DE1543058A1 - Process for the preparation of oxygen-containing compounds - Google Patents

Description

'PATFfJTASWXUB DR.-i ^: Jt>: - ^! -PJM
DFPL-I "·: r H3

M 20137-DroK / C

Case H. 17458 _v . f

Description of the patent application

of the company Imperial Chemical Industries Ltd ", London S, ff" 1

concerning:

"Process for the preparation of oxygen-containing compounds"
Priority:. Apr. 10, 1964 - Great Britain

The invention relates to the manufacture of oxygen cells organic compounds, especially propylene oxide «,

In German Patent Specification ... (Auslegeschrift 1,190,926) a process for the production of oxygenated organic compounds, including carboxylic and Olefinoxyde _(acids is described and claimed, which is carried out by reacting a liquid (iemisch of an aldehyde having two or more carbon atoms, and an olefinic compound in which the double bond is in the terminal position and which contains three or more carbon atoms, at a temperature in the range of 40-150 ° C with a molecular oxygen-containing gas, as The most favorable temperatures for this process are given as 60 - 90 ° C

909837/1466 ^BAÖ

In this patent it is also stated that the Gooxy dation preferably using a diluent, such as, _o Bo acetone, methyl acetate, ethyl acetate or acetic acid, is carried out.

It has now been found that under co-oxidation reactions Use of propylene as a starting material very suitable reaction temperatures in the range of 90-130 ° C are »Furthermore it was found that the co-oxidation of olefinic Compounds with a terminal double bond, the three or contain more carbon atoms, and aldehydes that contain two or contain more carbon atoms, in general, and co-oxidation of propylene and acetaldehyde in particular in cheaper Manner is carried out in the presence of a solvent containing methyl acetate and methanol «.

So wire ieiüi.3 of the present invention a process for the production of 7oii propylene oxide and acetic acid proposed, in which propylene with acetaldehyde and a molecular oxygen-containing gas in the liquid phase at a temperature in the range of 40-150 ° C in the presence of a solvent that a mixture of methyl acetate and methanol contains, or a mixture which contains one or more esters of

contains, is brought into contact "

90 9 8 3 7/1466 BAD ORiGiNAL

A particularly suitable methyl acetate / methanol solvent is one that contains these compounds in a weight ratio of 80:20

In the manufacture of propylene oxide and acetic acid by acetaldehyde Cooxydation of propylene and the propylene oxide and acetic acid from the Verfahreneprodukt be removed together with other less than 140 ° G at Atraosphärendruek boiling products "The lingering * Material boiling oberfc-.lb 140 ° G and can vorteilhafterweiee In daa process can be returned, where it serves as a solution. This material comprises u "a _e a high boiling Semisch of esters of propylene glycol including dee Biacetats of -fropylen glycol" · Since this material is continuously formed, it may also partially removed and optionally have been hydrolyzed, wherein said products free propylene glycol and acetic acid.

The co-oxidation of propylene and acetaldehyde is preferred carried out at a pressure of at least 40 at and especially JB at a pressure in the range of 80-100 at.

The propylene oxide obtained by the process of the invention came "used in the manufacture of polymers, ·, or it can be hydrolyzed to propylene glycol,

909837/1466 _B AD ORIGINAL *

The invention is illustrated in more detail by the following examples. purged

example 1

An autoclave was charged with 1060 g of ethyl acetate and 1260 g of propylene. This charge contained. So much cobalt naphthanate that a cobalt concentration of 50 ppm by weight was obtained. This liquid was brought to the desired reaction temperature and kept at a pressure of 80 atm. 176 g of acetaldehyde were added continuously over a period of 2 hours. Through the reaction mixture 'was at a rate of 2.85 nr / et a _mixture: 4 ^ VoIk- oxygen and nitrogen 96 V0I0-7 & directed "

The reaction products were found by analysis to have compositions corresponding to the conversions and yields shown in Table 1. The propylene glycol was mainly in the form of JSstern, especially form distillates and acetates, in front _o include the amounts stated below and levels of Propylene: Iycol obtained as esters. .

BATH ORIGINAL

909837 / U66

154305B

Table 1

conversion Sl- P. »- ---- - ·»
x ^ -JO py · = '■ 's yield 57 in. VLi , based > ■ - Acetic acid Tempe "£ ro- de- lenoxyd Propylene = 67 consumption- - .-. ■ - '* ■' ^: - ϊ / - '
* r "" ir * '" related to mil rature py- based oxide, be 77 Propylene glycol aldehyde 9 consumption- hyd on off Pro pulled up col, 10 tien aldehyde ^r d len get pylen consumption on 9 "subsided" ne products
* - ψ ten aide th l3.ch.der, al 82 58 hyd 90 24 / 88 57 70 LOO ^; 43 85 62 84 LlO 46 ¹

Example .2

In dienjir. For example, the procedure of Example 1 was repeated ₉ v / ofcei the same reaction substances and the same conditions but different Löaurigi agents were used o In experiments 1 and 2 the solvent was methyl acetate / methanol, the weight ratio of the two compounds being 80:20 In in experiments 3 and 4 the solvent was ethyl acetate / methanol, the weight ratio of the two compounds being 85 J Ib »In experiment 5 the solvent was ethyl acetate / ethanol, the weight ratio of the two compounds being 80:20. In experiments 6 and 7 the solvent was methanol itself

909837 / U 6 6

BATH ORIGINAL

_{Propylene glycol diacetate o} Table 2 summarizes the results obtained, whereby the remarks made to Table 1 apply again o

Tem
pera
door
⁰ G conversion
in fo Alde
hyd Table 2 yield in mol .- ^ .: Ver
search
2Jr, 80 Propy
len 68 propylene
oxide, be
pulled up
consumption
ten aldehyde Propylene
glycol,
based
on ver
needed
aldehyde acetic acid
based
on ver-i *
needed
Aldehyde,
including
lent the
as Ao et air
are present
the ■ 1 ' ίου 20th 75 Propylene
oxide, related
gen on ver
need it
Propylene 71 9 57 _ 2 80 3Ö 68 60 65 _— 75 3 90 25 - ■ 70 63 53 => ei: -, 4th 100 5.0 80 ■ 35 64 6th 67 5 80 21.; 25th 43 55 6th 92 6th 80 12th 80 83 . 15th 90 7th 32 - 57 - 70 55

From this table, it is seen that methanol as sole solvent is very unsatisfactory "On the other hand, a Methylace ^ at / methanol solvent at 80 ⁰ C ^to-very-: satisfactorily, but it seems that there is less satisfactory

—7—

COPY

909837 / U66

It is important if the working temperature is 100 ° C _o Example 3

Di @ aes example illustrates the benefits of using a temperature of 115 ° C for the deoxidation of acetaldehyde and propylene using ethyl acetate can be obtained as a solvent. A reactor was charged with ethyl acetate as a solvent. So much became Cobalt naphthenate added; that a cobalt concentration of 10 ppm, based on the sum of the solvent, propylene and aldehyde, which were used, was present "This ·

The liquid was then brought to the desired reaction temperature

brought. Acetaldehyde and propylene were in the reactor introduced so that a propylene: aldehyde ratio of 8.0: 1 was obtained with the feed rate

of acetaldehyde of 4.0 mol / st was «- The pressure was < on

de / lOO at held. Through the reaction mixture and afterwards on it through a condenser kept at minus 40 ° C, to remove unreacted reactants, an oxygen / nitrogen mixture was passed. The conditions were set so that the oxygen content in the escaping gas would never exceed 3.0 vol «.- # the The results obtained are given in Table 3 »

-8th-

909837 / U66

"8th-

Table 3

Temperature ⁰ C Yield in mol- #
(Propylene oxide, be
attracted consumption.
ten acetaldehyde) 95
115
125
150 53
82
53
35

Zusainmengenommen with the results in Table 1 show this Zah ~! _R s that the yield of propylene oxide, based on Acetaldehydj, the more expensive reactant, at approximately 115 ° ^C rising to a maximum when Äthylacetatals Lösungamittel used wirdo

Example 4

The procedure of Example 3 was repeated, wherein a previously formed in the product of the process was used as solvent, of the propylene oxide, acetic acid and other boiling at temperatures below 140 ° C products were removed _o This material is with the Ausdruk "heavy residues ".designated"

-9-

909837/14 6

Table 4

solvent

temperature

Propylene / aldehyde molar ratio

Aldehyde feed rate Jftol speed in mol / at

Yield in

py

oxide, based on aldehyde consumed)

(1) heavy
Residues

(2) heavy
Residues

115 ° C

140 ° C

8.0

20.0

1.5

80

230

These figures explain the favorable yields of propylene

based

oxide / on used aldehyde, if "heavy residues" are used as a solvent "In addition, it must be noted that when using" heavy residues " as a solvent, the yield of propylene oxide, based on aldehyde consumed, tends to increase as it increases the TeDiperatur to become larger towards 150 ° G.

Claims;

-10 =

9098 37 / U66

Claims (1)

Patent claims: Process for the production of propylene oxide and acetic acid, in which propylene is brought into contact with acetaldehyde and a gas containing molecular oxygen in the liquid phase at a temperature in the range of 40 - 150 ° C, according to patent » _oo (BAS 1 190 926) , characterized in that a mixture of methyl acetate and methanol or a mixture containing one or more esters of propylene glycol is used as the solvent. 2ο The method according to claim 1, characterized in that the mixture, which contains one or more esters of propylene glycol and is formed in the process, is returned to the process as a solvent. 3ο Verfahr η according to claim 2, characterized in that a part of the mixture, which contains one or more esters of • ^ ropylenglyool and is formed in the process, separated from which and hydrolyzed , so that products containing propylene glycol and acetic acid are obtained will" 909837 / -U 6 6 8AD ORH 4 ·· procedure according to. Claim 2 or 3 »characterized in that the mixture, which contains one or more esters of propylene glycol, is produced in the process by removing essentially all of the propylene oxide, all of the acetic acid and all other products from the product of the process Boiling atmospheric pressure at temperatures below 14O ⁰ C, are removed, 5 × The method according to one of the preceding claims, characterized in that the temperature at which the propylene with the acetaldehyde and a molecular oxygen-containing gas is brought into contact, is in the range of 90 to 13O ⁰ C. 6. A process for the production of propylene oxide and acetic acid, in which propylene with acetaldehyde and a gas containing molecular oxygen in the liquid phase in the presence of a solvent, which contains one or more compounds from the group consisting of acetone, methyl acetate, ethyl acetate and acetic acid are selected, is brought into contact, according to patent ... (DAS 1 190 926), characterized in that the temperature at which the propylene is brought into contact with the acetaldehyde and a gas containing molecular oxygen is in the range from 50 to 13O ⁰ C is. PAtEN ^ ANWXlTE ML-INS K nixr.t OIPL-INö.aiOH * 909837 / U66 _Λ1ΜΑΙ BATH ORIGINAL