Organic hydroperoxide production process

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 present invention relates to a method of preparation of organic hydroperoxides. Such organic hydroperoxides useful for use in a variety of ways, such as obtaining compounds of oxirane and receiving alkynylaryl.

Methods for producing propylene oxide using organic hydroperoxides are well known in this field. As described in US-A-5883268, this method usually includes perechislenie ethylbenzene with subsequent interaction of the reaction product of perechisleniya with water in a quantity sufficient to neutralize acidic components, separation of the mixture into the stream of water and neutralizing the acidity of the organic stream. Contaminated base flow hydroperoxide with neutralized acidity washed with water and the resulting mixture is divided into contaminated by organic compounds in the aqueous phase and organic phase with a low content of alkali metal. Contaminated by organic compounds in the aqueous phase is brought into contact with the extracting hydrocarbon and separating the purified aqueous phase with low level of organic impurities. Described that the purified water stream may go with minimal additional processing, because the level of organic impurities is reduced.

From the point of view of environmental safety pre is respectfully, to the volume flow of waste materials, resulting from the implementation of the method was as little as possible. Moreover, there is usually more appropriate to receive the flow of exhaust materials containing concentrated organic waste compounds. Therefore, it is preferable that the concentration of the organic waste compounds in the water flow of waste materials was high.

Unexpectedly, it was found that waste water, preferably, the waste water received at one or more stages of the present method, can be used in aqueous solution for the treatment of contaminated base flow hydroperoxide. Unexpectedly it was discovered that the impurities present in one or more wastewater flows do not interfere with the cleaning hydroperoxides hydrocarbon phase. If this is not detected negative impact on operating as a catalyst, when the stream containing alkylarylsulfonate treated waste water is subjected to interaction with the olefin in the presence of a catalyst as described in EP-A-345856, with the aim of obtaining alkylarylsulfonate and compounds of oxirane.

The present invention relates to a method of preparation of organic hydroperoxides, including:

(a) oxidation of organic compounds with obtaining p is oduct interaction containing organic hydroperoxide,

(b) contacting the at least partially containing organic hydroperoxide reaction product with a basic aqueous solution,

(c) separating the hydrocarbon phase containing organic hydroperoxide, from the aqueous phase, (d) contacting the at least partially separated hydrocarbon phase containing organic hydroperoxide with an aqueous solution containing wastewater, as specified aqueous solution contains less than 0.2% wt. alkali metal and/or salt, which is determined by the ratio of metal to the total amount of solution, and

(e) separating the hydrocarbon phase containing organic hydroperoxide, from the aqueous phase.

Organic hydroperoxides useful in a number of ways. One of such ways is the interaction of organic hydroperoxide with an olefin order to obtain compounds of oxirane. In this way, the organic compound usually means alkylaryl, and the method further includes:

(f) interaction, at least partial, of the hydrocarbon phase containing organic hydroperoxide obtained in stage (e), with the olefin and the catalyst to obtain alkylarylsulfonate and compounds of oxirane, and

(g) separating at least a partial connection of oxirane from alkylarylsulfonate.

Alkylaryl XID, obtained in stage (g), can be used in a wide variety of ways. This way is getting alkynylaryl by dehydration alkylarylsulfonate. Another way is to hydrogenation alkylarylsulfonate with getting alkylaryl. If the method according to the present invention is used for dehydration of alkylarylsulfonate, method, respectively, further includes:

(h) converting at least a partial, alkylarylsulfonate obtained in stage (g). Usually as a result of such conversion are formed of the reaction product and water.

Preferably, step (h) includes either dehydration or hydrogenolysis reaction product. Hydrogenolysis means the interaction of alkylarylsulfonate with hydrogen, preferably in the presence of a catalyst. Dehydration usually gives alkynylaryl and water, while hydrogenolysis usually gives alkylaryl. Preferably, the hydrogenolysis gives alkylaryl used as the source of the connection.

Although organic compound used in the method according to the present invention, can be, in principle, any connection, the most commonly used organic compounds are alcylaryl connection. The most commonly used alcylaryl compounds are benzene compounds containing at least 1 alkyl substituent, where the specified alkyl substituent contains from 1 to 10 carbon atoms, preferably from 2 to 8 carbon atoms. Preferably, the benzene compound contains on average from 1 to 2 parts. The most common alcylaryl compounds are ethylbenzene, cumene, di(isopropyl)benzene.

Oxidation of organic compounds can be performed in any appropriate way known from the prior art. The oxidation can be carried out in the liquid phase in the presence of a diluent. This diluent is preferably a compound that is a liquid under the reaction conditions and does not react with the starting substances and the resulting products. However, the diluent may also be a connection, by necessity, present in the reaction mixture. For example, if alkylaryl means ethylbenzene, the diluent may also be ethylbenzene.

In addition to the required organic hydroperoxide wide range of contaminants can be formed during the oxidation of organic compounds. Although most of the impurities present in small amounts, was found, in particular, that due to the presence of organic acids sometimes there are problems with the continued use of organic hydroperoxides. As described in US-A-5883268, the method of reducing the number is TBA contaminants is the contacting of the product, containing organic hydroperoxide with an aqueous solution of alkali. However, as a result of contact with the aqueous alkaline solution, a certain amount of the alkali metal enters containing organic hydroperoxide reaction product. Although the amount of organic acids can be reduced by washing with alkali, alkaline metal as impurities remains elevated.

According to the method according to the present invention, an organic hydroperoxide containing reaction product is brought into contact with a basic aqueous solution, more precisely with the basic aqueous solution containing one or more compounds of an alkali metal. Suitable for use in aqueous alkaline solution alkaline sources include hydroxides of alkali metals, carbonates of alkali metals and hydrogen carbonates of alkali metals. Examples of such compounds are NaOH, KOH, Na2CO3, K2CO3, NaHCO3and KHCO3. Given the easy availability, it is preferable to use NaOH and/or Na2CO3. The rate of attainment of equilibrium where the majority of the salts neutralized compounds of alkali metals acids present in the aqueous phase can be increased by methods known to experts in this field. Process stage (b) is preferably carried out at Eskom contacting containing organic hydroperoxide reaction product and the basic aqueous solution. This close contact can be achieved by any known from the prior art method, for example by intensive mixing. The specific conditions in which carry out stage (b), are highly dependent on future circumstances. Preferably, stage (b) is carried out at a temperature from 0°C to 150°C, more preferably from 20°C to 100°C.

At the stage (c) the hydrocarbon phase is separated from the aqueous phase. A preferred method includes providing a hydrocarbon phase and aqueous phase to precipitate in the settling tank and subsequent separation of the hydrocarbon phase from the aqueous phase. Preferably, the hydrocarbonaceous phase containing organic hydroperoxide, subsequently sent to the coagulator, which produces further removal of the aqueous phase. Preferably, stage (c) is carried out at a temperature from 0°C to 150°C, more preferably from 20°C to 100°C.

At stage (d) at least a portion of the separated hydrocarbon phase is brought into contact with a water solution containing waste water, preferably from one or several technological stages in this way. An aqueous solution containing waste water can be added to the separated hydrocarbon phase at any stage after at least part of the aqueous phase is removed from the hydrocarbon phase. Site is preferably, characteristic of an embodiment includes adding waste water or an aqueous solution containing waste water, the flocculating agent used in stage (c).

After stage (d) of the hydrocarbon phase is separated from the aqueous phase to phase (e). A preferred method includes providing a hydrocarbon phase and aqueous phase to precipitate in the settling tank and subsequent separation of the hydrocarbon phase from the aqueous phase. The hydrocarbon phase containing organic hydroperoxide, preferably subsequently sent to the coagulator, which produces further removal of the aqueous phase. Preferably, stage (e) is carried out at a temperature from 0°C to 150°C, more preferably from 20°C to 100°C. Next, water, unconverted organic compounds and impurities are preferably separated by distillation from the hydrocarbon phase obtained from the coagulator. Typically, the distillate contains unconverted organic compounds, water and impurities. The obtained distillate can be further divided into phases in the tank, which allows to obtain the organic phase and aqueous phase. Thus obtained aqueous phase contains organic impurities, and particularly suitable for use as wastewater on stage (d).

Aqueous solution used in stage (d), which may be any aqueous solution, consisting, at least partially, from wastewater. The aqueous solution may be a combination of fresh water, essentially not containing impurities, and one or more different streams of sewage, or the specified solution can only consist of various types of wastewater, or the specified solution may consist of a separate type of waste water.

Preferably, step (d) comprises contacting the at least partially separated hydrocarbon phase containing organic hydroperoxide with an aqueous solution containing as the waste water that was previously used for washing the hydrocarbon phase containing organic hydroperoxide and another type of wastewater. Preferably, the other type of waste water means one or more specific flows of wastewater, described below.

Waste water previously used for washing the hydrocarbon phase containing organic hydroperoxide, preferably by means of waste water obtained by contacting hydrocarbonaceous phase containing organic hydroperoxide, with the aqueous phase, preferably clean water, and subsequent separation of the aqueous phase from the hydrocarbon phase. Thus obtained aqueous phase is preferably used as the waste water without additional treatment. Most p is edocfile, thus obtained aqueous phase to be used in combination with other wastewater.

The hydrocarbon phase is separated and obtained in stage (c), is preferably brought into countercurrent contact with the aqueous solution of stage (d). It is assumed that the mode counter includes contacting with clean water hydrocarbon phase, which has already been washed one or more times, while the hydrocarbon phase, which has not yet been washed, is in contact with the aqueous phase, which has already been in contact with the hydrocarbon phase. It is preferable to add the waste water to aqueous solution for processing hydrocarbon phase, which has not yet been washed.

The source of wastewater for use in stage (d) is not essential for the method according to the present invention. However, it is preferable that the waste water was obtained at the technological stage, close to the present method, since it reduces the risk of a possible interaction of the compounds present in the hydrocarbon phase, with compounds present in the aqueous solution. Moreover, it is preferable not to introduce in the way of new features. Discovered that you can use waste water containing significant amounts of pollutants, such as 1,2-propandiol.

The authors of the present invention discovered that h is about the presence of contaminants does not usually adversely affect the cleanup of hydrocarbon phase, containing organic hydroperoxide. Moreover, we discovered that the presence of contaminants, such as organic acids, often improves the washing efficiency of the flow of the organic hydroperoxide. It is noticed that the flow of hydroperoxide obtained in stage (d), contains less sodium, when used for washing waste water containing organic acids than when using just clean water. In addition, in many cases improved the separation of organic and aqueous phase.

Also found that the use of stage (d) an aqueous solution comprising an acid waste water, gives good results, because the purpose of the preceding process steps consisting in the removal of organic acids formed as by-product during the oxidation stage (a). When this acidic waste water which can be used in the aqueous wash solution of stage (d), gives good results without negative effects on subsequent catalyst such as the catalyst described in EP-A-345856.

Waste water, which has been found particularly suitable for use in aqueous solutions according to the present invention is an acidic waste water. Preferably, the acidic waste water includes one or more organic to the slot. Found that organic acids are generally compatible with compounds optionally used in the present method. Found that particularly preferably, if present, the acid is an organic acid containing from 1 to 20 carbon atoms. Preferred organic acids present in the waste water, include gidrotermokarstovye acid containing a total of from 1 to 10 carbon atoms. Particularly preferred acids are formic acid, acetic acid, propionic acid and butyric acid. It was found that formic acid is particularly suitable because it has detected a formic acid causes only a limited decomposition of the organic hydroperoxide.

The concentration of acid in aqueous solution is preferably from 0.0001 to 5 wt.%. in the calculation of the total amount of the aqueous solution, more preferably from 0.001 to 2 wt.%, most preferably from 0.001 to 1% wt.

At stage (d) the separated hydrocarbon phase containing a hydroperoxide, put in contact with a water solution containing waste water in order to remove organic contaminants, particularly organic salts, more specifically, organic salts of alkali metals. Therefore, the aqueous solution containing the waste water that must be so, h is usually used for processing hydrocarbon phase, containing organic hydroperoxide aqueous solution containing waste water, reduced the amount of contaminants present in the hydrocarbonaceous phase containing organic hydroperoxide. Because a wide range of contaminants may be present in the hydrocarbon phase, you cannot specify which connections in what quantities, valid in aqueous solution. The person skilled in the art it is clear that harmful, if an aqueous solution containing waste water that contains a high concentration of impurities to be removed. Preferably, the aqueous solution contains less than 20 wt.%. compounds that are removed from the containing organic hydroperoxide stream. Preferably, the aqueous solution contains at least 80 wt.%. water, more preferably at least 90% wt. The amount of water is at most of 99.99 wt.%, more preferably at most 99 wt.%.

Part of the contaminants can usually be introduced into the hydrocarbon phase containing organic hydroperoxide, the basic aqueous solution used in stage (b). Therefore, it is preferable that the waste water used in aqueous solution for the stage (d), did not contain significant amounts of the basic aqueous solution used in stage (b). Preferably, less than 10% wt. the main water races the thief, used in stage (b), used in aqueous solution stage (d), more preferably less than 5 wt.%, most preferably, the lack of a basic aqueous solution. The amounts correspond to the amounts presented in the way, regardless of what number of such solutions are recirculated. An aqueous solution containing the waste water that contained less than 0.2% wt. compounds and/or salts of alkaline metal, determined by the ratio of metal to the total amount of solution, preferably less than 0.1 wt.%, more preferably less than 0.05 wt.%, most preferably less than 0.01 wt.%.

Preferably, the aqueous solution for use on stage (d) consists of water and wastewater, as specified aqueous solution has a pH from 2 to 7, preferably from 3 to less than 7, more preferably from 3.5 to 6.5.

Wastewater flows can be used as such. However, in some cases it may be advantageous to concentrate the flow of waste water before use in the method according to the present invention.

Wastewater flows, which can be used in stage (d) according to the present method will have a variety of ways in the method according to the present invention. The preferred wastewater flows for use in aqueous solution for use in the present invention consist, at least partially, the C one or more of the following streams of wastewater: wastewater, obtained as a by-product in the oxidation of organic compounds at the stage of (a), the waste water obtained in the purifying filters for waste gas, water distillate obtained by distillation of the hydrocarbon phase obtained in stage (e), and water obtained by converting alkylarylsulfonate on stage (h). Such flows are described in more detail below.

It has been found that the oxidation of organic compounds can form water. It is believed that this water occurs when adverse reactions, such as decomposition of hydroperoxide. The flow of wastewater, which can be used in stage (d)can be recovered by condensing the exhaust from the reactor gas and the separation of the hydrocarbon phase. Such a flow of waste water is particularly suitable for use in stage (d) due to low pH values.

In the oxidation of organic compounds formed exhaust gas containing organic impurities. One of the possible treatment options such exhaust gas is cleaned by the filter, more specifically a carbon filter. The filter should be cleaned regularly to remove the absorbed contaminants. This is usually carried out with water, optionally containing minor amounts of other compounds. Found that such waste water, poluchena is in cleaning filters for flue gas particularly suitable for use in an aqueous solution containing waste water.

Another stream of wastewater, is suitable for use in an aqueous solution containing waste water is the water distillate obtained by separating the hydrocarbon phase from the aqueous phase by distillation of the hydrocarbon phase and the subsequent separation of the hydrocarbon distillate water from the distillate. Preferred variants of receipt of such aqueous distillate for use as wastewater on stage (d) described above in the discussion stage (e). Such aqueous distillate is particularly suitable for use in the aqueous solution used in stage (d). Typically, the conversion gives the reaction product and water.

Another stream of waste water, particularly suitable for use in aqueous solution, water is produced during the conversion of alkylarylsulfonate on stage (h). As indicated above, the conversion of predominantly means dehydration or hydrogenolysis. If stage (h) includes dehydration, the product of dehydration preferably distilled, the distillate contains water and organic compounds. This distillate is a phase that is allocated by the separation of the hydrocarbon phase in the settling tank and the feed of the aqueous phase in the coagulator. Received in the chamber of the coagulator podnapisi very convenient for use as wastewater on stage (d). If stage (h) includes the hydrogenolysis, the resulting water can be used as a waste water on stage (d), preferably after separation of the hydrocarbon phase by phase separation. If hydrogenolysis gives alcylaryl compound used as the source of the product obtained at stage (h) alcylaryl connection it is convenient to return for re-processing at stage (a).

It was found that in a limited number of cases when contacting the hydrocarbonaceous phase containing organic hydroperoxide with an aqueous solution containing the waste water that is formed emulsion layer at the interface between the phases or layers. Without going into theory, it is believed that this layer can be generated when there is a significant amount of metal-containing impurities, such as compounds containing iron. Metal compounds are sometimes present in the acid flows due to corrosion of metal surfaces in contact with some of the flows of waste materials. Therefore, the most common methods for removing metal compounds from waste water in many cases are easy to prevent the formation of a layer with this method. It is generally preferable implementation of the method at elevated temperatures, preferably at a temperature of, for men is our least 40°C, preferably at least 50°C, more preferably at least 60°C.

The preferred method of preventing the formation of the layer is to filter waste water and/or aqueous solution containing waste water. Preferred filter is a filter with a pore size of 50 micrometers or less, preferably 30 μm or less, preferably 20 micrometers or less.

Another way to prevent the formation of a layer is the dilution of wastewater by adding to the aqueous solution of pure water that does not contain impurities. The number of added pure water depends on the type and quantity (quantities) present contaminants. Found that in many cases it is enough to add 30% wt. clean water from the total amount of waste water.

Less attractive option to prevent the formation of a layer is the distillation of the waste water and the use of treated wastewater in aqueous solution.

Depending on the amount of impurities present in the hydrocarbon phase containing the organic peroxide, process steps (d) and (e) can be performed either once or several times. Preferably a combination of these process steps to perform from 1 to 3 times.

At stage (f) method of producing propylene is xida, at least part of the hydrocarbonaceous phase containing organic hydroperoxide obtained in stage (e), interacts with the olefin, preferably propene in the presence of the catalyst to obtain alkylarylsulfonate and compounds of oxirane. The catalyst, which is useful when the specified method includes titanium dioxide silica and/or silicate. The preferred catalyst described in EP-A-345856. The interaction usually takes place at moderate temperatures and pressures, in particular at temperatures in the range from 0 to 200°preferably in the range from 25 to 200°C. the Exact value of the pressure is not critical as long as the pressure is sufficient to maintain the reaction mixture in liquid form or in the form of a mixture of vapor and liquid. Atmospheric pressure may be sufficient. In most cases, the pressure may be in the range from 1 to 100×105N/m2.

Connection oxirane can be separated from the reaction product containing alkylacrylate, any appropriate method according to the expert in this field. The liquid reaction product can be treated by fractional distillation, selective extraction and/or filtration. The solvent, the catalyst and any unreacted olefin or alkylarylsulfonate may return the equipment to recycle for recycling.

Obtained according to the method of alkylacrylate may be subjected to dehydration in the presence of the catalyst in order to obtain styrene and water. The method, which can be used at this stage, is described in WO 99/42425 and WO 99/42426. However, any suitable method known to the person skilled in the art, in principle, can be used.

The present invention is additionally illustrated by the following examples.

Example 1

In the reactor blow air through ethylbenzene. The resulting product contains ethylbenzonitrile. The specified product is brought into contact with a solution containing 0.5% wt. NaOH in water and stirred at a temperature of 60°C. the Mass ratio of the product containing ethylbenzonitrile and containing NaOH solution, equal to 4.5:1 (wt.:wt.). The obtained neutralized mixture is sent to a clarifier, where the neutralized hydrocarbon phase containing ethylbenzonitrile, is separated from the aqueous phase.

The neutralized hydrocarbon phase containing ethylbenzonitrile, sent to the coagulator, which produces further removal of the aqueous phase. Obtained from the coagulator neutralized solution ethylbenzothiazoline contains 127 ppm of sodium.

The neutralized hydrocarbon phase containing ethylbenzonitrile, washed, blending the neutrons which became centralized solution ethylbenzothiazoline of the coagulant with the water solution, the separation obtained in the sump mixture into an aqueous phase and a hydrocarbon phase, subsequent separation of the hydrocarbon phase obtained from the clarifier, the first flocculating agent and separating the hydrocarbon phase obtained in the first flocculating agent, the second flocculating agent. Each of these stages is described in more detail below. In the second coagulator hydrocarbon phase contains ethylbenzonitrile, ethylbenzene, water and impurities. Specified hydrocarbon phase is distilled. The distillate contains ethylbenzene, water and impurities. The specified distillate is divided into phases in the tank, getting a hydrocarbon phase containing ethylbenzene and impurities, and the aqueous phase containing water and impurities. The aqueous phase has a pH of 3 and is used as the waste water for use in water solution for washing the neutralized hydrocarbon phase.

The neutralized solution ethylbenzothiazoline mixed with an aqueous solution in a ratio of 4.5:1 (wt.:wt.). An aqueous solution containing 85 wt.%. aimed at recycling at this stage of water, to which add 1.3% wt. clean water and 13.7% wt. the waste water used for washing the hydrocarbon phase containing organic hydroperoxide.

The resulting mixture is sent to a clarifier, where glevodorodnogo phase is separated from the aqueous phase.

To the obtained aqueous phase add NaOH specified containing NaOH aqueous phase is designed to neutralize the hydrocarbon phase containing ethylbenzonitrile.

Obtained in the sump of the hydrocarbon phase is sent to the first coagulator, which add to 1.1 wt.%. (in the calculation of the hydrocarbon phase as a whole) of the aqueous phase of the distillate containing water and the above-mentioned impurities, and 1.7 wt.%. (in the calculation of the hydrocarbon phase as a whole) of clean water. In the first coagulator obtain an aqueous phase and a hydrocarbon phase. The hydrocarbon phase from the first flocculating agent is sent to the second coagulator, where optionally add a 1.4% wt. (in the calculation of the hydrocarbon phase as a whole) of clean water.

It was found that obtained from the second coagulator hydrocarbon phase contains from 0.1 to 0.2 ppm of sodium.

Example 2

Repeat example 1, except that instead of the aqueous phase of the distillate containing water and impurities in the first coagulator add the appropriate amount of clean water.

It was found that obtained from the second coagulator hydrocarbon phase contains from 0.2 to 0.3 ppm of sodium.

Example 3

In the reactor blow air through ethylbenzene. The resulting product contains ethylbenzonitrile. The specified product is brought into contact with a solution containing 0.3 wt.%. NaOH in water and displaced the more at a temperature of 70° C. the Mass ratio of the product containing ethylbenzonitrile and containing NaOH solution is 3:1 (wt.:wt.). The obtained neutralized mixture is divided into phases. Obtained after separation of the phases are neutralized solution ethylbenzothiazoline contains 11,5 mg sodium per kg of solution.

The neutralized hydrocarbon phase containing ethylbenzonitrile, washed, blending the neutralized solution ethylbenzothiazoline with an aqueous solution, as described below, and share phase. The specified mixing and separation of the phases is repeated once. Obtained after phase separation of the hydrocarbon phase contains ethylbenzonitrile, ethylbenzene, water and impurities. The specified phase is distilled. The obtained distillate contains ethylbenzene, water and impurities. The specified distillate is divided into phases in the tank, getting a hydrocarbon phase containing ethylbenzene and impurities, and the aqueous phase containing water and impurities. The aqueous phase has a pH of 3 and is used as the waste water for use in water solution for washing the neutralized hydrocarbon phase.

The neutralized hydrocarbon phase containing ethylbenzonitrile, washed as follows. 300 grams of the neutralized solution activesolid is peroxide mixed with 75 grams of the above aqueous phase of the distillate. The mixture shaken for 2 minutes and left to stand for 14 minutes. The specified procedure is performed at 60°C, using plastic separating funnel and flask.

Found that the resulting hydrocarbon phase contains less than 0.1 ppm of sodium.

Example comparison 1

300 grams of the neutralized solution ethylbenzothiazoline obtained according to example 3 are mixed with 75 grams of pure water having a pH of 7.8. The mixture shaken for 2 minutes and left to stand for 14 minutes. The experiment performed at 60°C, using plastic separating funnel and flask.

Found that the resulting hydrocarbon phase contains 0.1 part per million of sodium.

Example 4

In the reactor blow air through ethylbenzene. The resulting product contains ethylbenzonitrile. The specified product is mixed at a temperature of 70°C with a solution containing 0.35% of wt. NaOH and 5% wt. sodium benzoate in the following dehydration water and mix. The mass ratio of the product containing ethylbenzonitrile and containing sodium benzoate solution, equal to 4:1 (wt.:wt.). then the resulting mixture is divided into phases with the help of the vessel.

The obtained neutralized solution ethylbenzothiazoline contains 8 parts per million in relation to wt. (ppm) sodium.

Then the neutralized solution was washed with a stream of the m wastewater obtained in the following way. 1-phenylethanol obtained by a method including the above steps (a)-(g)is converted into styrene. The resulting reaction mixture contains styrene, water and organic impurities. The reaction mixture is distilled. This distillate is divided into phases. Obtained after separation of the phases the aqueous phase, referred to here as "dehydration water is used for washing the neutralized solution ethylbenzothiazoline.

600 ml of the above neutralized solution ethylbenzothiazoline washed with 150 ml of dehydration water. The mixture is divided into phases.

Found that the resulting hydrocarbon phase after separation of the phases contains less than 0.05 ppm of sodium.

Example 2 comparison

Repeating the method of example 4, except that the dehydration water replace with clean water. 600 ml of the neutralized solution ethylbenzothiazoline, obtained as described in example 4, washed with 150 ml of pure water.

Found that the resulting hydrocarbon phase after separation of the phases contains 0,12 ppm of sodium.

1. The method of obtaining organic alkaloidshenobarbital, including

(a) oxidation alcylaryl connection with the formation of a reaction product containing alkylarylsulfonate,

(b) contacting at least part of reactionamajorproduct, containing organic alkylarylsulfonate, with a basic aqueous solution,

(c) separating the hydrocarbon phase containing alkylarylsulfonate, from the aqueous phase,

(d) contacting at least part of the separated hydrocarbon phase containing alkylarylsulfonate, with a water solution containing waste water, and the specified aqueous solution contains less than 0.2 wt.% alkali metal and/or salt, which is determined by the ratio of metal to the total amount of solution, and

(e) separating the hydrocarbon phase containing alkylarylsulfonate, from the aqueous phase.

2. The method according to claim 1, wherein the basic aqueous solution in stage (b) contains one or more compounds of an alkali metal.

3. The method according to any of claim 1 or 2, characterized in that the waste water used in the aqueous solution in stage (d)is an acid.

4. The method according to any of claim 1 or 2, characterized in that the waste water used in the aqueous solution in stage (d), contains one or more organic acids.

5. The method according to any of claim 1 or 2, characterized in that the aqueous solution in stage (d) contains the waste water used for washing the hydrocarbon phase containing the hydroperoxide, and other type of waste water.

6. The method of producing propylene oxide, comprising obtaining al is railwayrelated by means of the method according to claims 1 to 5, where the specified method further includes

(f) communicating at least part of the hydrocarbon phase containing alkylarylsulfonate obtained in stage (e), with propylene and the catalyst to obtain alkylarylsulfonate and propylene oxide, and

(g) separating at least part of the propylene oxide from alkylarylsulfonate.

7. The method of producing alkynylaryl, including obtaining alkylarylsulfonate the method according to claim 6, the method further includes (h) dehydrating at least part of alkylarylsulfonate obtained in stage (g), with alkenylamine connection.

8. The method according to any one of claims 1, 6 or 7, characterized in that the aqueous solution in stage (d) contains, at least partially, one or more of the following streams of waste water: waste water produced as a by-product in the oxidation alcylaryl connections on the stage (a), the waste water obtained in the purifying filters for waste gas, water distillate obtained by distillation of the hydrocarbon phase obtained in stage (e), and water, obtained by conversion of alkylarylsulfonate on stage (h).



 

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The invention relates to the technology of production of ethylene oxide, in particular to a method for separation of ethylene oxide from a mixture containing ethylene oxide

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for interaction of an organic compound with hydroperoxide. Invention describes a continuous method of interaction of organic compound comprising at least one C-C-double bond with hydroperoxide in the presence of a catalyst. Method involves interaction of organic compound at the reaction step (R1) under the range of the own pressure below 100 bars, temperature in the range 0-120°C and in the molar ratio of reacting organic compound to hydroperoxide in the range 0.7-20 with hydroperoxide in the presence of a zeolite-containing catalyst to yield at least one flow of the product (P1). Then at least one flow of the product (P1) is fed to intermediate treatment (Z1) wherein (Z1) forms at least one the hydroperoxide-containing product flow (PZ1) and wherein the intermediate treatment represents distillation separation of hydroperoxide from at least one the product flow (P1) or addition of a base to at least one the product flow (P1) and at least one the product flow is fed to at least in the reaction step (R2) wherein under pressure in the own pressure up to 100 bars, temperature in the range 0-120°C and in the molar ratio of the reacting organic compound to hydroperoxide in the range 0.7-20 hydroperoxide is subjected for interaction with an organic compound in the presence of a zeolite-containing catalyst to yield at least one the product flow (P2) wherein at least one of reaction steps (R1) and (R2) the method involves using the reactors system comprising at least two reactors joined in parallel. Also, invention describes a device for carrying out the interaction of an organic compound with hydroperoxide.

EFFECT: improved method for interaction.

9 cl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for synthesis of oxirane compounds comprising the following steps: (i) oxidation of alkylaryl wherein alkyl substitute comprises from 2 to 10 carbon atoms to yield alkylaryl hydroperoxide; (ii) contacting at least part of alkylaryl hydroperoxide prepared at the step (i) with olefin at the temperature range 0-200°C and under pressure in the range 1-100 x 105 H/m2 in the presence of a catalyst comprising titanium on silicon dioxide and/or silicate to yield oxirane compound and alkylaryl hydroxyl; (iii) optional interaction of at least part of alkylaryl hydroperoxide prepared at the step (i) to yield phenol and ketone; (iv) separation of oxirane compound from the reaction product from the step (ii0, and (v) contacting at least part of the reaction product no containing oxirane with hydrogen at temperature 100-330°C and under pressure 0.1-50 x 105 H/m2 in the presence of the hydrogenation catalyst to yield alkylaryl and at least part of the latter is re-circulated to the step (i) wherein the hydrogenation catalyst represents catalyst comprising copper compound, zinc compound and at least one compound chosen from the group consisting of aluminum, zirconium, magnesium rare-earth metals and their mixtures. Invention provides the possibility for synthesis of oxirane compounds without necessity for simultaneous synthesis of other compounds.

EFFECT: improved method of synthesis.

5 cl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for synthesis of oxirane compounds comprising the following steps: (i) oxidation of alkylaryl to yield alkylaryl hydroperoxide; (ii) contacting at least lesser part of alkylaryl hydroperoxide prepared at the step (i) with olefin in the presence of catalyst to yield oxirane compound and alkylaryl hydroxyl; (iii) separation of oxirane compound from the reaction product from the step (ii), and (iv) contacting at least part of the reaction product no containing oxirane compound with hydrogen to yield alkylaryl and at least of part of the latter is re-circulated to the step (i) and wherein alkylaryl means an alkylaryl compound representing di-(isopropyl)-benzene. Invention provides the possibility for preparing oxirane compound without the necessity for preparing other compounds and reducing the amount of the parent alkylaryl.

EFFECT: improved method of synthesis.

3 cl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of compounds of oxirane, phenol and ketones and/or aldehydes. Proposed method involves the following steps: (i) oxidation of alkylaryl wherein alkyl substitute comprises from 2 to 10 carbon atoms to yield alkylaryl hydroperoxide; (ii) contacting at least part of alkylaryl hydroperoxide prepared at the step (i) with olefin in the presence of catalyst to yield oxirane compound and alkylaryl hydroxyl; (iii) reaction of at least part of alkylaryl hydroperoxide prepared at the step (i) to yield phenol and ketone and/or aldehyde; (iv) separation of oxirane compound from the reaction product from the step (ii), and (v) contacting at least part of the reaction product no containing oxirane with hydrogen to yield alkylaryl and at least part of the latter is re-circulated to the step (i). Invention provides the development of the combined method for synthesis of oxirane, phenol, ketones and/or aldehydes that allows reducing the amount of by-side products due to their conversion to useful compounds.

EFFECT: improved method of synthesis.

8 cl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for synthesis of organic hydroperoxide comprising the reduced amount of impurities. Method involves the following steps: (a) oxidation of organic compound to yield the reaction product comprising organic hydroperoxide; (b) contacting at least part of the reaction product comprising organic hydroperoxide with the basic aqueous solution; (c) separation of hydrocarbon phase containing organic hydroperoxide from an aqueous phase; (d) washing out at least part of the separated hydrocarbon phase containing organic hydroperoxide, and (e) contacting at least part of hydrocarbon phase containing organic hydroperoxide with a protective layer comprising a solid adsorbent wherein a solid adsorbent shows porosity 50-98% by volume. Except for, invention proposes a method for preparing oxirane compound from hydrocarbon phase obtained at the step (e) by the method described above and containing alkylaryl hydroperoxide. The presence of the protective layer reduces the pressure increment in the catalyst layer that is caused by the declined content of impurities in the raw comprising alkylaryl hydroperoxide.

EFFECT: improved preparing method.

7 cl, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: molybdenum is recovered from catalytic olefin epoxidation products using organic hydroperoxides. Method comprises treating heavy epoxidate fraction with alkali solution, treating resultant spent alkali stream with extractant, and subsequent precipitation of molybdenum trisulfide using sulfur-alkali effluents formed in production of olefins by pyrolysis of hydrocarbon feedstock.

EFFECT: increased molybdenum recovery degree and simplified operation.

11 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes method for epoxydation of olefins with ethyl benzene hydroperoxide in the presence of molybdenum-containing catalyst and nitrogen-containing compound. Derivatives of quinolines or Mannich base or their mixtures are used as nitrogen-containing compound and the mole ratio molybdenum : nitrogen-containing compound is maintained = 1:(0.05-0.4). Invention provides enhancing conversion and selectivity of the epoxydation process of olefins with organic hydroperoxides.

EFFECT: improved method for epoxydation.

3 cl, 15 ex

The invention relates to a method of producing accelerated, and more particularly to a method of producing accelerated of the alkene, which used the epoxidation reactors operate in such a way that the service life of the catalyst in the epoxidation increases significantly
The invention relates to the field of petrochemicals

The invention relates to an improved method of epoxidation, which uses a titanium-containing catalyst composition

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
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