Method for liquid-phase oxidation of ethylbenzene to ethylbenzene hydroperoxide

FIELD: chemistry.

SUBSTANCE: invention relates to a method for liquid-phase oxidation of ethylbenzene to ethylbenzene hydroperoxide, where concentration of ethylbenzene hydroperoxide is kept below 20 wt % with respect to total weight of the reaction mixture and where styrene and/or a styrene derivative is added to ethylbenzene. Concentration of said styrene and/or styrene derivative can range from 0.01 to 5.0 wt %. The styrene derivative is a styrene derivative in which one or more unsubstituted carbon atoms of the styrene have an alkyl group and/or a halogen atom as a substitute. The invention also relates to a method of producing an alkylene oxide, preferably styrene and propyelene oxide.

EFFECT: improved method.

10 cl, 3 dwg, 1 tbl, 4 ex

 

The present invention relates to a method of liquid-phase oxidation of ethylbenzene to gidroperekisi ethylbenzene.

Gidropress ethylbenzene can be obtained by liquid-phase oxidation of ethylbenzene with oxygen-containing gas such as air. Such methods of oxidation are well known in the art. An example of such a method is described in US-A-5883268.

In such reactions the oxidation of ethylbenzene, methylphenylcarbinol (1-phenylethanol) and methylvinylketone (acetophenone) are formed as by-products. Subsequent oxidation of the alkene such as propene) hydropredict ethylbenzene gives the alkene oxide (oxirane or epoxide; such as propylene oxide) and methylphenylcarbinol. Methylvinylketone can be transformed with the use of hydrogen in methylphenylcarbinol. Methylphenylcarbinol can be digidrirovanny to styrene. Styrene and propylene oxide are valuable commercial products.

Processes combined production of styrene monomer ("MS") and propylene oxide ("OP") are known in the art and are marked as "MS/OP". For example, the process MS/OP described in WO 00/05186. In General, the process MS/OP involves the following stages:

(a) interaction of Athena and benzene to obtain ethylbenzene,

(b) interaction of ethylbenzene with oxygen-containing gas to obtain gidroperekisi ethylbenzene,

(c) interaction hydro is ercise ethyl benzene with propene in the presence of an epoxidation catalyst to obtain propylene oxide and 1-phenylethanol, and

(d) the dehydrogenation of 1-phenylethanol to styrene in the presence of a suitable dehydrogenation catalyst.

During these stages (b) and (c) methylvinylketone is formed as a by-product. Before this stage (d), this methylvinylketone can be transformed with the use of hydrogen in methylphenylcarbinol (1-phenylethanol).

During this stage (b) oxidation of ethylbenzene to gidroperekisi ethylbenzene, not the whole ethylbenzene reacts. So do not enter into the reaction of ethylbenzene may be recycled to the oxidation reactor. The oxidation reaction is carried out at concentrations below 20 wt.% the gidroperekisi ethylbenzene relative to the total mass of the reaction mixture. In General, at this concentration or higher, the formation of by-products of methylphenylcarbinol and methylvinylketone increased in comparison with the amount of gidroperekisi ethylbenzene, which leads to inefficient loss of reagent ethylbenzene.

Therefore, the concentration of gidroperekisi ethylbenzene in the reaction mixture remains relatively low. There is a continuing need in the art in achieving a high rate of oxidation at the work exceeding a specified maximum concentration of gidroperekisi ethylbenzene.

Unexpectedly, it was found that, although the presence of styrene slows okelani the ethylbenzene to gidroperekisi ethylbenzene, if Gidropress ethylbenzene is present in a concentration of 20 wt.% or higher, adding a relatively small amount of styrene and/or a derivative of styrene to ethylbenzene has a promoting action, if the concentration of gidroperekisi ethylbenzene below 20 wt.%. Therefore, the recycled stream of ethylbenzene may preferably contain styrene and/or a derivative of styrene as an impurity, which makes continuous purification step is unnecessary.

The above finding was even more unexpected when he discovered that this technology is commonly believed that the styrene and derivatives of styrene, such as α-methylsterols, have an inhibiting effect on the oxidation of compounds of alkylaryl, such as cumin (isopropylbenzene), second-butylbenzoyl etc. for Example, G.A. Russell described in J. Am. Chem. Soc. 77, 4583-4590, 1955, styrene slows down the oxidation of cumene. α-Methylsterol has no effect when added to Kumano: that is inhibiting effect on the oxidation of cumene was not observed in Russell. In G. P. Armstrong et al., in J. Chem. Soc., 666-670, 1950, described, styrene and α-methylsterol retard the oxidation of cumene. Considering the above, quite unexpectedly and surprisingly, the authors of the present invention have found that the oxidation of ethylbenzene (connection alkylaryl), styrene and derivatives of styrene do not provide in ibrowse action and, in fact, have a promoting effect on the oxidation, thereby achieving the desired high rate of oxidation.

Therefore, the present invention relates to a method of liquid-phase oxidation of ethylbenzene to gidroperekisi ethylbenzene, where the concentration of gidroperekisi ethylbenzene remains below 20 wt.% in relation to the total weight of the reaction mixture, and where the styrene and/or a derivative of styrene added to the ethylbenzene. The specified styrene and/or a derivative of styrene may be added to the ethylbenzene before or during its oxidation. Further, it can be added to the ethylbenzene before and during its oxidation.

In example 3 of US-A 4602118 also described the oxidation of ethylbenzene, but this oxidation takes place in the presence of benzophenone promoter.

The oxidation method according to the present invention may be implemented using any suitable technique known in the art, where the oxidizable compound (ethylbenzene) is in the liquid phase, and the oxidant is oxygen gas. In General, such liquid-phase oxidation of ethylbenzene to gidroperekisi of ethylbenzene is carried out at a temperature of from 50 to 250°C., preferably from 100 to 200°C. and, more preferably, from 120 to 180°C. the Reaction vessel typically contains a heat exchanger to heat the reaction mixture at the beginning of the operation and to cool it when eacce sufficiently advanced.

The amount of added oxygen and the amount of added ethylbenzene depends on certain process conditions such as the amount and shape of the reaction vessel and the concentration of gidroperekisi, which, in accordance with the present invention, should remain below 20 wt.% in relation to the total weight of the reaction mixture. Preferably, the concentration of gidroperekisi ethylbenzene in the reaction mixture below 15 wt.%, more preferably, below 12 wt.%. The concentration of gidroperekisi ethylbenzene in the reaction mixture may be from 10 to 15 wt.%, more preferably, from 10 to 12 wt.%.

The pressure in the method according to the present invention is not critical and may be chosen to best fit the specific conditions. In General, the pressure in the upper part of the reaction vessel is from atmospheric up to 10×105N/m2more preferably, from 1 to 5×105N/m2.

The oxidation of ethylbenzene is carried out in the liquid phase and, optionally, in the presence of a diluent. Such a diluent, preferably, is a compound that is liquid under the reaction conditions and does not react with the starting materials and the resulting product. The diluent may be the ethylbenzene. In a preferred variant of the method according to the present invention can be applied to obtain the solution hydrop is rekishi of ethylbenzene to ethylbenzene.

After discharge from the reaction vessel, the reaction mixture is separated into (i) a product stream containing Gidropress ethyl benzene, dissolved in benzene, where the concentration of gidroperekisi ethylbenzene can be from 20 to 50 wt.%, and (ii) a stream of ethylbenzene. This separation may be carried out by a single evaporation, in which a portion of the ethylbenzene Argonauts from the top.

Because a relatively large number of ethylbenzene does not interact in the process of oxidation, ethylbenzene usually recycle into the inlet of the oxidation reactor after removal of impurities from such recycled stream. One of these impurities contained in the specified recirculated stream of ethylbenzene in the integrated process of obtaining oxide alkylene (e.g., propylene oxide), using gidroperekisi ethylbenzene and styrene (for example, the process MS/OP)may be styrene. In the present invention there is no need to remove styrene, if present, of this recirculated stream of ethylbenzene. In fact, the specified styrene may preferably be used as the promoting substance in the oxidation of ethylbenzene. In this case, there is no need for the big stage purification for removal of styrene. Therefore, it is preferable to add styrene to ethylbenzene, preferably, through p is tsirkulirovanija stream of ethylbenzene, containing styrene as an impurity.

The method according to the present invention can be conducted in continuous mode. In General, the reaction vessel used in a continuous process for the oxidation of ethylbenzene, equipped with an inlet for liquid at one end and an outlet for liquid at the other end. Further, the lower part of the reaction vessel typically contains a device for intake of gas, which may be a bubble pipe (or perforated pipe). Usually the gas is removed along with the liquid via the liquid. However, depending on specific conditions, it may be preferable to remove the excess gas through a separate exit for gas during normal operation. Can be one or more separate outputs for gas. Typically, the outlet for the liquid is at the bottom of the vessel, and an optional output for gas in the upper part of the vessel. However, this is not required. The preferred height, which is each of the outputs depends on many factors that may be considered by a person skilled in the art. One such factor is the level of which is usually a liquid.

The gas removed through the specified one or more outputs for gas in the oxidation reaction vessel may contain a significant amount of ethylbenzene vapor. The exact number depends on the conditions of the process. If desired, a pair of ethylbenzene can be condensed in the liquid ethylbenzene and recycled.

It was found that not only styrene contributes to the oxidation of ethylbenzene, but that the derivatives of styrene also have a similar effect. In the context of the present invention derived from styrene can be compounds containing a benzene skeleton, to which is directly attached to one Attila group and to which is attached one or more other substituents. Further, in the context of the present invention, Attila the group of styrene and specified derivatives of styrene may be substituted. Specified Attila group may be substituted by an alkyl group and/or halogen atom. Preferably, such alkyl group is a straight or branched alkyl group containing from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms, and may be, for example, stands, ethyl, n-propylene, isopropyl, n-bootrom, second-bootrom or tert-bootrom. The alkyl group or alkyl groups may be attached to carbon atoms in the α and/or β-position of the styrene skeleton. Examples of such styrene derivatives used in accordance with the present invention include α-methylsterols, α-atistical and α,β-dimethylstyrene, where the latter compound was present who can then use them as a mixture of two geometric isomers.

In accordance with the present invention, derivatives of styrene, thus, may include derivatives of styrene, in which one or more of the unsubstituted carbon atoms of the substituted alkyl group and/or halogen atom. Preferably, such alkyl groups are straight or branched alkyl groups containing from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms, and may, for example, include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl. The halogen atom in the above styrene derivatives may be fluorine, chlorine, bromine or iodine.

Any carbon atom in the styrene skeleton in the above-mentioned derivatives of styrene, other than a carbon atom that is attached Attila group, may be mentioned alkyl group and/or halogen atom as a substituent. The carbon atom in the para-position relative to the substituted carbon atom of styrene, for example, may be substituted. Examples of such styrene derivatives used in accordance with the present invention include 4-tert-butalbiral and 4-chloresterol.

Preferably, during the start-up phase (induction period) of the oxidation reaction, a small quantity of an organic peroxide, such as hydropeaking ethylbenzene add to benzene as an initiator. The number of doba is offered with the gidroperekisi ethylbenzene should be the same to start the oxidation of ethylbenzene. The number of gidroperekisi ethylbenzene may be from 0.1 to 2.0 wt.%, preferably, from 0.25 to 1.0 wt.% in relation to the weight of the entire reaction mixture.

The amount of styrene and/or styrene derivatives, are added in the process of the present invention must be such that the amount of styrene and/or styrene derivatives in the reaction mixture was promoting. More preferably, the amount should be such that a certain transformation was achieved in a shorter period of time compared to the situation in which the styrene and/or derivatives of styrene is added. Preferably, the amount of styrene and/or styrene derivatives, are added to the process of the present invention, such that the concentration of styrene and/or styrene derivatives in the reaction mixture, relative to the total mass of the reaction mixture, was, at least 0.01 wt.%, more preferably at least 0.03 wt.%, more preferably, at least, of 0.05 wt.%, more preferably, at least, of 0.075 wt.%, more preferably, at least 0.1 wt.%, more preferably, at least 0.3 wt.%, more preferably, at least 0.5 wt.%, more preferably, at least 0.7 wt.%, more preferably at least 0.9 wt.% and most pre is respectfully, at least 1.0 wt.%. Further, it is preferable that the amount of styrene and/or styrene derivatives, are added in the process of the present invention, was such that the concentration of styrene and/or styrene derivatives in the reaction mixture, relative to the total mass of the reaction mixture, was at most 5.0 wt.%, more preferably at most 4.0 wt.%, more preferably at most 3.5 wt.%, more preferably at most 3.0 wt.%, more preferably at most 2.5 wt.%, more preferably at most 2.0 wt.%, more preferably at most 1.7% by weight and most preferably at most 1.5 wt.%. Preferably, the concentration of styrene and/or styrene derivatives in the reaction mixture ranged from 0.01 to 5.0 wt.%, preferably, from 0.05 to 3.0 wt.% and, most preferably, from 0.1 to 2.0 wt.% in relation to the total weight of the reaction mixture.

The oxidation is performed by loading the oxygen-containing gas in the reaction mixture in the form of incoming gas flow. The oxygen concentration in the gas stream can range from 5 to 100 vol.%, preferably, from 10 to 60 vol.%, more preferably, from 20 to 50 vol.%, where the balance is, preferably, an inert gas, such as nitrogen. The air, which on average contains 21% vol. oxygen is the preferred oxygen-containing gas feedstock. Pace is the atur gas inlet for gas can vary from ambient temperature to 250°C. The outlet gas temperature for the gas is usually higher than the ambient temperature and may be as high as the temperature in the reactor. To avoid risk of explosion, the oxygen concentration in the exit gas stream after cooling to ambient temperature is usually below 10 vol.%, preferably below 8% vol. and, more preferably, below about 7.%. For example, the exiting gas stream may contain 5% vol. the oxygen.

Oxygen-containing gas may be introduced into the oxidation reactor in any way, for example, using a bubble pipe. Bubbler pipe (or perforated pipe), which is typically installed in the lower part of the oxidation reactor, contain holes in the walls, through which oxygen-containing gas can be loaded into the reaction mixture.

The process of the present invention can be conducted in continuous mode. In this continuous process oxidation reactor, preferably, oriented horizontally, which means that the flow of the reaction mixture flows horizontally through the reactor. Preferably, if the oxidation reactor is oriented horizontally, is used in virtually horizontal reaction vessel, which has a bottom portion and two opposite end, where the reaction vessel contains an inlet for liquid at one end, an outlet for liquid in Apolonas end and device for input of gas, installed in the lower part, where the reaction vessel contains at least one almost vertical bumper partition, disposed in the direction of fluid flow through the reaction vessel during normal operation. This reaction vessel described in WO 2006/024655, and described therein, the reaction vessel may be used in accordance with the present invention.

Further, in this continuous process, the oxidation reactor may consist of two or more separate reaction zones (sometimes also designated as a separate camera). Alternatively, you can apply two or more oxidation reactor, connected in series, where some or all of them may consist of two or more separate reaction zones. In this case, the exit for fluid from one reaction vessel connected to the input of liquid to the next reaction vessel.

If the oxidation reactor comprises two or more separate reaction zones, the flow of the reaction mixture flowing from the first reaction zone into the second reaction zone, and from this second reaction zone to the next reaction zone or into the next reactor or separator. The reaction zone may differ from each other in various aspects, such as the degree of transformation that occurs. A separate reaction zones can be created in one of the reactions is nom vessel means, which are known to the person skilled in the art. The best-known methods of achieving this include the location of the vertical plate between the reaction zones perpendicular to the flow direction so that the plate had a hole that allows fluid to flow from one reaction zone to the next reaction zone. Detailed device one reaction vessel containing multiple reaction zones, described in US-A-4269805. This reaction vessel may be used in accordance with the present invention.

Gidropress ethylbenzene obtained by the method according to the present invention, mainly can be used in methods for producing oxides alkylene of alkenes. Alkene used in such methods, preferably, is an alkene containing from 2 to 10 carbon atoms and, more preferably, the alkene containing from 2 to 4 carbon atoms. Examples of alkenes, which can be used include Aten, propene, 1-butene and 2-butene, from which can be obtained from the corresponding ethylene oxide, propylene oxide and butylene oxide.

For additional stages of the process Gidropress ethylbenzene, obtained as described above, communicates with the alkene with obtaining oxide alkylene. This additional stage itself Gidropress ethylbenzene turns into metalfan carbinol (1-phenylethanol). Preferably, this reaction is carried out in the presence of a catalyst. The preferred catalyst for such processes includes titanium on silica and/or silicate. Other preferred catalysts are described in EP-A-345856. The reaction usually takes place at moderate temperatures and pressures, in particular at a temperature of from 25 to 200°C, preferably from 40 to 135°C. the Exact pressure is not critical, as it allows you to keep the reaction mixture in liquid form or in the form of a mixture of vapor and liquid. In General, the pressure can be from 1 to 100 bar, preferably from 20 to 80 bar.

The oxide alkylene can be separated from the reaction product by any suitable method known to the person skilled in the art. For example, the liquid reaction product may be subjected to fractional distillation and/or selective extraction. The solvent, catalyst and any do not enter into the reaction of the alkene or hydropeaking can be recycled for further use.

Another additional process stage 1-phenylethanol separated from the reaction mixture is converted into styrene by dehydration. As described above, the specified 1-phenylethanol can be formed in the reaction of alkene epoxidation using gidroperekisi ethylbenzene, and also in the oxidation of ethylbenzene and/or hydrogenation methylvinylketone, which is brasaetsa as a by-product. It is preferable to make the entire 1-phenylethanol obtained at these different stages, only one stage of dehydration.

Processes that can be applied at the stage of dehydration of 1-phenylethanol described in WO 99/42425 and WO 99/42426. However, it can be applied to any process known to a person skilled in the technical field.

Therefore, the present invention also relates to a method for producing oxide alkylene and styrene, which includes stages:

i) oxidation of ethylbenzene to gidroperekisi ethylbenzene according to the above method;

ii) interaction of gidroperekisi ethylbenzene with alkene with obtaining oxide alkylene and methylphenylcarbinol; and

iii) dehydration of methylphenylcarbinol to styrene. Preferably, the specified alkene is propylene.

The invention is further illustrated by the examples.

Comparative example 1

1 kg of ethylbenzene, having a styrene content of <100 mg/kg, placed in 2-liter glass reaction vessel equipped with a stirrer, an inlet for gas at the bottom and outlet for gas. The exit gas is combined with a reflux condenser.

The concentration of gidroperekisi ethyl benzene in the reactor is brought to a certain amount specified in table 1, using 35 wt.% the original solution of gidroperekisi of ethylbenzene to ethylbenzene. In the reaction vessel to create the providing nitrogen to 2.9 bar, and the contents of the reactor are heated to 156°C. once reached the specified temperature, the gas mixture air/nitrogen supplied into the reaction vessel with vigorous stirring, the reaction temperature constant support at 156°C. the Total gas flow is 110 liters/hour (under normal conditions). The experiment is carried out semi-continuous periodic manner in which the specified gas mixture is fed continuously.

The boiling point under reflux in the reflux is 95°C, which allows you to condense any captured organic compounds. After passing through the reflux condenser exit gas stream is further cooled in a cold trap at -78°C. After passing through the cooled trap facing the gas flow is heated under ambient temperature and then fed to an analyzer that measures the concentration of oxygen. The ratio of the air/nitrogen gas coming adjusted so that the concentration of oxygen in the output gas was 4.5%vol.

Samples of the reaction mixture taken during the reaction at different points in time. The concentration (in wt.% in relation to the total weight of the reaction mixture) components of the reaction mixture measured by gas chromatography for methylphenylcarbinol (IFAC) and methylvinylketone (IFC), and by iodometric titration for g is propercase ethylbenzene (GPEB).

Example 1

Repeat the experiment of comparative example 1, except that used ethylbenzene contains 1.2 wt.% styrene.

Example 2

Repeat the experiment of comparative example 1, except that used ethylbenzene contains 1.0 wt.% 4-chloresterol.

Example 3

Repeat the experiment of comparative example 1, except that used ethylbenzene contains 1.5 wt.% 4-tert-butylstyrene.

Comparative example 2

Repeat the experiment of comparative example 1, except that the reactor temperature is 145°C and the boiling point under reflux is 80°C.

Example 4

Repeat the experiment of comparative example 2, except that the applied ethylbenzene contains 1.1 wt.% styrene.

The results of experiments

The results of the experiments described in comparative examples 1 and 2 and examples 1 to 4 shown in table 1 and Fig.1-3. Figure 1-3 shows the concentration of GPIB, IFAC and the IFC (in wt.% in relation to the total weight of the reaction mixture), respectively, to the time (in minutes).

The results show that in experiments in which the temperature of the reactor was 156°C. and the boiling temperature under reflux at 95°C, the addition of only small amounts of styrene already gave mn is considerably higher performance GPIB per unit of time. Such a positive effect on productivity was even higher when the styrene was replaced with 4-klaarstroom.

The results of experiments in which the reactor temperature was 145°C. and the boiling temperature under reflux was 80°C show the same effect, provided that the addition of only small amounts of styrene (for example, as in example 4) provides even greater performance GPIB per unit of time (for example, in comparison with example 1) in comparison with samples without addition of styrene (for example, comparative examples 1 and 2, respectively).

In the above experiments have shown that the period achieve a specific concentration GPIB, for example, 10 wt.%, reduced by adding relatively small amounts of styrene or a derivative of styrene. For example, the concentration of GPEB 10 wt.% achieved within 56 minutes adding 1.0 wt.% 4-chloresterol to the reaction mixture, which is approximately 21% less than in the absence of added 4-chloresterol when such concentration GPEB can only be achieved for 68 minutes.

Such a reduction of the reaction time (faster reaction) is very preferable. As can be concluded from the experimental results, the performance of GPEB after a certain period of time is much higher the ri, the addition of relatively small amounts of styrene or a derivative of styrene to the reaction mixture. This, preferably, gives, after a certain period of time, higher output GPIB compared with the number of downloaded ethylbenzene.

Further, the results of experiments show that the addition of styrene or a derivative of styrene to produce more of IFAC and the IFC. Due to this selectivity to gidroperekisi ethylbenzene is actually declining. However, the IFC can be preferably converted into styrene, which is a valuable product. Such education styrene, for example, can be integrated in the process of obtaining oxide alkylene (for example, propylene oxide and styrene, for example, the process MS/OP, as described above.

Table 1
Example No.time (min)GPIB (wt.%)IFAC (wt.%)IFC (wt.%)
Comparative example 100,330,040,05
323,370,110,13
47 5,940,220,27
61charged 8.520,370,48
7210,770,540,75
8312,910,731,06
Example 100,270,030,05
242,750,390,19
354,880,640,38
446,850,840,62
548,810,990,89
6310,421,151,20
Example 20 0,360,040,07
202,680,400,22
304,950,700,46
406,940,960,77
498,701,181,10
5910,411,411,51
Example 300,270,030,05
252,390,370,17
354,400,620,36
46to 6.430,810,60
588,430,99 0,92
6910,131,151,26
Comparative example 200,290,030,05
502,040,070,09
854,480,150,19
1056,070,220,29
1207,460,280,38
1358,760,370,51
Example 400,320,040,06
272,370,280,23
444,290,54 0,49
676,150,770,78
93of 7.900,991,12
1189,421,181,46

1. The method of liquid-phase oxidation of ethylbenzene to gidroperekisi ethylbenzene, where the concentration of gidroperekisi ethylbenzene support below 20 wt.% in relation to the total weight of the reaction mixture, and where the styrene and/or a derivative of styrene added to the ethylbenzene, where styrene derivative is a derivative of styrene, in which one or more of the unsubstituted carbon atoms of the styrene have as substituents alkyl group and/or halogen atom.

2. The method according to claim 1, where the concentration of gidroperekisi ethylbenzene support below 15 wt.%.

3. The method according to claim 1 or 2, where the concentration of styrene and/or a derivative of styrene is from 0.01 to 5.0 wt.% in relation to the total weight of the reaction mixture.

4. The method according to claim 1 or 2, where the styrene is added to ethylbenzene.

5. The method according to claim 4, where the styrene is added by a recirculating stream of ethylbenzene.

6. The method according to claim 5, where the alkyl group is a straight or branched alkyl group, with whom containing a series of from 1 to 10 carbon atoms.

7. The method according to claim 6, where the alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

8. The method according to claim 1, where the halogen atom is a chlorine atom.

9. The method of producing oxide alkylene and styrene, which includes stages:
i) oxidation of ethylbenzene to gidroperekisi ethyl benzene by the method according to any one of claims 1 to 8;
ii) interaction of gidroperekisi ethylbenzene with alkene with obtaining oxide alkylene and methylphenylcarbinol; and
iii) dehydration of methylphenylcarbinol to styrene.

10. The method according to claim 9, where the alkene is propylene.



 

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9 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: method involves treatment of heavy olefin fraction by an alkali solution, processing of obtained discharge alkali flow by extragent, and further precipitation of molybdenum trisulfide by precipitator. According to invention, sodium hydrosulfide is applied as molybdenum trisulfide precipitator. The method allows regulation of molybdenum trisulfide precipitator feed, reduction of precipitation reactor dimensions and energy consumption of heating and stirring, significant reduction waste and hydrogen sulfide discharge at high molybdenum extraction degree of 90.5-97.6%.

EFFECT: improved method of molybdenum extraction from products of catalytic olefin epoxidation by organic hydroperoxides.

6 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of alkylene oxides. Method involves contacting organic hydroperoxide and alkene with a heterogeneous epoxidation catalyst and removal of products flow containing alkylene oxide and alcohol. Fresh catalyst contacts with a feeding mixture taken in the mole ratio of alkene to organic hydroperoxide by at least 1.2-fold more as compared with their the mole ratio in the usual regimen of work. Invention allows enhancing the catalytic activity of catalyst and conversion of hydroperoxide.

EFFECT: improved method of synthesis.

5 cl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of styrene. At the first step the method involves interaction of ethylbenzene hydroperoxide with propene in the presence of catalyst to yield propylene oxide and 1-phenylethanol followed by separate treatment of reaction flow and removing propylene oxide. At the second step the method involves interaction of 1-phenylethanol-containing distillate with a heterogenous dehydration catalyst at temperature 150-320°C to obtain styrene. Distillate contains 0.30 wt.-%, not above, compounds of molecular mass at least 195 Da. Invention provides decreasing the content of by-side compounds in styrene and to enhance it's the conversion degree.

EFFECT: improved method of synthesis.

3 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to synthesis of hydroperoxides of alkylaromatic hydrocarbons which can serve as a source of oxygen-containing organic compounds (phenol, methylphenols, acetone, cyclohexanone etc) and as an initiator of emulsion polymerisation of unsaturated hydrocarbons. The invention discloses a method for synthesis of hydroperoxides of alkylaromatic hydrocarbons through liquid-phase oxidation of these hydrocarbons with atmospheric oxygen at atmospheric pressure, process temperature of 110-130°C, for 1-3 hours in the presence of a 4-methyl-N-hydroxyphthalimide catalyst in amount of 1.0-2.0 wt %.

EFFECT: catalyst prevents use of an initiator and alkaline additives, which considerably simplifies the process, higher conversion of initial alkylaromatic hydrocarbons while preserving high selectivity of the process.

2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemical industry and can be used in combined production of styrene and propylene oxide. Ethylbenzene hydroperoxide is obtained in accordance with the invention by oxidising ethylbenzene with atmospheric oxygen in a continuous reactor at atmospheric pressure in the presence of N-hydroxyphthalimide as a catalyst in amount of 0.5-3 wt % and temperature of the process of 125-130°C until achieving content of ethylbenzene hydroperoxide of 19.2%.

EFFECT: increased conversion of ethylbenzene and selectivity of the process.

1 cl, 1 ex

FIELD: pharmacology.

SUBSTANCE: invention concerns cyclic hydrocarbons, particularly obtainment of cyclohexyl-p-xylol hydroperoxide, which can serve as source for simultaneous xylenol and cyclohexanol obtainment and as emulsion polymerisation initiator for unsaturated hydrocarbons. Cyclohexyl-p-xylol hydroperoxide is obtained by cyclohexyl-p-xylol oxidation by air oxygen at atmospheric pressure in the presence of N-hydroxyphthalamide catalyst in amount of 0.5-2.5 wt % and process temperature of 110-150°C for 1-3 hours till cyclohexyl-p-xylol hydroperoxide content reaches 9.8%.

EFFECT: reduced duration of oxidation process, reduced power cost.

1 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to the method for preparation of cyclohexyl-o-xylol hydroperoxide which can be used as the source of combined obtaining of xylenols and cyclohexanone and as the initiator of emulsion polymerisation of unsaturated hydrocarbons. According to the invention cyclohexyl-o-xylol hydroperoxide is prepared by oxidation of cyclohexyl-o-xylol with air oxygen at temperature 100-150°C and atmospheric pressure in the presence of catalyst N-hydroxyphthalimide during 1-3 hrs. up to cyclohexyl-o-xylol hydroperoxide concentration 34%.

EFFECT: enhancing of the cyclohexyl-o-xylol hydroperoxide formation rate; decrease of the process time and energy consumption during oxidation process.

1 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to the method for preparation of cyclohexylisopropylbenzene hydroperoxide which can be used as initiator of unsaturated hydrocarbons emulsion polymerisation. According to the invention cyclohexylisopropylbenzene hydroperoxide is prepared by oxidation of cyclohexylisopropylbenzene with air oxygen at temperature 100-120°C and atmospheric pressure during 1-3 hrs in the presence of catalyst N-hydroxyphthalimide up to cyclohexylisopropylbenzene hydroperoxide concentration 64%.

EFFECT: enhancing of the cyclohexylisopropylbenzene hydroperoxide formation rate; decrease of the process time and energy consumption.

1 cl, 3 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining cyclohexyltoluene hydroperoxide, which can serve as source of joint obtaining of cresols and cyclohexanon and as initiator of emulsion polymerisation of unsaturated hydrocarbons. According to claimed method obtaining of cyclohexyltoluene hydroperoxide is carried out by oxidation of cyclohexyltoluene with air oxygen at atmospheric pressure in presence of catalyst N-hydroxyphtalimide at temperature of process 110-140°C, during 2-3 hours until content of cyclohexyltoluene hydroperoxide is 22.2%.

EFFECT: increase of target product formation rate, reduction of process duration and reduction of power consumption for its carrying out.

1 cl, 3 tbl, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of alkylaryl hydroperoxides useful as starting material in production of propylene oxide and alkenylaryl. Process of invention comprises following stages: oxidation of alkylaryl compound to form reaction product containing alkylaryl hydroperoxide; contacting at least part of reaction product with basic aqueous solution; separation of hydrocarbon phase containing alkylaryl hydroperoxide from aqueous phase; containing at least part of above hydrocarbon phase with aqueous solution containing waste water, said aqueous solution containing less than 0.2% alkali metal and/or salt (determined as ratio of metal component to total amount of solution); and separation of hydrocarbon phase from aqueous phase. By bringing at least part of above hydrocarbon phase containing alkylaryl hydroperoxide into interaction with propylene and catalyst, alkylaryl hydroxide and propylene oxide are obtained. At least part of propylene oxide is then separated from alkylaryl hydroxide. Dehydration of at least part of alkylaryl hydroxide results in formation of alkenylaryl.

EFFECT: reduced amount of contaminating by-products in alkylaryl hydroperoxide preparation stage.

8 cl, 4 ex

The invention relates to a method of obtaining-generatingcapacity of ethylbenzene oxidation of the latter with oxygen in the presence of a ternary catalyst system comprising a bis-acetylacetonate Nickel, electron-donor complexing compound, for example an alkali metal stearate - sodium or lithium, N-organic-2, hexamethylphosphorotriamide and phenol concentration (0,5-3,0)10-3mol/l,-generatingcapacity is used to obtain propylene oxide, the world production of which is more than 106tons per year, and 44% of production based on the use of EVP as epoxidised agent

The invention relates to a method of producing hydroperoxides by oxidation of hydrocarbons oxygen-containing gas in the presence of certain compounds for the selective conversion of hydrocarbons to the corresponding hydroperoxide
The invention relates to the petrochemical industry and can be used in the process of joint production of propylene oxide and styrene

FIELD: chemistry.

SUBSTANCE: disclosed is a method of producing organic hydroperoxide involving: a) oxidation of an organic compound to obtain an organic reaction product containing organic hydroperoxide; b) mixing at least a portion of the organic reaction product from step (a) with a basic aqueous solution to obtain a mixture of basic aqueous solution and an organic reaction product; c) separating the mixture from step (b) to obtain a separated organic phase containing organic hydroperoxide, and a separated aqueous phase; d) mixing at least a portion of the separated organic phase from step (c) with water to obtain a mixture of aqueous and organic phases; and e) separating the mixture from step (d) to obtain a separated organic phase containing organic hydroperoxide and a separated aqueous phase in separation of the organic phase and the aqueous phase at step (e) is carried out using a coagulator containing glass fibre. The invention also discloses a method of producing alkylene oxide where said organic hydroperoxide is used, as well as an industrial installation for realising said method.

EFFECT: improved removal of impurities of basic materials.

9 cl, 3 dwg, 2 tbl, 26 ex

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