobutyraldehyde 250 g per hour

Air intake rate ... 450J per hour

Bath temperature 120 °

Pressure ^{2 atm}

The following results were obtained:

Not implemented

Isobutyraldehyde 112.5 g per hour

Isopropanol recovered .. 34.5 g per hour

Acetone recovered 47.1 g per hour

Isobutyric acid recovered .. 10.1 g per hour

These results show

a conversion ratio of the
Isobutyraldehyde per pass of ... 55%

a molar yield of isopropanol
of 30.1%

a moderate 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 initial bath consists of a dispersion of 100 g of molybdenum oxide (MoO ₃ ) in a silicone oil with the trade name "Fluide SI 550".

The working conditions are as follows:

Feed rate of the

isobutyraldehyde 273 g per hour

Amount of air supplied ... 300 1 per hour

Bath temperature 130 g

Pressure 1 atm

The following results are obtained:

Not implemented

Isobutyraldehyde 137 g per hour

Won

Isobutyraldehyde 33.3 g per hour

Acetone recovered 36.3 g per hour

Isobutyric acid recovered .. 13.8 g per hour

The volume of gas flowing off after washing was 3031 per hour. It contained 2.41 carbon dioxide, 1.61 propane, 211 carbon monoxide and 26) Oxygen. The rest consists of nitrogen.

The results reported above show:

a conversion ratio of the

Isobutyraldehyde per pass of ... 49.8% a mola.e yield of isopropanol

from 29.4%

a molar yield of acetone of ... 33.1% a molar yield of isobutyric acid of 8.3%

The procedure of this example is repeated except that as a diluent this time Trimethylolpropane tripivalate can be used. The results are essentially the same.

Example 6

The process is carried out in the device according to Example 1. The exit bathroom consists of a dispersion of 40 g of silver oxide in 21 of the silicone oil according to Example 5.

The process conditions are as follows:

Feed rate of the

Isobutyraldehyde 230 g per hour

Air intake rate ... 3001 per hour

Bath temperature 130 °

Pressure atmospheric pressure

The following results are obtained:

Not implemented

Isobutyraldehyde 145.5 g per hour

Isopropanol recovered .. 25.5 g per hour

Acetone recovered 24.5 g per hour

Isobutyric acid recovered 14.9 g per hour

These results show:

a conversion ratio of isobutyraldehyde per pass of .. 36.7%

a molar yield of isopropanol of 36.2%

a molar yield of acetone of ... 36%

a molar yield of isobutyric acid of 14.4%

Example 7

The process is carried out in the device according to Example 1 with the bath specified in Example 6. The procedural conditions are as follows:

Addition amount of the Isobutyraldehyde 253g per hour

Air supply rate ... 3001 per hour Bath temperature 120 ° Atmospheric pressure

pressure

The following results are obtained:

compulsory Isobutyraldehyde 1613g per hour

Isopropanol recovered .. 24 g per hour Acetone recovered 21g per hour

Isobutyric acid recovered 14.2 g per hour

These results show

a conversion ratio of isobutyraldehyde per Drgg of ... 36.2%

a molar yield of isopropanol of 31.4%

a molar yield of acetone of ... 28.4%

a molar yield of isobutyric acid of 12.7%

Example 8

The process is carried out in the device according to Example 1. The starting bath consists of a dispersion of 100 g of chromium oxide (Cr ₁ O ₈ ) in 2-ethylhexyl 2-ethylhexanoate.

The working conditions are as follows:

ίο Feed quantity of the

Isobutyraldehyde 275 g per hour

Air intake rate ... 3001 per hour

Bath temperature 120 °

Pressure atmospheric pressure

The following results are obtained:

Not implemented

so isobutyraldehyde 141 g per hour

Isopropanol recovered .. 24.5 g per hour

Acetone obtained 35.6 g per hour

Isobutyric acid recovered .. 25.2 g per hour
These results show
a conversion ratio of the

Isobutyraldehyde per pass of .. 48.8%
a molar yield of isopropanol

of 21.9%

a molar yield of acetone of ... 32.9%
a molar yield of isobutyric acid of 15.4%

The procedure of this example is repeated, but this time instead of chromium oxide, oxides of Nickel, vanadium, tungsten and titanium can be used. Those involved in these different procedures The results obtained are not significantly different from each other. Under the same conditions Ceria gives essentially the same results, but with a lower catalyst content of the bath, namely at 1.25 percent by weight instead of 5 percent by weight.

Example 9

The initial reaction bath consists of 11 isobutyric acid, which contains 3 percent by weight of molybdenum oxide (MoO ₁ ) and is housed in a stainless steel container with a capacity of 31.

$ 0 585 g of isobutyraldehyde and 9001 (measured under normal conditions) air are introduced into the bath per hour. The working temperature is 130 °, the overpressure 3.5 bar, and stirring is done ankerfönnigen with the aid of a mechanical stirrer which rotates at a speed of 1000 rpm.

The isobutyraldehyde is introduced with the aid of a measuring pump and the air is fed in with HMe of a rota meter through a tube protruding into the liquid . The vapors entrained by the gases from the bath are condensed and the balance of the process is adjusted taking into account the condensate and the non-condensed gases.

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

The total isobutyraldehyde conversion in a single pass is 64.5%.

The molar yields are as follows:

n 33.6%

Isopropanol 24.9% Isopropyl formate 9.15% Isopropyl isobutyrate 3.4% Isobutyric acid 10%

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

Example 10

The procedure is carried out as in Example 9, but after a filtration of the starting bath, which contains the catalyst in a dispersed state in order to remove the only suspended catalyst portion far away and only to leave the dissolved portion in the bath.

The dissolved amount of MoO ₁ is 1 g per liter. The results are as follows: Peroxide content of the bath 8 g per liter

Total conversion amount of isobutyraldehyde single pass 64%

Molar yields:

Acetone 35.8 ° ₀

Isopropanol 23.1% Isopropyl formate 7.15% Isopropyl isobutyrate 3.1% Isobutyric acid 14% Conversion to acetone 109 g per hour

per liter of the bath

Example 11 Example 12 The reactor is made up of a vertical tube

stainless steel of 4 m high and 57 mm internal

Diameter. The pipe is of an ordinary one Surrounding jacket for temperature control. On the ground

the pipe is the facility for fine

Distribution of air within the liquid. she

consists of a perforated plate with 7 holes

ίο has a diameter of 1.5 mm.

Above the reactor there is a distillation column 2.5 m high with packing material is filled. The gases and vapors leaving the top of the column are passed through a condenser and an appropriate proportion of the condensed liquid is passed to the top of the column Returned column. The reflux is adjusted so that a constant level of the liquid bath is maintained within the reactor. Another purpose of the reflux is to allow the isobutyric acid vapors to escape from the to avoid the upper end of the column.

The starting reaction bath consists of 41 isobutyric acid, which in dissolved state 100 parts per as Million contains manganese, which is used in the reaction in the form of its acetate.

The working conditions are as follows: Bath temperature 123 ° Overpressure 1 bar Isobutyraldehyde feed ... 880 g per hour Air supply 2200 normal liters

per hour

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

Overpressure 1 bar Temperature 110 °

Under these conditions it is necessary to increase the conversion amount of isobutyraldehyde from about To maintain 65%, the feed rates of isobutyraldehyde and air are compared change considerably with Example 9. Ss were

Isobutyraldehyde 115 g per level Air 150 normal liters

Total conversion rate per hour

of isobutyraldehyde

emmahgem passage .. 65.4%

Molar yields:

Acetone 42 ^%

Isopropanol 13.5% Isopropyl formate 144% IsopropyBsobutyrate 5.25% Isobutyric acid 14.1% Yield of acetone 25.6 g per hour

per liter of the bath

In this procedure, an increase in the formation of isopropyl formate and a decrease in Isopropanol exposure observed.

The total amount of conversion of isobutyraldehyde in a single pass is 79%.

The molar yields are as follows:

Acetone 62%

Isopropanol 23% Isopropyl formate 1.5% Isopropyl isobutyrate 0.8% Isobutyric acid 4.4%

The amount of acetone obtained is 83.5 g per hour per liter of the bath.

Example 13

The process is carried out in the same apparatus as in Example 12, with one Starting bath, which consists of 2.91 isobutyric acid, which in the dissolved state contains 15 parts per million of manganese, which in the form of its acetate is involved in the reaction is brought. The working conditions are as follows:

Bath temperature 126 " Overpressure ι bar Isobutyraldehyde feed

amount 1440 g per hour

Air supply amount 2200 normal liters

per hour

The total amount of isobutyr ι, ΐΑ- * Λ * converted in a single pass is 72%.

The molar yields are as follows:

Acetone f ₀

Isopropanol 26% Isopropyl formate 1.2%

11 12

Isopropyl isobutyrate 0.9% softening vapors are condensed, whereby one

Isobutyric acid 1.8% on the one hand receives a condensate and on the other hand non-condensed gases. The process balance sheet, d. H. the

The amount of acetone obtained is 134 g per calculation of the amount of conversion, the off hour per liter of the bath. 5 hives and production takes place on the basis of _. ...... analyzes that both the condensate and the gases

^Beis P ^ie114 considered.

A bath is used as the starting material, which The peroxides content of the bath is expressed in 11 isobutyric acid, the 0.05 weight perisobutyric acid, is 21 g / l. percent manganese isobutyrate and 0.05% cobalt iso- io contains the total amount of conversion of isobutyrbutyrate. The catalyst is aldehyde in this way in one pass is 76.5%. completely resolved. The bath is located in a reaction vessel made of acid-proof steel with a capacity of 31 The molar yields are as follows: assets. Acetone 45 2 ° /

493 g of isobutyr- 15 _% propanol * are passed into the bath per hour. '.'. '.'. '.'. '.'. '.'. '.'. '.'. '.'. '.'. '.'. '.'. '.'. 3 ^ 8%

aldehyde and 9001 air an isopropyl formate 112%

The working temperature is 125 ° and the pressure isopropyl isobutyrate 2.16%

3 bar. The stirring is ensured by a mechanical isobutyric acid 5 9 ° /

Anchor stirrer worried that makes 100 rpm. The isobutyraldehyde is with the help of a dosing μ of acetone are 108 g / hour per liter of the bath

pump and air obtained with the help of a rotameter. The production of isopropanol is

immersed pipe initiated. That with the gas is 81.5 g / hour per liter of the bath.

Claims (6)

Preferably, the gas, which molecular patent claims contains: oxygen, air Examples of suitable dilution or solution 1. Process for the catalytic production of medium are oxidation-resistant esters, such as carb-isopropanol and acetone, characterized by the fact that oxyl esters with a branched chain in their molecule are characterized by the fact that they have isobutyraldehyde with at least 12 carbon atoms, such as molecular oxygen Gas in counter-2-ethylhexyl-2-ethylhexanoate, 4-methyl-2-äthyIpenwart a normally solid catalyst, the tyl-4-methyl-2-ethylpentanoate or acids, such as from one or more oxides, hydroxides, aliphatic carboxylic acid with normal Chain, which or salts of molybdenum, chromium, silver, nickel, io 8 to 12 carbon atoms contain, such as pelargon, vanadium, tungsten, titanium, cerium, manganese or caprylic and capric acid, or aliphatic or cobalt, within a liquid Reaction aromatic ethers with a high boiling point, such as dimediums at a temperature of 100 to 170 ⁰ C (2-ethylhexyl) ether and diphenyl ether, or also converts. aliphatic hydrocarbons containing 12 to 16 carbon 2. The method according to claim 1, characterized in that they contain 15 substance atoms, such as n-dodecane and n-tetra drawing, that one decane the reaction at a pressure, or silicone oils, or mixtures of these from 0.5 to 5 bar. Fabrics. 3. The method according to claim 1 or 2, characterized in that when carrying out the method can also be characterized in that the reaction is advantageously used a diluent or solvent-use a catalyst content of the reac- 20 det has a boiling point below 200 ^c , tion medium from 1 to 10 percent by weight, as such a low-boiling diluent or calculated as oxide. Isobutyric acid is particularly suitable as a solvent. 4. The method according to any one of claims 1 to 3, the interest in the use of isobutyric acid, characterized in that the liquid is given because precisely this acid is one of the reaction medium chemically inert diluent 25 by-products of the oxidation reaction of the isobutyr or solvent with represents a boiling point above aldehydes, so that when used as 200 ⁰ C used. No foreign sub- 5. The method according to claim 4, characterized in that it is introduced into the reaction. This simplifies draws that the following methods of separation of the products obtained are used as dilution or solution, medium 2-ethylhexanecarboxylic acid 2-ethylhexyl ester 30 Preferably, the process is continuous used. performed by drawing currents of a molecular 6. The method according to claim 1 or 2, characterized in that the oxygen-containing gas and the liquid Iso is introduced as diluent or butyraledhyds into the heated reaction bath. Solvent isobutyric acid used, whichever contains the catalyst in a dispersed state one carries out the reaction using a 35. At the beginning, the bath advantageously consists of a catalyst content of 10 to 1000 ppm through a suspension of the catalyst within the leads. liquid diluent or solvent and will either mechanically stirred or by the fact that the oxygen-containing gas dispersed within the liquid 40 is yawed. The turbulence within the bath should be sufficient for an intimate contact of the gas with the liquid and even distribution The invention relates to a method for the catalyst within the entire liquid catalytic production of isopropanol and acetone. Mediuns to ensure. In accordance with the invention, isobutyraldehyde is used atü and a catalyst content, calculated as oxide, or salts of molybdenum, chromium, silver, nickel, calculated as indicated on the bath, of 1 to 6 GeVanadin, tungsten, titanium, cerium, manganese or cobalt 50 percent by weight. The choice of the working pressure depends on the temperature and the flow rate within a liquid reaction medium at a temperature of 100 to 170 ⁰ C around. Preferred of the oxygen-containing gas. The pressure should be wise to carry out the reaction at a pressure that is not too high to be 0.5 to 5 bar within the bath. According to a preferred embodiment, to avoid the collection of isobutyric acid, which is a form of the process, the implementation is a by-product of the oxidation reaction. When using a catalyst content of the reaction, on the other hand, the amount of the high-boiling substances, tion medium of 1 to 10 percent by weight, calculated in particular of the diluent or solvent, as oxide, through. Advantageously, used by the bath gases leaving taken as a liquid reaction medium a chemically inert be, are due to insufficient pressure to considerably diluent or solvent having a boiling point 60, it is easy and expedient behind the Reakpunkt than 200 ⁰ C. As To install a dilution or solution gate a distillation plant that uses the medium preferably 2-ethylhexanecarbon products with a low boiling point including 2-ethylhexyl isoate. After separating off butyric acid and removing this Verbinzugten embodiment of the fertilization according to the invention, while the total amount or driving is used as a diluent or 6 ₅ a portion of the compounds with high boiling points in the solvent isobutyric acid, with the Reaction bath are sent back,
setting using a catalyst content If isobutyric acid, which is a proportionate from 10 to 1000 ppm. has a low boiling point, as a diluent or