DE2415700C3 - Process for the production of acetic acid - Google Patents

Description

If the process according to the invention is continuous acetic acid) this can

^ carried out, so * it is often advisable to use the atmospheric ^ * ^! ^^

Turning a number of reaction devices. At higher temperatures, however, the upper pressure must be:

S such arrangement will be the acetic acid which turns the benefit ^ te Ajjffldugvon

Contains catalyst, fed into a first device, 5 overpressure is then to «* ^ * 5«

from which they are divided into a second and a third and antagonism and dissolution of the ^

if necessary, acid is achieved even in a fourth reaction device. Em excessively J ^^

flows. Oxygen-containing gas is not ^ ertaiy ^ - ^ in every single one

Reaction device introduced. The contact between costs - no nighttime fees. The pressure can

See liquid and gas can be obtained by mechanical atmospheric pressure and about 70%

Stirring can be effected, or the gas can be used with, however, a pressure of about ι, * ο

introduce such a speed that a good approx. _ra ",", w "is a catalyst

M see is ensured in this case can the inventively ^v ^ ^ead 5 ^ ^K Ä ^S _e? U _b he

Reaction devices made of long tubes or one in acetic acid ■■ ^^ Jf ^^^ S ^ a

Bundling of pipes with a relatively high ratio of 15 common metal, d. hemes metal m.t different

exist from length to diameter. Suitable values of the groups VB vIB VIIB ™ * ^V11

iäUuiie from length to diameter lie between the periodic system ^^ taking the Ede ^

about 3 1 and about 40: 1. preferably between about metals of group VIII, such as Mbdrom and PIaUn,

5 1 and about 15: 1. The liquid can especially manganese, vanadium, cobalt NgMjMo

and the gas is introduced at the bottom of the reaction tube: lybdenum, iron, tungsten J ^ J ^ SS ₅ a Sak d ^ r

or, if necessary, both will be metallic on the ground. Preferably the metal salt is t. Sa |: aer

Listed, and the acetic acid obtained by this mixing. If necessary, the metal of the bss.g

iSlenz then effects the necessary stirring. acid also ζ B. in the form ^ Ctoäs ^ & A ^

The reaction time depends on the temperature and added, which is in the

the effectiveness of the gas-liquid contact. , 5 converts into the acetate ^ Von

At high temperatures and a very good consistency ^^

between gas and liquid, this can only be about sator

sÄsr SsESSSwa

According to the invention, an inert gas, e.g. B. neitSer tssigsaure unuoducni « _nao -" _nMt ,

Nitrogen diluted air is used. The holdings are not attacked. <Suitable

At the same time, the temperature is the space above which is stainless steel, titanium, glass or the below ^ FlssWkider reaction device with acetic acid- 35 trade names »Hastelloy«, »Inconel« and »Monel«

Saturated steam. At a temperature of e.g. B. 125 ⁰ C ^^ nSSKgSe procedure is expedient-

is a saturated with acetic acid vapor gas, the ^erh The ™ e ^s f * ^m *; ^e · _semi-pure acetic en

Acceptable speed runs The cheapest can be formed a. _considerable

The range for the oxygen concentration of the gas 45 becomes. A Kuctcstana aer co _»e ieentlich

Between about 5 and about 11 percent by volume. As Mengeteteül ^ n ^ ^ f ⁸ ggVJejgentl.ch

Diluent is nitrogen from economic e ne solution of ^ 3J _ine ^B _{r {step Sä} ure-

ltual considerations, although naturally every gJ ^ JSiÄeVwSd «. That way you can

G dt can be ^b f KSk d

ltual considerations, although naturally every gJ ^ JSiÄeVwSd «. That way you can

inert gas can be used. ^b f KSito be continuously returned,

The amount of impurities in the edible acid 50 of the Kata [^ r «ntinmeriw B _tto . _{Loss at}

is low, so the actual amount of oxygen and it only occurs em senr low

containing gas per part by volume of acid up to about 500 vol

by volume of gas or more per volume of acid.

A range of about 5 volume ν is preferred

share up to about 100 parts by volume of gas per part by volume of treatment of common (plant-grade) acid

Acetic acid solution. These values relate to each batch-wise process _{without a catalyst}

5 6

110 ppm methyl isopropenyl ketone, 20 ppm methyl- 423 cc / min for 30 minutes. Air through the solution vinyl ketone and about 0.25% formic acid. The per- were headed. Then the liquid was cooled Manganate time test resulted in this material and distilled according to Example 1. The permanganate-0 Hours. Time test of the main faction lasted only 10 seconds.

A 1-1 Pyrex flask was fitted with a stirrer, 5
Equipped with gas injection device, reflux condenser and thermometer and charged with 400 g of the acid. Example 5
He was heated to 117 ° C and - while with

good speed - with a treatment of common acetic acid in one

Gas mixture from 400 ccm / min. Air and 400 ecm / n> continuously operating device

Min. Nitrogen charged. The loading was

Continued for 90 minutes. Three series-connected reaction upstream

The mixture was then cooled and the acid directions used. These reaction devices at atmospheric pressure through an Oldershaw were pipes about 76 cm in length and one Distilled column with 40 trays. A weight of 20 g and a diameter of about 2.5 cm. A pipe consisted of Pre-fraction was made at a reflux ratio of glass and the other two made of 304 stainless steel. 10: 1 collected. The main fraction weighed 340 g and at the top of the first reaction tube it was half-turned at a reflux ratio of 1: 1 total refined acid of Example 1, the 0.1 wt. The permanganate time test that contained this major fraction percentage of manganese acetate was introduced and on tion resulted in only 15 seconds. 20 bottom pulled off again, to the head of the second Reak

tion tube and passed from its bottom to the head of the third reaction tube and finally drained at the bottom of this third reaction tube.

Example 2 Air and nitrogen were added at one rate

25 of 13.6 ccm / min each. at the bottom of each

Treatment of common acetic acid with catalyst - fed to reaction tubes. The feed rate approach Process speed of the acid was 900 ccm / h, so that the ge

total residence time in the reaction device

The device of Example 1 was placed at 346 g for 60 minutes. Throughout the process of the same semi-refined acetic acid, in 30 a reaction temperature of 118 ° C was maintained 0.34 g of manganese acetate were dissolved. Get the solution.

was heated to 117 ° C and, with vigorous stirring, the product was collected and continuous

were running at 235 cc / min for 60 minutes. Air and through a 55 tray and Oldershaw column 235 cc / miu. Nitrogen passed through the solution. a pasteurization zone, being distilled at the top The acid was then distilled as in Example 1. 35 of the column an upper fraction was removed, the A preliminary fraction of 17 g and a main fraction constituted 6.6 percent by weight of the charge. One of 301 g were collected. The permanganate time main fraction (90% by weight of the feed) The main fraction was tested for 4 hours. was withdrawn on the 45th floor. The permanganate

The time test of this main fraction gave 2.5 hours.
40

Example 3 Examples 6 to 10

Treatment of common acetic acid with catalyst - treatment of common acetic acid in one

Batch Process - Long response time ₄₅ continuous device at elevated pressure

The device of Example 1 was 346 grams The device used in these examples

Semi-refined acid charged containing 0.1 weight per unit of three stainless steel tubes one cent in length of manganese acetate. The solution was of about 76 cm and a diameter of about 117 ⁰ C. and stirred vigorously while 120 micro 50 2.5 cm. They were arranged in a row, and the grooves were 148 cc / min long. Air and 148 ccm / min. semi-refined acetic acid of Example 1 with 0.1 g of nitrogen bubbled through the solution. Then containing percent by weight manganese acetate, was - how the liquid was cooled and described according to Example 1 in Example 5 - distilled in each case at the top of the. The permanganate time test. of the main individual reaction tubes. The gas was released in fraction 7 hours. 55 introduced the bottom of the individual tubes. The liquid

Capacity of the device was a total of 1050 ecm.

The results of five experiments in which tem-

Example 4 temperature, contact time, gas flow and oxygen content

60% of the gas have been varied are summarized in the table on the treatment of common acetic acid. The device was provided with a pressure-batch process - low temperature - _reg ier, and all experiments were carried out at 2.1 atmospheres short reaction time. They were evaluated using a standard method using about 800 grams of the product

The apparatus of Example 1 was charged with 476 g of 65 through an Oldershaw column with 40 plates of distilled hajbra-refined acid, in which 0.1 gels were made. After an approximately 10% upper fraction, percent by weight manganese acetate was dissolved. The solution was a main fraction of approximately 85% gewurde to 117 ⁰ C. and stirred vigorously while collected and tested with the permanganate time test.

Continuous treatment of common acetic acid in stainless steel reaction tubes at 2.1 atm

example temperature
⁰ C Overall Management
time in the system
Minutes O ₂ in the gas
% Ratio of gas /
liquid
Volume in each
Reaction tube Example 13 Permanganate Zcit
Tcst of the distilled
Product
hours 6th 115 60 10 24.6 2 ³ A 7th 125 60 10 25.3 8th 8th 125 40 7th 23 5 9 115 60 10 10 6th 10 120 50 8.5 17th 2 ¹ A Example 11

Treatment of common acetic acid with a

Cobalt Acetate Catalyst - Batch Process The apparatus of Example 1 was charged with 400 g of the semi-refined acetic acid in which 0.40 g of cobalt (II) acetate was dissolved. The solution was ^{heated to 117 °} C. and stirred vigorously for 60 minutes at 250 cc / min. Air and 250 ccm / min. Nitrogen were passed into the solution. The acid was then distilled in the usual manner; after a preliminary fraction of 24 g, a main fraction weighing 321 g was obtained. Your permanganate time test gave 4 ¹ I ₂ hours.

Example 12

Treatment of common acetic acid with a
Iron (III) acetate catalyst

The apparatus of Example 1 was charged with 400 g of the semi-refined acetic acid in which 0.60 g Iron (III) acetate were dissolved. While the liquid was heated to 117 ° C and stirred vigorously, were at 300 cc / min for 60 minutes. Air and '300 cc / min. Nitrogen introduced. The acid was distilled, and a preliminary fraction of 22 g and a main fraction of 305 g were collected. the The permanganate time test of the main fraction gave 3 hours.

Treatment of common acetic acid with a
Nickel acetate catalyst

The apparatus of Example 1 was charged with 400 g of the semi-refined acetic acid in which 0.40 g of nickel (R) acetate was dissolved. While the liquid was ^{heated to 117 °} C. and stirred vigorously,

“5 became 300 cc / min for 60 minutes. Air and 300 ccm / min. Nitrogen passed into the solution. The acid was distilled and a preliminary fraction of 25 g and a main fraction of 308 g were collected. The permanganate time test of the main fraction gave 3 ¹ A hours.

Example 14

Treatment of common acetic acid with a
Vanadium catalyst

The apparatus of Example 1 was charged with 400 g of the semi-refined acetic acid to which 0.60 g of ammonium vanadate had been added. The mixture was heated to 117 ° C and stirred for 60 minutes while 300 ccm / min. Air and 300 ecm / min. Nitrogen were sprayed in. The acid was then distilled, an upper fraction of 25 g and a main fraction of 301 g being collected. The permanganate time test of the main fraction gave 2V ₂ hours.

Claims (2)

Acetic acid contains ζ. B. often about formic acid and claims: traces of acetaldehyde. These two compounds, like other oxidizable compounds, react 1. Process for the production of acetic acid with permanganate The unsaturated ketones are each one Rating at least 2 hours in the 5 but most responsive, and they must be practical Potassium pennanganate time test from a semi-pure can be completely removed before the acidity of beacetic acid, the «, ^ - unsaturated ketones and other conditions of at least 2 hours with permanganate-oxidizable Contains impurities, corresponds to by loading time test. treatment with oxygen in the presence of a catalytic converter.There are already various processes for developing lysators, characterized io removal of the oxidizable impurities known that the semi-pure acetic acid at temperatures by hydrogenation over a noble metal iiatalyst of 75 to 150 ⁰ C and optionally at excess, the unsaturated ketones in non-disturbing, pressure in the presence of about 0.01 to 1 weight of saturated alcohols converted The oxidizable percent, based on the weight of acetic acid, impurities can also be destroyed by reaction with an alkanoic acid salt which is soluble in acetic acid 15 ozone. The reaction with water of a transition metal with a gas such as substance peroxide at elevated temperatures is also 2 to 14 volume percent molecular oxygen relatively effective. But all of these procedures contain about 20 to 90 minutes of treatment and have certain drawbacks. The hydrogenation finally yields distilled. although acetic acid of usable quality, requires 2. The method according to claim 1, characterized in that the oxygen treatment in a treatment device and operates at a very expensive temperature of about 110 to 140 ⁰ C carried out catalysts. A source of hydrogen must be available, and if hydrogen is not available as a by-product, it must be produced separately »Become 5. Ozone generating devices are also expensive, and the handling of ozone at elevated temperatures in organic liquids is associated with The present invention relates to a risk associated with a certain degree. If acetic acid is treated with hydrogen peroxide in order to obtain acetic acid on a large scale, the degree of purity by reducing the content of 3 °, certain dangers also arise here.
oxidizable impurities. The new process for the production of acetic acid Acetic acid is a significant product with many uses with a rating of at least 2 hours. One of the most important ver. Potassium permanganate time test from a semi-pure drive for the production of acetic acid is the liquid acetic acid, which contains «, ^ - unsaturated ketones and other phase oxidation of hydrocarbons with low-oxidizable impurities, by treating molecular weight, such as B. butane. The on lung with oxygen in the presence of a catalyst, such as acetic acid obtained is characterized, albeit of high is characterized in that the semi-pure quality, however, contains trace amounts of impurities, acetic acid at temperatures of 75 to 150 ⁰ C and their applicability for some purposes Restrict if necessary at overpressure in the presence of about ken. Examples of these 40 0.01 to 1 percent by weight, based on the weight of impurities, which are often present in traces, are the ", /" - unsaturated ketones, acetic acid, an alkane soluble in acetic acid such as methyl vinyl ketone and methyl isopropenyl ketone, acid salt of a transition metal with a gas, which cannot simply be removed by conventional cleaning methods, which are about 2 to 14 percent by volume molecular acidic processes, such as distillation 110 to rialien is generally between about 100 Ge 140 ⁰ C are preferred. parts by weight and about 300 parts by weight per million The process of the present invention can be used batchwise Parts by weight of acetic acid ("TPM"). or be carried out continuously. In the case of The Λ, / 3-unsaturated ketones can be vapor-wise carrying out the acid, which is the phase chromatography to be established; mostly contains 50 impurities, with the catalyst in one However, their presence is given with the aid of a reaction device and on the .desired Fahrens determined that heated as potassium permanganate-time elevated temperature. The one containing oxygen Test is known. In this experiment exactly gas is passed through the liquid with stirring, 2 ecm of the acid, the traces of unsaturated ketones, in order to achieve a good mixture. According to the salary, The liquid is cooled with 10 ecm of distilled water and exactly 55 of the desired reaction time 0.1 ecm of aqueous 0.1 N potassium permanganate and drained from the reaction device. at mixes. Then the mixture is left in room-continuous process, the catalyst is in stand temperature and note the time in which the pink of the acetic acid to be treated dissolved. Then the Permanganate staining disappears completely. Acetic acid containing the catalyst with more uniform acid at which this permanganate time test passed at least 60 speeds into a reaction device Takes 2 hours, is generally used for trading and flows out again at the same speed suitable (see: Reagent Chemicals; Am. Chem. Soc. of the device, so that a known Ver-Specifications 1960; Chapter on acetic acid, p. 35; because time is achieved. The oxygen containing gas Publisher: Applied Publications Inc., Washington, is made by the liquid in the reaction device D. C). 65 performed while this liquid is on the desired With the help of the permanganate time test, the reaction temperature can be maintained. The product will not only the unsaturated ketones but all of the oxides which can be accumulated on leaving the reaction device Detect any impurities in the acetic acid. melts.