Method of producing olefin oxides

IPC classes for russian patent Method of producing olefin oxides (RU 2461553):

C07D303/04 - containing only hydrogen and carbon atoms in addition to the ring oxygen atoms

C07D301/19 - with organic hydroperoxides

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FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing olefin oxides. According to the invention, olefins undergo epoxidation with isopropylene benzene hydroperoxide at temperature 90-120°C in the presence of a molybdenum-containing catalyst obtained by dissolving molybdenum metal in isopropylene benzene hydroperoxide and ethyl alcohol in volume ratio 1:1, into which a Mannich base is added with molar ratio of molybdenum to Mannich base equal to (0.2-0.5).

EFFECT: simple method of producing olefin oxides through a process without solvents and high technological parameters of the epoxidation process.

1 tbl, 2 ex

The invention relates to the field of petrochemical industry, specifically to the processes of production of oxides of olefins with organic hydroperoxides.

A known method of producing olefin oxides, in particular octene oxide by the epoxidation of olefins with organic hydroperoxides at a temperature of 50-140°C in the presence of a molybdenum-containing catalyst Mo(CO)₆and secondary or tertiary saturated With alcohol₃-C₉when the molar ratio of alcohol and hydroperoxide equal to (1-3):1 in the environment of organic solvent [1].

The closest technical solution of the invention is a method of producing olefin oxides by epoxidation of organic hydroperoxides at a temperature of 90-130°C in the presence of a molybdenum catalyst (propilenglikolem, acetylacetonate, abietic molybdenite) and saturated aliphatic monohydroxy alcohol as a last use the primary C₂-C₈- alcohol in a molar ratio of alcohol and organic hydroperoxide (0,2-6) - 1 or secondary₃-C₄- alcohol in a molar ratio of alcohol and organic hydroperoxide, equal(0,4-0,9):1 [2].

The disadvantage of this method is the process of epoxidation in the presence of aliphatic alcohol, which complicates the technological process, in addition, leads to updat the additional cost of the solvent, since the molar ratio of alcohol:the hydroperoxide is (0,2-6):1.

The objective of the invention is to simplify the method of producing olefin oxides by the epoxidation of olefins by of cumene hydroperoxide (GPIB), and improving the technological parameters of the process.

The technical problem is solved by the epoxidation of olefins by of cumene hydroperoxide at a temperature of 90-120°C in the presence of a molybdenum-containing catalyst, where the catalyst used molybdenum-containing catalyst obtained by dissolving metallic molybdenum in of cumene hydroperoxide and ethanol in a volume ratio of 1:1, which is then injected under manniche in a molar ratio to molybdenum (0.2 to 0.5):1, respectively.

Example 1 (the prototype)

Epoxidation octene-1 exercise 20%of cumene hydroperoxide in a glass reactor equipped with a reflux condenser and a magnetic stirrer at a temperature of 120°C, maintaining a constant temperature by a thermostat, in the presence of propilenglikolem molybdenum MoO₂(C₃H₇O₂)₂.

The process of epoxidation is carried out at a molar ratio of cumene hydroperoxide:octene-1, equal to 1:6, of cumene hydroperoxide:molybdenum equal to 1:0,001, of cumene hydroperoxide:isopropyl is the first alcohol, equal to 1:2, for 90 minutes. Conversion of cumene hydroperoxide in the process of epoxidation is 89,57% wt., the selectivity of the formation of the oxide, octene - 81,05% wt.

Example 2 (the claimed object)

The epoxidation process carried out analogously to example 1, but in the presence of a molybdenum-containing catalyst obtained by dissolving metallic molybdenum in of cumene hydroperoxide and ethanol in a volume ratio of 1:1, which is then injected under manniche in a molar ratio to molybdenum (0.2 to 0.5):1, respectively. Isopropyl alcohol in the process of epoxidation not add.

Conditions and results of epoxidation in the table. The molar ratio of olefin:of cumene hydroperoxide in all experiments was 6:1, while the reaction is 90 minutes.

In the table we have adopted the following abbreviations:

MK - molybdenum-containing catalyst obtained by dissolving metallic molybdenum in of cumene hydroperoxide and ethanol in a volume ratio of 1:1, which is then injected under manniche; OHM - based manniche.

Technical solution allows to simplify the method of producing olefin oxides by the process of epoxidation in the absence of solvent (aliphatic alcohol) and to increase the conversion rate hydro is eroxide of cumene with 89,57 up to 99.6% and selectivity of oxide to 92%.

Example No.	olefin	catalyst	The molar ratio of molybdenum OHM	The concentration of the catalyst 10^-3	The reaction temperature, °C	Conversion GPIB, %	The selectivity of the formation of the oxide %
1	Octene-1	Impregnated-singlecast	-	1	120	89,6	81,1
2	Octene-1	MK	-	0,2	120	93,2	82,6
3	Octene-1	MK	1:0,2	0,2	120	98,5	86,9
4	Octene-1	MK	1:0,4	0,2	120	of 99.1	89,2
5	None	MK	-	0,5	90	95,4	86,9
6	None	MK	1:0,2	0,5	90	96,2	88,2
7	None	MK	1:0,4	0,5	90	97,6	91,5
8	None	MK	-	0,5	110	96,6	89,0
9	None	MK	1:0,2	0,5	110	99,4	to 91.6
10	None	MK	1:0,4	0,5	110	99,8	96,7

Literature

1. The application of Germany No. 2149918, CL 07D 1/08, publ. 1972

2. Inventor's certificate SU 1066995, CL 07D 303/04, 07D 301/19, publ. 1984

A method of producing olefin oxides by the epoxidation of olefins by of cumene hydroperoxide at a temperature of 90-120°C in the presence of a molybdenum-containing catalyst, wherein the catalyst used molybdenum-containing catalyst obtained by dissolving metallic molybdenum in of cumene hydroperoxide and ethanol in a volume ratio of 1:1, which is then injected under manniche at a molar ratio of molybdenum and Mannich bases of 1:(0.2 to 0.5), respectively.