DE2061522B2 - Process for the production of olefin oxides and carboxylic acids - Google Patents

Description

2061

522

a mechanically stirred autoclave, a multi-point introduction system or use a vein reactor in which the reactants are pressurized through the system. Man can also use a spray system. In the method according to the invention it was found that increased Reaction speeds through constant good contact between gas and liquid can be achieved and that this contact is given by stirring. The homogeneity of the liquid reactants, which is rubbed off by stirring. is also beneficial. With the continuous Carrying out the process according to the invention achieves these results since stirring is continuous Procedure is inherent. However, the measures described for stirring serve to improve of continuous work.

As olefins, terminal olefins from the Group of monofunctional and difunctional olefins of the following formulas

R ₂ -C = CH ₁

in which R _{1 represents} hydrogen or a straight or branched alkyl chain with 1 to 20 carbon atoms and R _{2 represents} a straight or branched alkyl chain with 1 to 20 carbon atoms; and

Such olefins are preferably propylene, butene-1, butene-2, isobutylene, pentene-1, hexene-1, pentene-2. Cyclopentene, cyclohexene and cyclooctene. Other olefins are 2-methylbutene-l, 3-methylbutene-l, heptene-1, Octene-1, hexene-2, hexene-3, octene-2, heptene-3, Pentadecene-1. Octadecene-1, dodecene-2, 2-methylpentene-2, Tetramethylethylene, methylethylethylene. Cyclobutene, cycloheptene, 2-methylheptene-1,2,4,4-trimethylpentene-1, 2-methylbutene-2, 4-methylpentene-2

ίο and 2-ethyl-3-methylbutene-1.

The aldehydes used are those which only contain carbon, hydrogen and oxygen as well as 2 to Contain 7 carbon atoms, e.g. B. acetaldehyde. Propionaldehyde. n-butyraldehyde. Isobutyraldehyde.

n-valeraldehyde. Isovaleraldehyde. n-caproic aldshyd. n-heptanoic aldehyde and trimethylacetaldehyde. as well as benzaldehyde. Acetaldehyde is preferred.

The use of the nitrile is essential to the invention, as the use of other solvents will reduce the effectiveness. Suitable nitrides are primary, secondary and tertiary nitriles, with the primary and tertiary being preferred. The appropriate ones Nitriles can be represented by the following formulas:

R ₁ -C- CN

R ₁ R ₂

CH ₂ = CR '- C = CH ₂

in which R ₁ and R ₂ stand for Wr.ssersloffatome or alkyl chains with 1 to 10 carbon atoms and R stands for 2 to 10 methylene groups, can be used. The definition also includes cyclic olefins and internal olefins. The ring portion of the cyclic olefin can contain up to 10 carbon atoms and one unsaturated bond and can be substituted with 1 or 2 alkyl radicals having 1 to 10 carbon atoms. The cyclic olefins can be represented by the following formula:

R ₃ -R ₁ - CH

I I!

Rt R ₂ CH

in which R ₁ and R _{2 represent} alkylene radicals with 1 to 4 carbon atoms and R _{1 and R 4 represent} hydrogen atoms or 1 or 2 straight or branched chain alkyl groups with 1 to 10 carbon atoms. The internal olefins can be represented by the following formula:

R ₁ - CH = CH - R,

in which R, and R ₂ stand for straight or branched chain alkyl chains with 1 to 10 carbon atoms. In the given definitions of the radicals R ₁ to Rj, the condition given above that the olefin should contain 3 to 22 carbon atoms must be adhered to.

and

R ₁

40 NC —C —R '—C —CN
I ι

R ₂ R ₄

in which R ₁ . R ₂ . R ₃ and R _{4 represent} hydrogen atoms. Are alkyl groups or alkylene parts of an acyclic ring and R 'denotes a covalent bond or an alkylene group and are selected so that they correspond to the above definition. The following are suitable, for example: acetonitrile. Propionitrile. Butyronitrile. Isobutyronitrile, valeronitrile. Isovaleronitrile. Capronitrile. Isocapronitrile. Heptanonitrile. Isoheptanonitrile.

Caprylonitrile. 3-methylheptanonitrile. Pivalonitrile. Dimethylacetonitrile. Succinonitrile. Adiponitrile. Giutaronitrile. 2.5 - dimethyladiponitrile). 4 - methyl 1.7 - heptanodinitrile. Cyclopentanecarbonitrile. Cyclohexane carbonitrile. 1.2 - Cyclopentanedicarbonitrile.

U-cyclohexanedicarbonitrile. The preferred nitriles are acetonitrile. Propionitrile. Butyronitrile and methylcyclohexyl nitrile.

The amount of nitrile present can be between about 0.05 and 5 parts by weight of nitrile per part by weight Olefin and aldehyde (taken together) lie. About 1.5 to 2.5 parts by weight are preferred Nitrile per part by weight of combined olefin and aldehyde. Other amounts of nitrile can also be used as long as the amount is sufficient to reverberate the reaction in the liquid phase.

It has been found that the advantages resulting from the use of a Nilril can be achieved. even if up to 80 percent by weight (based on the

ranges given above) of the same and by inert hydrocarbon solvents, such as saturated aliphatic, saturated cycloaliphatic and aromatic solvents that are unsubstituted or substituted can be replaced; such solvents are e.g. B. hexane, cyclohexane and benzene. It is desirable that the solvent increase the solubility of the gaseous reactants. In order to take advantage of such a solvent substitute, however, a minimum amount should be added Nitrile, i.e. at least one cyano group (C = N) for each aldehyde group present in the reaction mixture (CHO), be present. If a mononitrile is present, the molar ratio is therefore Nitrile to aldehyde at least 1: 1, while in the case of a dinitrile it is at least 1: 2.

It has also been found that the use of a nitrile medium or solvent as described above improves the effectiveness of the new process regardless of the olefin to aldehyde ratio, so long as the olefin to aldehyde molar ratio is no greater than 15 mol of olefin per mole of aldehyde. However, in order to achieve the highest possible efficiencies of olefin oxide and acid, based on the aldehyde, the use of special molar ratios of olefin to aldehyde is preferred. These molar ratios result from the following two findings: The molar ratio necessary for terminal olefins is between 1.5 and 10 mol, preferably about 2 to 5 mol of olefin per mol of aldehyde; for cycloolefins and internal olefins it is from 5 to 5 moles, preferably about 0.8 to 2 moles of olefin per mole of aldehyde. Furthermore, the stated ratios should occur during the reaction in the reaction phase, ie in the liquid phase. be maintained. By using a continuous process and by analyzing the discharge ratio and adjusting the feed ratio, the ratios can be kept constant. In a "backmixing" reactor, the feed is adjusted until the exit ratio is in the specified range. When using two or more reactors in series or a tubular reactor with multipoint introduction, the _4S reactions occurring are considered to be a series of batch reactions and are carefully monitored so that the molar ratio in any of the reactions does not deviate above or below the prescribed range. In practice this usually _means stopping the aldehyde feed.

The mixture is brought to a temperature of up to about 140 ° C., preferably with stirring. The preferred temperature range for terminal olefins is between about 80 and 120.degree. C., with the optimal temperature being considered to be about 90 to 120.degree. At temperatures above 120 C the efficacies gradually decrease and fall rapidly above 140 C. For cycloolefins and internal olefins, the preferred range is somewhat lower, that is, _{f, 0} to about 50 C. IOD the optimum temperature is about 60 to 90 C. Here, too, the effectiveness drops at higher temperatures. The method may also at lower temperatures such as 20 ° C are carried out, but with _{(, ς} long reaction times result.

The pressure under which the reaction vessel is held is not critical and there is no upper pressure Limit other than practical considerations related to the cost and size of the reactor. Are suitable Pressures between atmospheric and about 70 ata to bring a substantial portion of the olefin in to keep the liquid phase. However, pressures between about 1 and 42 atmospheres are commonly used.

The pressure and charge determine how much olefin is in the liquid phase; this is just important im In view of the fact that the excess olefin can be easily recycled. The presence of a Vapor phase is not harmful; but since the reaction takes place in the liquid phase, must be achieved in order to achieve this the prescribed ratios correspond to the specified values for the best results. Therefore, maintaining a particular ratio during the reaction means maintaining it this ratio in the liquid phase.

The atmosphere in the reaction vessel before the introduction of oxygen can be made from nitrogen or optionally from another inert gas.

An oxygen-containing gas in which the other components are inert to the reaction, e.g. B. a mixture of nitrogen and oxygen. Air, or oxygen itself, is then introduced into the reaction vessel. Usually the oxygen is introduced at partial pressures of about 3.5 to 7 kg cm ² , the pressure not being critical. Pressure losses due to the consumption of oxygen are adjusted to a constant pressure by adding more oxygen. The amount of oxygen used can be based on the aldehyde with which it immediately reacts. Suitable molar ratios of O ₂ to aldehyde are about 1: 1 or less, and preferably about 1: 2 or less with an optimum of about 1: 4. However, a molar ratio of 1:20 or less is not productive and, while a molar excess of O _{2 is} applicable, it is a waste of oxygen, reduces efficiency and can be dangerous. With regard to the oxygen partial pressures, very low pressures can be used, and the better the oxygen transfer, the lower the partial pressures. For good oxygen transfer, stirring is the decisive measure, which can be carried out as described above, but high partial pressures can also be used if necessary.

The inventive method can be carried out batchwise or continuously, wöbe the latter is preferred. The order in which the reaction participants are introduced is determined by the specialist determined on the basis of the most practical points of view under prevailing conditions and is not decisive.

Catalysts and initiators are not necessary for the reaction, but they can be present It is pointed out, however, that some metal catalysts, such as coballnaphlhenate, of the reaction are harmful.

The extraction. Separation and analysis of the pro dukle and unreacted materials takes place i usual way.

The reaction described here has the Voitei compared to the reaction initiated by aldehyde functions to be easier to control; and weilerhi will only have a minimum amount of carbon dioxide un Methanol »ebildct. The nitrile and part of the a

By-product carboxylic acids are preferred to reduce the amount of distillation returned.

The following is also stated on the technical progress of the new process. The known procedures were, as far as the formation of olefin oxides from the olefins was concerned, partly not unsatisfactory. One disadvantage, however, is that, based on the aldehyde used, only a little carboxylic acid was obtained. So there was a not inconsiderable one Loss of aldehyde, which made the process uneconomical. According to the invention against it Aldehyde and carboxylic acid in ratios up to 1: 1 are obtained and the overall process is therefore economical. It must be pointed out that the formation of a larger amount of Carboxylic acid as received in the new process

if not desired. There are procedures for technical usability and economic viability desirable, in which the ratio of olefin oxide and carboxylic acid is about 1: 1 and the efficiencies. B. based on the propylene oxide and acetaldehyde used, are at about 100%. According to the invention, these values can, as can be seen from the following examples (in particular: Table I) be achieved. When using other solvents (see Table V. in Examples 55 and 58 as well as the Selectivity numbers in example 26) do not achieve these results. This special effect of the The solvent used according to the invention was not to be expected.

The percentage effectiveness of olefin oxide. based on the aldehyde consumption, is calculated as follows:

Number of moles of olefin oxide

-, .. - .- 100.

Number of moles of aldehyde feed minus number of moles of aldehyde recovered

Other potencies are calculated in a similar manner.

The following examples illustrate the present invention without restricting it. All Parts are parts by weight.

Examples 1 to 14

The process was carried out continuously in a 316 stainless steel circulation reactor which was provided with a circulation loop and pump for circulating the reactants, an inlet tube for introducing the liquid reactants and solvent, and another inlet tube for charging the gaseous material. The circulation system gave sufficient agitation. Means were provided for collecting the reaction product from an exit tube by cooling the effluent in a series of traps. The non-condensable gases were vented. The system was provided with instruments for controlling and recording the charging rate of the liquids and gases and for measuring the rate of evolution of gases such as CO ₂ . Mistake. The liquid feed stream contained acetonitrile. Acetaldehyde and propylene and the gaseous feed stream oxygen and nitrogen. The effluent contained acetonitrile. unreacted propylene and acetaldehyde. Propylene oxide. Acetic acid and smaller amounts of methanol. Carbon dioxide and water.

Table I shows the conditions and results of each example:

oxygen Table I. "' nitrogen Propylene acetaldehyde SId. -_ -. -
Propylene acet Temp. Original load lbs, aldehyde
molar 0.997 3.36 7,765 2,898 Acetonitrile relationship 100 Example no. 0.804 2.85 7,786 2,643 2.68 100 0.648 0.743 7,359 2,702 19,437 2.94 100 I. 0.648 0.749 9,703 1603 19,286 2.72 110 2 0.852 3,146 4,890 2,708 20,250 3.73 90 3 0.886 2,987 7,085 2,686 24,562 1.81 100 4th 1,350 4,814 5,062 2. S58 13,586 2.64 110 5 0.351 1.27 9,625 2,601 20,437 1.77 105 6th 0.879 3.00 7,063 2,729 13,562 3.70 110 7th 0.139 0.471 5,265 1,419 26.56 2.59 90 8th 0.436 1,505 5.57 1.35 20.23 3.71 110 9 0.845 3,027 5.64 1.376 14.06 4.11 120 10 0.509 1,778 7.21 2,773 14.03 4.10 100 11 1,195 4,245 8,698 2,751 14.21 2.60 110 12th 20.23 3.16 409 526/450 13th 13.12 14th

10

Drue! .. R.iunv / ei: - Xusheule
a'u rn'i ^ ki! ^ Table I. Effective! ope. 'ί : 28 4,268 (Continued ι Prop \ kno \\ d
Effectiveness, j
Κνομοη .ml "Pri> p_ \ lcn! Piojnler.ov.u
Wnk-amkei '.
hc / v> i! cn on
Λ eel aide InJ j 28 3,469 ^; 92.1 j 79th? Example no : -s 2,776 in lb>. ^S ; Y a; i;
\> u E ^ igsauri I 94.5 j 86.7 1 : 28 3,096 5.S62 ■ 95.4 j 106.0 ^; 28 3,166 4,369 93.6! 124.9 -, 18th 3.62 2,528 97.5 j 57.5 4th : s 5.69 2,218 99.1 j 80.7 5 : s 1.40 ^; 6,715 96.8 62.2 6th '.8th ; 4.10 4.95 94.3: 105.4 7th :.8th ; 0.40 Π.04 99.3 j 85.0 8th :: s 1,887 1.31 97.4: 107 /, 9 : s 3.90 5.42 9p.4 105.1 10 28 ; 1.94 0.39 99.C. 92.0 Π 28 '■■ 4.7? l. "90 98.0; S p. 5 12th 4.16 99.0 i "" .4 13th 2.42 14th 6.99

B e i s pi e 1 i; 15 to 28

These examples were done in the same way as described above Examples 1 to 14. except that no acetaldehyde was introduced into the reactor. This took place no noticeable reaction. Therefore it was concluded that there was a practically direct oxidation of propylene does not occur in the method according to the invention.

Examples 29 to 31

The process was carried out in a glass-lined stainless steel autoclave coated with olefin tetrafluoroethylene. A mixture of 33 parts (0.75 mol) of acetaldehyde and 352 parts of acetonitrile was introduced into the autoclave. Then 105 parts (2.5 Moll propylene were added and the mixture was heated to 100 ° C. with stirring. The autogenous pressure of the system was 20 kg cirr. At this pressure, 3.8 kg cm ^: nitrogen and then 4.2 kg cm ² oxygen were introduced to bring the total pressure in The oxygen consumption was compensated for by the addition of more oxygen at the rate of its consumption, the reaction time in each example was varied and the final olefin to aldehyde ratios and the oxygen efficiency were determined on the basis of aldehyde These examples show the advantage of keeping a relationship within a specific range during response.

The conditions and listening results were like focus

example

Original molar ratio before. Olefin

to Aldehvd

Final molar ratio of olefin to aldehyde

Response time: min.

Oxide effectiveness based on aldehyde:%

10

84.5

-.0

HU «SS

"0.0

Examples 32 bi>

These examples were made like examples 2 ^> until where, however, use air as s.uieistofllialtigcs G.is! became

Conditions and results are shown in Table 11 below:

Table U

Example

temperature

Pressure (atü)

Ratio of acetonitrile to propylene in the

Loading (based on weight)

Ratio of propylene to acetaldehyde in the

Loading (based on weight)

Surface contact riding, min

110
28

2.2

3.9 4 «

110 HO -S : s 1.7 5.0 4.0 33 16

110 2S

10

Continuation line

Results:

Propylene conversion,%

Acetaldehyde conversion. % j

Propiliability to propylene oxide, "· < > I.

Productivity (propylene oxide + acetic acid) j

lbs / hr / cu.ft!

Ratio of acetic acid to propylene oxide in the product based on weight

Example 36

This example was carried out in the same manner as Examples 1 through 14. The reactor was a complete one fragmentary, single-stage reactor similar to the one described.

The conditions and results were as follows:

Pressure; atü 28

Temperature; C 110 ² - ^s

Parts acetonitrile per part in the

Propylene introduced into the reactor 2

Parts propylene per part in the

Reactor imported acetaldehyde. . 5 ·>, ο

Propylene conversion; % 12

Acetaldehyde Conversion:% 80

Propylene oxide effectiveness on that

Propylene base:% 95

example

10.5
79.9
97.6

4.5
1.3

7.0
61.0
99.8

4.8

4.0 23.0 99.6

4.6 1.0

.15

5.9

27.7 98.9

8.9 1.3

Reactor productivity (propylene oxide plus acetic acid: lbs./hour./cuft.). . .

Parts of acetic acid per part of propylene oxide formed

Examples 37 to 44

The procedure was carried out in batches in a glass-lined, polytetrafluoroethylene-covered one Stainless steel autoclave. In this a mixture of acetaldehyde and hexene-1 introduced together with acetonitrile. The mixture was released under a nitrogen pressure of 21 atm 100 C heated. Then 4.2 atü Ch were in the reactor introduced. A drop in pressure in the system indicated oxygen consumption. The pressure drop was through intermittent addition of acid off at a rate which was equal to that of consumption. balanced. After the reaction was over, the autoclave became cooled down. Conditions and results are shown in Table III.

Tabel Example ]

37
3 pp
39
40
41
42
43
44

Original delivery to us:

Ί empe-

Π1ΗΙΙ

ι Cl

100 100 100 100 100 100 IfX) 100

Accl- Aceto Witches-1 uldch> ii nitrile (Minor ι MnI) (Parts) 1.0 0.25 234 1.0 0.38 351 1.0 0.38 351 1.0 0.50 351 1.0 0.50 351 1.5 0.75 351 1.0 0.75 ■ • 34 1.0 1.0 234

Olein

Reaction uivmand / eii j Uni:

(Min.I! ΓΊ.)

250

130 44 80

124 48 85 50 2 LO
19.4
22.3
24.5
21.8
17.0
23.9
25.4

AUlellinglnni;

l "cil

71.8
64.0
55.4
67.4
54.1
54.5
50.8
38.9

l'rodiikie

O \> d
(Minor

0.14
0.16
0.14
0.20
0.15
0.23
0.16
0.12

1 minor

0.10
0.13
0.12
0.19
0.16
0.27
0.23
0.23

Meihano '(minor

0.07 0.05 0.04 0.05 0.05 0.05 0.03 0.02

speed.

hc / ogen to Acctaldeh \ d

88.3 72.6 87.1 63.8 65.4 64.4 47.8 35.9

Examples 45 and 46

The procedure of Examples 29-31 was followed by the repeats the following changes:

Propylene ...
acetaldehyde
Propionitrile

45

110 33

352

example

Parts

46 110

33 352

6o

Reaction time; Min

Results

Propylene oxide

acetic acid

Propylene oxide effectiveness
based on the
Acctaldehyde Consumptioncs;

example

45 I 46

Parts

28

9.3 9.0

93.5

19.3 16.9

89

Examples 47 to 50

These examples were done in a glass-lined, poly-tetrafluoroethylene-coated one Autoclave batchwise. A cold (about 0 C) solution of acetaldehyde in 234 parts of acetonitrile was added to the Autoclave introduced, which was then closed. 100 parts of propylene were then added to the system and the mixture is heated to 100 ° C. while stirring. At this point the autoclave was through Adding nitrogen to a pressure of 3.5 to 6.3 atmospheres and then brought to 7 to 11.9 atmospheres by adding oxygen. One through oxygen consumption Caused drop in the reaction pressure was due to the continuous addition of oxygen with consumption balanced at the same speed. The initial reaction was very quick in the course however, the rate of the reaction decreased. After the completion of the reaction, the entire autoclave became cooled to OC.

Conditions and results are listed in Table IV.

Table IV

Original loading:

Propylene parts

Mo!

Acetaldehyde parts

Mole

Acetonitrile parts

Temperature, ° C

Propylene, atm

Nitrogen, atm

Oxygen, atm

Response time, min

Reacted acetaldehyde. Mole

Propylene oxide. Mole

Acetic acid, mole

Methanol, mole

Propylene oxide effectiveness based on acetaldehyde.

B e i s ρ i e 1 e 51 to 63

The cooxydalion of cyclohexene with butyraldehyde took place in an entirely made of glass Oxidation device from a reaction vessel which was given away with an inlet tube. The outlet pipe was in series with a dry ice cooler, a dry ice trap. Drying tube ("drierite tube"). Ascarite pipe and a double bellows pump for the circulation of gaseous oxygen. That The reaction vessel was kept in a constant temperature bath, and the oxidation system was connected to a vacuum system.

example

47

84.0
2.0

11.0
0.25
234
100

18.9
3.5
5.6

95

0.134
0.123
0.088
0.046

92

84.6
2.0
22.0
0.50
234
100
17.9
4.2
4.2
180
0.307
0.314
0.228
0.079

102

84.1 84.3 2.0 2.0 33.0 44.0 0.75 1.0 234 234 100 100 18.2 18.2 4.2 6.3 4.2 4.2 126 120 0.567 0.548 0.426 0.404 0.382 0.445 0.185 0.103

50

68.4

In order to show the effect of different solvents on the co-oxidation, a mixture from 10 parts (119 millimoles) of cyclohexene and 10 parts Butyraldehyde (139 millimoles) was introduced into the reaction vessel: then 100 parts by volume of solvent were added and 1 part of benzoyl peroxide introduced. The mixture was stirred and under vacuum kept at a temperature of 70'C, then gaseous oxygen at 760 mm pressure for the specified Time circulated through the reaction mixture. For each example, solvents are time. Oxide- and acid yield and oxide efficiency based on aldehyde are listed in Table V below.

solvent Table V {Min. 1 CvclohcNcn AMcli \ d Cvclohcxen- Butyric acid 361 consumed consumed oxide (Millimoles) example Nitrobenzene 187 (Milhmol) (Millin.nl) (Millimoles) 10.4 Anisole 377 12.7 15.8 11.2 36.3 51 Bcnzonilril 370 39.6 46.0 29.4 47.7 52 Acetophenone 255 70.9 75.6 54.5 43.1 53 Benzo ¹ 215 57.7 72.7 44.6 61.0 54 Chlorobenzene 70.0 80.0 51.6 61.4 55 72.1 79.0 53.6 56

Ox> d effectiveness kit.

based
on aldehyde

("oil

70.9
63.7
72.1
61.3
64.5
67.8

Continued 16

solvent (Min.) Cyclohexene Alekhyd Cyclohtxene li * all IfhrT '] ι · γλ Oxide- 350 consumed consumed oxide JDUllCrSdUIC Effectiveness, example Iodine benzene 180 (MiSlimol) (Miilimol) (Mülimol) (Miilimol) based
on aldehyde Ethyl acetate 255 46.0 85.2 27.9 60.0 <% l 57 Cyclooctane 231 46.4 70.6 38.5 54.0 32.7 58 Acetonitrile 340 47.4 80.9 40.5 65.4 54.5 59 N, N-dimethylformamide 192 47.6 42.5 37.4 32.0 50.5 60 Dimethyl sulfoxide 88 45.2 70.0 24.5 53.2 88.0 61 no solvent 11.8 36.5 2.6 Π.4 35.0 62 77.3 80.9 37.4 55.0 7.1 63 46.3

Examples 64 to

The procedure of Examples 51 to 63 was repeated. The conditions and results varied are listed in Table VI below.

solvent Solution
middle Table VI Acet
aldehyde Tempe
rature Line Acet
aldehyde
implemented Propylene
oxide Ox \ d- effective- (Parts) (Parts) CC) (Min.) (Mole) (Mole) speed.
based
on Example] Ethyl acetate 352 Propylene 33 100 106 0.257 0.166 aldehyde Propionitrile 352 33 100 60 0.427 0.339 (%) Acetonitrile 352 (Parts) 33 100 120 0.307 0.314 64.6 64 115 79.5 65 113 102.0 66 105

Example 67

Although the high olefin oxide effectiveness on the Aldehyde base is viewed as the best feature of an industrially suitable co-oxidation process in which the reactants are olefin, aldehyde and oxygen, is removed, that this high effectiveness is the result of a strong selective power of co-oxidation, which by the Nitrile medium is applied to the reaction. The selectivity number can be used to represent this selective force the relative selective forces exerted by the various solvents can be calculated shows. The calculation is based on the following equation:

Selectivity number = rate of olefin epoxidation rate of aldehyde oxidation

24.1.

24.1 was selected as the normalization number!

The method used to achieve the above speeds is a competitive method known. It is as follows: 10 moles of cyclohexene, 10 moles of butyraldehyde and a large excess of solvent were placed in a glass reaction vessel, then 1 mole of peracetic acid was added. The mixture was heated to 70C and the reaction continued until the peracetic acid had completely reacted is. The mixture was then used to determine the number of moles of olefin that was epoxidized per cell unit and the number of moles of aldehyde oxidized per unit time analyzed. This competitive process was performed for the following solvents, followed using the above equation the following selectivity numbers were calculated in each case:

solvent

solvent

Acetonitrile
Benzene ....

ClektiviUils / ahl
100.0

64.5

Bromobenzene

Nitrobenzene

Nitromethane

Anisole

p-xylene

Benzonitrile

Carbon tetrachloride ..

Chlorobenzene

toluene

Acetophenone

Cyclohexane

Ethyl acetate

Cyclooctane

N.N-dimethylformamide tetrahydrofuran

Selectivity number

64.5 59.9 59.2 57.0 46.4 43.5 42.8 42.3 37.4 36.2 29.5 24.9 20.5 3.6 2.7

Claims (1)

Claim: Process for the production of olefin oxides and carboxylic acids in the sweet phase by mixing of an epoxidizable olefinically unsaturated hydrocarbon compound with 3 to 22 carbon atoms with an aldehyde from the group of the unsubstituted straight or branched chain Aldehydes with 2 to. 7 carbon atoms and benzaldehyde and one containing oxygen Gas in an organic liquid medium, the molar ratio of olefin to aldehyde is not more than 15: 1, characterized in that mm is an organic liquid Medium used because: s contains mono- or dinitriles belonging to the group of saturated aliphatic Nitriles with up to 10 carbon atoms in the non-nitrile part and the saturated cycloaliphatic part Nitriles with up to 15 carbon atoms in the non-nitrile part and with up to 6 carbon atoms in each ring belong, and mixtures thereof, the non-nitrilic Groups made up of carbon and hydrogen atoms. The present invention relates to a process for the preparation of olefin oxides and Carboxylic acids in the liquid phase by a non-catalytic process. Olefin oxides are used in the chemical industry as intermediates in the manufacture of urethanes. Glycol solvents. Coating preparations. molded articles, surfactants, plasticizers and many other products of great importance. Hence the manufacturers of olefin oxides for many years after more efficient processes with higher yields, cheaper reaction participants and cheaper secondary end products are sought. Unfortunately, the cost of the initial one varies Respondents and the achievable prices of the end products from manufacturer to manufacturer, what exemplified by the well-known "chlorohydrin process" for making propylene oxide; in this case, a manufacturer to whom ke.nc has access to a cheap source of chlorine becomes the competition disadvantaged compared to. Another example is an organic hydroperoxide process also for the production of propylene oxide, in which an end product is tertiary butanol, which is of even greater value to a propylene oxide manufacturer also operating in the motor fuel field. It therefore recognizes the need for a more universal method to offset these competitive disadvantages. Furthermore, such a method should not require any special Atilage, as z. B. is needed for handling the corrosive chlorine: it should not be dangerous, like / .. B. when using peracids; and it should have a minimum of end products' line economic because, such as B. the carbon oxides formed by direct oxidation of propane. Many methods have been proposed. to meet the demands of the industry. and many of the problems have been overcome: a higher efficiency with respect to the oxides formed on the basis of the original reaction participants however, was not achieved. One such process is the direct oxidation of olefins in an organic liquid medium, such as. B. a nitrile. This procedure will be effective reduced by the direct reaction of oxygen and olefin by decomposing the olefin and other products than the epoxy supplies. Another proposed method is by reaction of olefin / aldehyde and oxygen in the liquid phase, with higher efficiencies through use Larger amounts of olefin than that of aldehyde are achieved and initiators or higher temperatures are used will. Although the efficacies are reported to have improved, they are not optimal, especially when since the aldehyde-based propylene oxide effectiveness is not as high as it is is necessary for an economically viable process. The inventive method for the preparation of olefin oxides and carboxylic acids in liquid Phase by mixing an epoxidizable olefinically unsaturated hydrocarbon compound mn 3 to 22 carbon atoms with an aldehyde from the group of the unsubstituted straight or branched chain Aldehydes with two to 7 carbon atoms and benzaldehyde and one containing oxygen Gas in an organic liquid medium, the molar ratio of olefin to aldehyde not is more than 15: 1, is characterized in that an organic liquid medium is used, contains the mono- or dinitrile belonging to the group of saturated aliphatic nitriles with up to 10 carbons Substance atoms in the non-nitrile part and the saturated cycloaliphatic ^! Nitriles with up to 15 carbon atoms in the non-nitrile part and with up to 6 carbon atoms in each ring, and mixtures thereof, the non-nitrile groups consisting of carbon and hydrogen atoms The co-oxidation occurs here as an indirect oxidation of the olefin via the oxidation of an aldehyde an acyl peroxy compound and / or peracid which epoxidizes the olefin. on and must not with proceedings be confused in which aldehydes are used as initiators. These initiated by aldehydes Processes are done by direct oxidation of the olefin with molecular oxygen with the use of it associated disadvantages, particularly in low epoxide efficiencies, based on the olefin, to express. The process can be carried out by adding a mixture of olefin, aldehyde and nitrile introduced into a reaction vessel. This can consist of glass, be lined with glass or made of aluminum or titanium. One lined with glass and coated with polytetrafluoroethylene is advantageous Stainless steel autoclave, and from an economic point of view, has not even been exaggerated Type 316 stainless steel (as defined by the American Iron and Steel Institute). One can also use a tubular reactor made of similar materials together with an introducer with multiple dots to establish a special ratio of respondents maintain. Some form of agitation is preferred to avoid a static system; can do this