Method for epoxidation of olefins

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for continuous epoxidation of olefins with hydrogen peroxide in the presence of a heterogeneous catalyst accelerating the epoxidation reaction. Aqueous reaction mixture comprises the following components: (1) olefin; (2) hydrogen peroxide; (3) less 100 ppm of alkaline metals, alkaline-earth metals in ionogenic, complex or covalently bound form, as bases or base cations possessing pH value pkB less 4.5, or their combination, and at least 100 ppm of bases or base cations possessing pH value pkB at least 4.5, or their combination. Values in ppm are given as measure for the total mass of hydrogen peroxide in the reaction mixture.

EFFECT: improved method of reaction.

20 cl, 2 tbl, 14 ex

 

The present invention relates to an improved method of continuous epoxidation of olefins using a heterogeneous catalyst for accelerating the reaction of epoxidation, considerably reducing the deactivation of the catalyst.

Background of invention

From EP-A 100119 known that using hydrogen peroxide propene can be converted into the oxide, propene, if the catalyst is to apply a titanium containing zeolite.

Unreacted hydrogen peroxide from the reaction mixture epoxidation cost-effectively recover impossible. In addition, the presence of unreacted hydrogen peroxide due to the additional effort and costs associated with the treatment of the reaction mixture. Thus, in a preferred embodiment, the process of epoxidation of the olefin is carried out with the use of an excess of olefin corresponding to the achievement of a high degree of conversion of hydrogen peroxide. In order to achieve a high degree of conversion of hydrogen peroxide is advisable to apply a flow reaction system of continuous action. Moreover, for the process on an industrial scale in order to achieve high values of the yield and reduce the cost of subsequent processing of important high selectivity for CE is avago oxide olefin.

However, over time during continuous epoxidation of olefins activity and selectivity of the above-described titanium containing zeolite catalysts dramatically reduced, causing the need for frequent regenerating the catalyst. Economic reasons for carrying out the process on an industrial scale, this is unacceptable.

The literature describes numerous ways to either improve the catalytic activity and/or selectivity or reduce the catalytic decontamination of the above titanium containing zeolite catalysts.

From EP-A 230949 known neutralization titanosilicate catalyst before its use in the epoxidation reaction or in situ by strong bases with the introduction thus in the reaction mixture of large quantities of ions of alkali or alkaline-earth metals. The result of the neutralization is increased activity and selectivity for target olefin oxide in a periodic process.

However, as described in EP-A 757043 experiments show that if in a continuous process, the catalyst is neutralized before or during the reaction, its activity is much lower. Therefore, the catalyst serves to process before or during the epoxidation reaction is neutral or acidic with the firm. Experimental data on the EP AND 757043 confirm that the addition of neutral or acidic salts increase the selectivity, but the activity is less low in comparison with that achieved by adding grounds. But in EP-A 757043 are only examples, in which the catalyst is treated with salt before the reaction and the catalyst used in the form of suspension. In addition, the experiments were conducted only for 8 hours, but nevertheless they show a sharp drop in catalyst activity after 4 h, which is in any way unacceptable for industrial process.

Similarly, in EP-A 712852 the idea is that during the process of epoxidation catalyzed by silicalite titanium, in the presence of a minor salt selectivity increases. The experiments are all examples of conduct in the form of a periodic process with a stirring suspension of catalyst in one hour. Despite the opportunity to confirm that the presence of minority salts can have a positive effect on the selectivity of the catalyst for a short-term experiment, it was found that even if the reaction mixture continuous epoxidation reaction are minor salts, activity and selectivity over time is significantly reduced. Thus, the information contained in EP-A 712852, don't bring what to the creation of the reaction system, which can be cost-effectively applied in a continuous process of epoxidation using hydrogen peroxide in the presence of a heterogeneous catalyst.

Some patent documents relate to the problem of optimization of activity and selectivity titanosilicate catalyst in epoxidation reactions by adding nitrogen-containing compounds and regulating the pH of the reaction mixture. For example, in EP-A 1072599 we are talking about adding to the reaction mixture of nitrogen-containing bases, whereas in EP-A 1072600 described the use of buffer systems, including salts of these nitrogenous bases to control pH. EP-A 940393 refers to the addition to the reaction mixture epoxidation containing amide group of organic compounds. In the US 6429322 described the addition of strong bases, such as hydroxides of alkali and alkaline-earth metal and tetraalkylammonium, and the addition of weak bases such as ammonium hydroxide and salts of alkaline or alkaline-earth metal weak acid to regulate the pH of the reaction mixture. But none of these links are not considered and not the influence of impurities normally contained in the commercially available aqueous solution of hydrogen peroxide, on a long-term activity and selectivity titanosilicate catalyst.

Now p is overwhelming quantity of hydrogen peroxide get on well known antrahinonovye method. Review antrahinonovye method and its numerous modifications described in G.Goor, J.Glenneberg, S.Jacobi: "Hydrogen Peroxide" Ullmann′s Encyclopedia of Industrial Chemistry, Electronic Release, 6thed. Wiley-VCH, Weinheim June 2000, p.14.

Crude solutions of hydrogen peroxide or concentrated solutions of hydrogen peroxide obtained by antrahinonovye method, in addition to hydrogen peroxide, contain low concentrations of many compounds. These compounds are either impurities or additives such as stabilizers. Impurities are compounds that are extracted from the working solution aqueous phase. They are mainly ionic or polar materials such as carboxylic acids, alcohols, carbonyl compounds, and amines. Therefore, these impurities are also contained in the technical solutions of hydrogen peroxide.

As examples of solvents hydroquinone, which is usually used in the above process, it should be mentioned nitrogen-containing compounds, such as amides and urea derivatives (see the above-mentioned work Ullmann, p.6). Especially preferred tetraalkylammonium, such as tetrabutyltin. The result of applying these solvents are contained in the final solutions of hydrogen peroxide amine impurities such as monoalkyl - and dialkyl, mainly monobutyl - and di is ethylamine. For example, the technical solution of hydrogen peroxide HYPROX®available on the company Degussa AG, contains up to 200 parts by weight per million of mono - and dibutylamino in terms of the weight of hydrogen peroxide.

In WO 00/76989 discusses the influence of ionic components in the commercially available aqueous solutions of hydrogen peroxide, which is used in epoxidation reactions as described in the above-mentioned dedicated to the art documents. To reduce the risk of decomposition of hydrogen peroxide in the commercially available aqueous solutions of hydrogen peroxide as stabilizers add ionic components, mainly phosphates and nitrates. In contrast to the abovementioned dedicated to the art documents WO 00/76989 the idea is that the presence of ionic components in the reaction mixture, even those that are added as stabilizers in technical hydrogen peroxide, has a negative impact on long-term selectivity during the continuous catalyzed silicalite titanium epoxidation reaction and, therefore, their content must be reduced to a minimum. In contrast to the abovementioned dedicated to the art documents continuous reaction, which was carried out for 300 hours, prodem who has Staropoli, what if the ionic components are contained in amounts greater than 100 ppm million, long-term selectivity is reduced. To resolve this problem prior to use in epoxidation reactions proposed removal of ionic components from solutions of hydrogen peroxide with the aid of ion exchangers. Moreover, in WO 00/76989 we are talking about the fact that ammonium compounds and ammonia should be avoided under any circumstances, because the presence of these compounds can lead to the formation of undesirable by-products due to reactions tripping oxiranes rings formed by the olefin oxide. Although the information contained in WO 00/76989, allows us to come to some improvement in long-term selectivity in comparison with the specified in the above documents, dedicated to the art, this improvement is still insufficient for carrying out the process on an industrial scale. Moreover, this improvement can only be achieved by the implementation of complicated and related costs for research and technology economically undesirable additional process stage of ion exchange. And finally, but not less importantly, the removal from solution of hydrogen peroxide stabilizing ions, such as phosphate and nitrate, makes the process more dangerous, and for the guarantee security during the process as a whole should be taken additional measures.

In contrast described in WO 00/76989 in WO 01/57012 says that the use of crude solutions of hydrogen peroxide directly obtained by antrahinonovye method, including, for example, large amounts of sodium, nitrate, phosphate and organic impurities, has an advantage in terms of selectivity with respect to the product, in comparison with the use of highly purified solutions of hydrogen peroxide, containing very small amounts of sodium, nitrate, phosphate. However, the experiments carried out within just several hours, resulting in a long-term activity and selectivity of the catalyst according to this link it is impossible to judge.

In addition, as another technical acceptance selected the one described in the application WO 01/92242, according to which the proposed method catalyzed by silicalite titanium epoxidation of olefins using crude solutions of hydrogen peroxide in the presence of compounds with aminocarbonyl functional group in which the nitrogen atom carries at least one hydrogen atom. In the examples shown, a process of periodic type, which spend up to 85%conversion of hydrogen peroxide. After two hours the reaction is stopped even if you do not achieve 85%conversion. Although experimental data demonstrate improvement in that is, with regard to the reaction rate, in comparison with the cases of using compounds with aminocarbonyl functional group containing a hydrogen atom bound to the nitrogen atom, according to information contained in WO 01/92242, long-term activity and selectivity of the catalyst in a continuous process it is impossible to judge.

In DE-A 19936547 describes how continuous catalyzed silicalite titanium epoxidation of olefins by hydrogen peroxide, in the exercise of which a constant degree of conversion is supported by the increase of the reaction temperature and the regulation of the pH of the reaction mixture. During the long term experiment (1000 h) could be sure that the regulation of pH temperature rise and rate of rise could be reduced in comparison with the data of the experiment without pH regulation. But the conversion and selectivity remained the same regardless of regulating the pH or not.

Thus, an object of the present invention is to develop a method of continuous epoxidation of olefins with hydrogen peroxide in the presence of a heterogeneous catalyst for accelerating the reaction of epoxidation, which improve long-term activity and selectivity of the catalyst in comparison with the previously discussed above is known for achieving cost-EF is an objective way without adding additional process steps.

The invention

This goal is achieved by providing a method of continuous epoxidation of olefins with hydrogen peroxide in the presence of a heterogeneous catalyst for accelerating the reaction of epoxidation, making water the reaction mixture includes:

I) an olefin;

II) hydrogen peroxide;

III) less than 100 parts per million of alkali metals, alkaline earth metals, regardless of whether those and other ionic or complex form, bases or base cations having a value PKInless than 4.5, or combinations thereof; and

IV) at least 100 parts by weight per million bases or base cations having a value pkBat least 4.5, or combinations thereof,

in accordance with the values in parts by weight per million specified in terms of the total weight of hydrogen peroxide in the reaction mixture.

Detailed description of the invention

It was found that even when taking into account the presence of ionic components in water solutions of hydrogen peroxide, these solutions can be used in the method according to the present invention without further purification such as ion exchange, if for implementing the method chosen by the hydrogen peroxide solution, containing less than 100 parts per million of alkali metals, alkaline earth metals, regardless of whether those and other ionage the Noi or complex form, bases or base cations having a value pkBless than 4.5, or combinations thereof, calculated on the total weight of hydrogen peroxide in the reaction mixture. The content of anions regardless of their nature above 100 parts per million, calculated on the total weight of hydrogen peroxide in the reaction mixture does not adversely affect long-term activity and selectivity of the catalyst, if only the reaction mixture consisted of at least 100 parts by weight per million bases or base cations having a value pkBat least 4.5, or their combinations in terms of the total weight of hydrogen peroxide in the reaction mixture.

Thus, contrary to the information contained in the documents on the art for a cost-effective process for the epoxidation of olefins is unacceptable neither the use of a crude solution of hydrogen peroxide obtained by antrahinonovye method, without careful control of the quantity of alkali metals and amines having a pk valueBbelow 4.5, nor the use of treated solutions of hydrogen peroxide, which, in addition to the metal cations, deleted stabilizing anions.

The implementation of the method according to the present invention unexpectedly provides long-term selectivity of 90% when the degree of conversion of hydrogen peroxide significantly in the above 90% even after the process for more than 2300 hours This result is reached without any costly stages of purification such as ion exchange.

The preferred reaction mixture further includes

V) at least 100 parts by weight per million anions or compounds that are capable of dissociate with the formation of anions, in total, in terms of the weight of hydrogen peroxide.

A special advantage of the proposed solution of hydrogen peroxide is that the anions may be contained in the usual stabilizing amounts. In the preferred embodiment, these stabilizing anions are anions of any type of oxaphosphorin anions, such as orthophosphates, acid phosphate, monopotassium phosphate, pyrophosphate, nitrate.

These stabilizing anions or compounds in which the hydrogen peroxide solution can dissociate with the formation of these stabilizing anions, in the preferred embodiment is contained in a quantity of at most 1000 parts by weight per million, preferably from 100 to 1000 parts by weight per million, more preferably from 200 to 800 parts by weight per million, most preferably from 200 to 600 parts by weight per million, calculated on the weight of hydrogen peroxide.

In accordance with the preferred implementation of the present invention, the number of components group III) in total is less than 80 parts by weight per million, preferably less than 70 parts by weight per million), more pre is respectfully less than 60 parts by weight per million, and most preferably less than 50 parts by weight per million, calculated on the total weight of hydrogen peroxide.

Particularly useful when the reaction mixture includes

IIIa) is less than 50 parts by weight per million of alkali metals, alkaline earth metals or combinations thereof in total, regardless of whether alkaline or alkaline-earth metals in cationic or complex form; and

IIIb) is less than 50 parts by weight per million amines having a pk valueBless than 4.5, or the corresponding protonated compounds in total;

in accordance with the values in parts by weight per million specified in terms of the weight of hydrogen peroxide.

In a preferred embodiment, in order to further improve the long-term activity and selectivity of the catalyst, the quantity of alkali metals, alkaline earth metals or combinations thereof in total, regardless of whether these are alkaline or alkaline-earth metals in cationic or complex form, is reduced to less than 40 parts by weight per million, more preferably less than 35 parts by weight of/million

The influence of the presence of such amines is even more pronounced than the influence of alkali or alkaline-earth metals. Therefore, in a particularly preferred embodiment, the number of amines having a pk valueBless than 4.5, in an aqueous solution of hydrogen peroxide which in total is reduced to less than 40 parts by weight per million, preferably less than 30 parts by weight per million, more preferably less than 20 parts by weight per million, and most preferably less than 10 parts by weight per million, calculated on the weight of hydrogen peroxide in the solution.

Another unexpected result of this invention is that the presence of bases or base cations having a value pkBless than 4.5, such as trimethylamine (pkB:4.26 deaths) or methylamine (pkB:3,36), has a long-term activity and selectivity of the catalyst a negative effect, whereas in order to achieve the target result of the presence of bases or base cations having a value pkBat least 4,5, such as ammonia (pkB:4,76)is mandatory. This is a fundamental difference in the behavior is quite similar compounds in the light of currently known information foreknowledge cannot be.

Especially negative impact on the activity and selectivity of the epoxidation catalyst due to the presence of alkylamines followed, mainly secondary and tertiary alkylamines followed.

In addition, preferably, when the number of components group IV) a total of at most 3000 parts by weight per million, more preferably from 150 to 2000 parts by weight per million, more preferably from 200 to 1500 parts by weight per million, and most preferably from 300 to 1200 parts by weight per million is calculated on the weight of hydrogen peroxide.

In accordance with a particularly preferred implementation of the present invention, the components of group (IV) is chosen from organic amines and amides having a value pkBat least 4,5, organic hydroxylamines having a value pkBat least 4,5, ammonia and hydroxylamine. In the preferred embodiment, no aminocarbonyl functional compounds in the reaction mixture did not add.

Hydrogen peroxide is used in the method in accordance with the invention in the form of an aqueous solution containing hydrogen peroxide is from 1 to 90 wt.%, preferably from 10 to 70 wt.%. Particularly preferred solution containing from 50 to 70 wt.% hydrogen peroxide, providing further improved long-term activity and selectivity of the used catalyst.

For implementing the method of the present invention can be used an aqueous solution of hydrogen peroxide, which is prepared according to the method of obtaining the solution of hydrogen peroxide in accordance with the technology with antrahinonovye circuit, comprising the following stages:

(a) hydrogenation of a working solution comprising an organic solvent or mixture of organic solvents and one or more active antrahinonovye connections

(b) oxidation of the hydrogenated working solution with obtaining perok the IDA hydrogen

(C) extraction of the hydrogen peroxide water,

(g) stabilizing the extracted aqueous solution of hydrogen peroxide,

(d) an optional concentration of the aqueous solution of hydrogen peroxide to a concentration of hydrogen peroxide of at least 50 wt.% in recalculation on weight of a solution of hydrogen peroxide,

(e) drying the working solution after extraction and

(g) regenerative and cleaned of mortar,

thanks to that during the whole process either alkaline or alkaline-earth metals or amines having a pk valueBless than 4.5, or compounds forming such amines during the process, do not enter in quantities which determine the concentration

III) 100 parts by weight per million or more of alkali metals, alkaline earth metals, regardless of whether those and other ionic or complex form, bases or base cations having a value pkBless than 4.5, or combinations thereof;

preferably

IIIa) 50 parts by weight per million or more of alkali metals, alkaline earth metals or combinations thereof in total, regardless of whether these are alkaline or alkaline-earth metals in cationic or complex form; or

IIIb), 50 parts by weight per million or more amines having a pk valueBless than 4.5, or the corresponding protonated compounds is third in total;

in the resulting aqueous solution of hydrogen peroxide, in accordance with the values in parts by weight per million specified in terms of the weight of hydrogen peroxide.

Another advantage of hydrogen peroxide solution, which can be used in the method according to the present invention is that it can be easily and economically efficient way to cook using well-known antrahinonovye method, allowing additional purification stages are optional, and if the preparation of a solution of hydrogen peroxide intended for use in the method according to the present invention, in a preferred variant, they do not exercise. The only requirement for the implementation of this method associated with the hydrogen peroxide solution, in comparison with obtained by known modifications antrahinonovye method is that the process must be carefully controlled in order to avoid the introduction of alkali metals, alkaline earth metals, amines having a pk valueBless than 4.5, or compounds that during the implementation antrahinonovye method capable of forming such amines upon receipt of a solution of hydrogen peroxide, in amounts that would have caused concentrations higher than specified in accordance with the present invention limits.

Although the application of the of this requirement may be many ways antrahinonovye method the purpose of drying the working solution of the above stage (e) without the use of compounds of alkali or alkaline-earth metals, which are usually used for drying in the implementation known in the art antrahinonovye method for regenerating a working solution in stage (g) the processing of active aluminum oxide is particularly preferred to use the working solution, which is almost free from organic nitrogen compounds. In a preferred embodiment, the drying is carried out by evaporation of water under vacuum.

The method according to the present invention is particularly expedient if the catalytic epoxidation is carried out in a flow reaction system of continuous action, in which the reaction mixture is passed through a fixed catalyst layer in the process flow during the reaction at least partially remove heat of reaction. Therefore, in a preferred variant of the method according to the present invention is carried out in a reactor with a fixed bed comprising the cooling means.

Especially preferred embodiment of the present invention is a method for the catalytic epoxidation of propene with hydrogen peroxide in a flow reaction system of continuous action, carried out in megafan the second reaction mixture, including liquid water rich in hydrogen peroxide phase containing methanol, and liquid organic-rich propene phase in which the reaction mixture is passed through a fixed catalyst layer in the process flow during the reaction at least partially heat of reaction away.

Contrary contained in the General guide information, an example of which is the work A.Gianetto "Multiphase Reactors: Types, Characteristics and Uses", in Multiphase Chemical Reactors: Theory, Design, Scale-up, Hemisphere Publishing Corporation, 1986, with the creation of the present invention, it was found that the cooled reactor with a porous layer capable of succeeding in the process flow with the increase of selectivity with respect to the product and therefore the overall product yield in comparison with achieved in the process according to the principle of the upward flow, which is still carried out in this field of technology. This effect is even more surprising since it is known that the epoxidation of the olefin is a highly exothermic reaction, the regulation of which involves the problems of a technological nature, because this reaction is characterized by a rather high activation temperature, and, consequently, to achieve an economically reasonable degree of conversion must be done at a certain minimum temperature is re. But on the other hand, the heat generated by an exothermic reaction, it is necessary from the reactor effectively to take, because at elevated temperatures occurring adverse reactions, which result in reduced selectivity for the product. The limited impact of increasing the temperature inside the catalytic layer to a certain extent discussed in EP-A 659473. As examples, they say that in the conventional tubular reactors the temperature rise in the catalytic layer exceeds 15°whereas in accordance with the examples in EP-A 659473 growth temperature is at most 8°and in the preferred embodiment, 51/2°C. Thus, as described in EP-A 659473 order to achieve high values of the yield of propylene oxide growth temperature inside the catalytic layer must be maintained as low as possible. In accordance with EP-A 659473, this reduced growth temperature could only be achieved by conducting the reaction in a single reaction zone to only partial conversion, resulting in the main part of the reaction mixture must be returned to the process, and intermediate cooling of the reaction mixture.

When in accordance with the work A.Gianetto etc. the process is carried out in a conventional tube of reaction is the er with a fixed layer, in the case of the process flow should expect poor heat dissipation and non-uniform temperature inside the catalytic layer. Thus, when carrying out the process flow in the usual cooled reactor with a fixed bed, without intermediate external cooling of the reaction mixture inside the catalytic layer due to poor heat dissipation should expect an indispensable high growth temperature, which should dramatically reduce the selectivity in respect of the product and hence its output. But contrary to this assumption, as is shown in more detail below in the examples, at the same time achieve improved selectivity with respect to the product with a similar degree of conversion in comparison with the results of the process based on the principle of the upward flow, and similar or even superior values of total output in terms of hydrogen peroxide in comparison with those which can be achieved in the most preferred embodiments, in EP-A 659473, despite the use of conventional reactor system, without intermediate external cooling.

When performing the present invention can be applied to any reactor containing a fixed catalyst layer and the cooling means. Adiabatic reaction conditions, as described in EP-A 659473 and US 5849937, you have escaped the th. In the preferred embodiment, used pipe, Novotrubny or mnogotarifnye reactors. In the most preferred embodiment, used pipe reactor equipped with a cooling water jacket, because they are usually available at a relatively low cost. As the cooling medium, which is pumped through the cooling means, preferably through a cooling jacket, you can use all standard cooling mediums such as oils, alcohols, liquid, salt and water. Most preferred is water.

Offer in accordance with the invention, a method of epoxidation of olefin, preferably propene, is generally carried out at a temperature from 30 to 80°C, preferably from 40 to 60°C. In accordance with the preferred implementation of the present invention, the temperature profile inside the reactor support so that the temperature of the cooling medium cooling medium pipe reactor was at least 40°and the maximum temperature inside the catalytic layer was equal to 60°C, preferably 55°C. In the preferred embodiment, the temperature of cooling environment regulate thermostat.

The maximum temperature inside the catalytic layer is measured using a variety of suitable means for measuring temperature, such thermocouples is whether the sensors Pt-100, placed approximately along the centerline preferably tubular reactor at an acceptable distance from each other. The ability to measure temperature in the catalytic layer inside the reactor as a whole with the precision that is needed to control the number of locations inside the reactor and distances between the means of the temperature measurement.

The maximum temperature of the catalytic layer can be adjusted by different means. Depending on the type of reactor maximum temperature of the catalytic layer can be adjusted by regulating the flow rate passing through the reactor the reaction mixture, the regulation of the flow rate of the cooling medium passing through the cooling means, or a loss of catalytic activity, for example by diluting the catalyst with an inert material.

In a preferred embodiment, the flow rate of the cooling medium adjusted so as to maintain the temperature difference between the cooling medium inlet in the cooling means and at the output is less than 5°S, preferably less than 3°S, most preferably less than 2°C.

The choice of such a specified narrow temperature profile inside the reactor can be achieved in an optimized balance between the degree of conversion of hydrogen peroxide and selectivity in who compared the olefin oxide.

The pressure inside the reactor is generally maintained at a level of from 5 to 50 bar, preferably from 15 to 30 bar.

In a preferred embodiment, the reaction mixture passed through the catalyst layer at a flow rate per unit cross section of the flow from 1 to 100 m/h, preferably from 5 to 50 m/h, most preferably from 5 to 30 m/h Flow rate per cross sectional area of flow is defined as the ratio of volumetric flow rate/cross-sectional catalytic layer. Therefore, the flow rate per unit cross section of the flow in this pipe reactor can be varied by regulating the speed of flow of the reaction mixture.

In addition, in the preferred embodiment, the reaction mixture is passed through a catalytic layer with an average hourly velocity of the fluid (SCSI) from 1 to 20 h-1preferably from 1.3 to 15 h-1.

Whenever the flow of the reaction mixture regulate in order to meet the above requirements in relation to the flow rate per unit cross-section of flow and average velocity of the fluid can be achieved for high values of selectivity.

In accordance with a particularly preferred implementation of the present invention the process is carried out so that in the catalytic layer supported mode "Oceania thin stream". It was found that if the mode Oceania thin stroika the layer support in certain conditions, expiry, the effect of the implementation of the present invention, i.e. high selectivity for propene oxide, is particularly pronounced.

These conditions include the following :

G/λ<2000 m/h and

Lψ<50 m/h, where

G denotes the flow rate per cross sectional area of the gas flow, defined in a flow reactor with continuous action as the velocity of the gas flow in m3/h divided by the cross-section of the catalytic layer in m2;

L denotes the flow rate per cross sectional area of fluid flow defined in a flow reactor with continuous action as the speed of fluid flow in m3/h divided by the cross-section of the catalytic layer in m2;

ρGdenotes the density of the gas phase in g/cm3,

ρLdenotes the density of the liquid phase in g/cm3,

ρWdenotes the density of water in g/cm3,

ρAirdenotes the air density in g/cm3,

σWindicates the water surface tension in Dyne/cm,

σLdenotes the surface tension of the liquid phase in Dyne/cm,

μLdenotes the viscosity of the liquid phase in centipoise,

μWdenotes the viscosity of water in centipoise.

In order to be able to carry out the process continuously, when ka is Aligator epoxidation replace and/or regenerate, you can also, if necessary, to use two or more reactors, placed in parallel or in series according to the above.

For implementing the method of epoxidation in accordance with the invention as catalysts suitable for use crystalline titanium containing zeolites, especially zeolite composition (TiO2)x(SiO2)1-xwhere x represents a number from 0.001 to 0.05, which is characterized by the crystal structure of the MFI or MEL, known as titanosilicate-1 and titanosilicate-2. Such catalysts can be obtained, for example, in accordance with the method described in US 4410501. Titanosilicates the catalyst can be applied in the form of a molded catalyst in the form of granules, extrudates, or other molded apply For opportunities molding process, the catalyst may include from 1 to 99% of the binder or of the material of the carrier, and all acceptable binders and materials carriers in the reaction conditions created for epoxidation, do not interact with hydrogen peroxide or an epoxide. In the preferred embodiment, as catalysts for stationary use layer extrudates with a diameter of from 1 to 5 mm

When performing the present invention in a preferred embodiment, entering the reactor, the total flow includes odny solution of hydrogen peroxide, olefin and an organic solvent. Thus, these components can be introduced into the reactor in the form of an independent source materials or prior to introduction into the reactor several of these source materials are mixed.

The application of the method in accordance with the invention allows to epoxidizing any olefins, particularly olefins containing from 2 to 6 carbon atoms. The method in accordance with the invention is most suitable for the epoxidation of propene to propene oxide. Economic reasons for carrying out the process on an industrial scale, preferably using propene not in pure form and in the form of technical mixtures with propane, which typically contains from 1 to 15 vol.% propane. Propa you can enter into the reaction system in liquid and in gaseous form.

In order to increase the solubility of the olefin, preferably propene, in the liquid phase, in the preferred embodiment, the reaction is carried out in the presence of a solvent. For use as a solvent suit all solvents that are in the selected reaction conditions, hydrogen peroxide is not oxidized or oxidized only to a low degree and are dissolved in water in amounts greater than 10 wt.%. Preferred solvents are completely mixed with water. Acceptable solvents include alcohols, such as methanol, ethanol and tert-butanol; glycols, such as ethylene glycol, 1,2-propandiol or 1,3-propandiol; cyclic ethers, such as tetrahydrofuran, dioxane or propylene oxide; glycol ethers, such as, for example, etilenglikolevye ether, etilenglikolevye ether, etilenglikolevye ether or propilenglikolmonostearata ether; and ketones, such as acetone or 2-butanone. Especially preferred for use as the solvent methanol.

In the preferred embodiment, to ensure that significant consumption of hydrogen peroxide olefin is used in excess relative to the hydrogen peroxide, and preferred is a molar ratio between the olefin, preferably by propene and hydrogen peroxide is chosen in the range from 1.1 to 30. In a preferred embodiment, the solvent is added to the value of mass attitudes towards the use of hydrogen peroxide solution from 0.5 to 20. The amount of catalyst can be varied within a wide range, and in the preferred embodiment, it is chosen so that the generated reaction conditions during the period from 1 min to 5 h, the consumption of hydrogen peroxide exceeded 90%, preferably more than 95%.

In accordance with one implementation of the present izaberete the Oia choice of the reaction conditions, in particular temperature and pressure, the choice of the olefin and the choice of solvent and the relative quantities of the components of the reaction mixture is performed to ensure the presence of only one aqueous liquid phase in which is dissolved olefin. May also be additional gaseous phase containing olefin.

However, in the preferred embodiment, the process of epoxidation of olefins with hydrogen peroxide is carried out in a multiphase reaction mixture comprising a liquid aqueous phase rich in hydrogen peroxide containing organic solvent with at 25°solubility in water of at least 10 wt.%, and liquid organic phase rich in olefins. Thus can be achieved even higher selectivity for the product.

As can be noted by a person skilled in the art, the presence of two immiscible liquid phases in the reaction system, comprising the olefin, is not miscible with water, an organic solvent and an aqueous solution of hydrogen peroxide, usually depends on many different factors. First of all, the presence of additional rich olefin liquid organic phases are usually created depends on the reactor temperature and pressure and the selected olefin. In a preferred embodiment, the generated pressure is equal to or greater than the vapor pressure of the olefin in the currently selected temperature. In addition, it usually depends on the choice of organic solvent. For use as an organic solvent suitable all solvents, which at 25°dissolved in water in amounts greater than 10 wt.%. Preferred solvents that at 25°dissolved in water in amounts greater than 30 wt.%, preferably at 25°With more than 50 wt.%. The most preferred solvents are completely mixed with water. In principle, this preferred embodiment can also be used all solvents, examples of which are given above, if only the conditions corresponded to guarantee the presence of two liquid phases.

Furthermore, the presence of a second organic phase rich in olefin, usually depends on the relative amounts of olefin, water and solvent. The amount of solvent is chosen in order to achieve rich in hydrogen peroxide aqueous phase solubility of the olefin sufficient to achieve the target rate of reaction. Under these conditions of temperature, pressure, olefin and the solvent relative to the number of components can be adjusted to guarantee the formation of a second liquid, the organic phase. In other words, in order to guarantee the formation of a second liquid, the organic phase rich in olefin selected number of olefin should be excessive relative to the amount of soluble the aqueous phase at the chosen temperature and pressure.

A simple remedy experimental confirmation of the presence in the reaction conditions of the second liquid, the organic phase is a sample of the reaction mixture in a container equipped with a sight glass in a temperature and pressure at which the conduct process. In another embodiment, the reactor may be equipped with a sight glass located in a convenient position for observation of the boundaries of the phases during the reaction. In case of a flow reactor continuous sight glass in the preferred embodiment, placed in the vicinity of the outlet openings for the exhaust from the reactor flow for optimum control of the presence of two liquid phases during the entire residence time inside the reactor.

Thus, when the approach to olefins, solvents and reaction parameters are to some extent selective, specialist in the art is able, without any effort to ascertain whether there is a system with two liquid phases, as required by the present invention, and the variation described above options is able to adjust the reaction system in such a way as to create a second liquid, the organic phase.

In accordance with the most preferred implementation of the present invention as olefin choose the prop is h, and the solvent is methanol. For example, in the case of a reaction mixture comprising propene, methanol and aqueous hydrogen peroxide, the reaction temperature in the range of 30 and 80°and under a pressure of from 5 to 50 bar for the formation of a second liquid, the organic phase ratio between the flow of propene and total flow in case of a flow reaction system of continuous action can be adjusted so that it was in the range of from 0.1 to 1, preferably from 0.2 to 1.

In accordance with the present invention may also be additional gas phase, comprising a pair of olefinic and optional inert gas, i.e. gas, which epoxydecane not. Adding an inert gas can be used to keep the inside of the reactor constant pressure and to remove gaseous oxygen formed by decomposition of a small part of the input to the reactor of hydrogen peroxide.

The essence of the present invention are described in more detail with reference to the following examples.

Examples

Example 1

Obtaining an aqueous solution of hydrogen peroxide intended for use in the method according to the present invention

In the experimental setup for the process circuit in accordance with antrahinonovye method policereported hydrogen, includes stage hydrogenation, oxidation, extraction, drying and regenerating, used working solution, consisting of 0.11 mol/l 2-ethylanthraquinone, to 0.29 mol/l 2-ethyltetrafluoroethylene, of 0.13 mol/l 2-isohexadecane and 0.12 mol/l 2-isohexadecane in a mixture of solvents, including 75% vol. With9/S10alkyl substituted aryl compounds and 25 vol.% Tris(2-ethylhexyl)phosphate. On stage hydrogenation reactor with circulation worked under hydrogen pressure of 0.35 MPa and at a temperature of 58°C. as the hydrogenation catalyst used, the palladium black (0,5:1 g/l). Equivalent of hydrogen peroxide in the process of hydrogenation was 13,0 g/l

After the hydrogenation portion of the hydrogenated working solution was regenerated using active alumina. After that, the combined working solution was oxidized using the method of oxidation Laporte so, as stated in the work G.Goor, J.Glenneberg, S.Jacobi: "Hydrogen Peroxide" Ullmann′s Encyclopedia of Industrial Chemistry, Electronic Release, 6thed. Wiley-VCH, Weinheim June 2000, p.14. Then hydrogen peroxide was extracted using deionized water. In the extraction water was added 50 PM/million N3RHO4and 20 hours/million HNO3both the number specified in terms of the weight of hydrogen peroxide. The concentration of the extracted aqueous solution of Perak the IDA hydrogen was 41%. The working solution was dried by evaporation of water under vacuum and then returned to the process at stage hydrogenation. The crude hydrogen peroxide solution stabilized with the use of 200 hours/million pyrophosphate of sodium, calculated on the weight of hydrogen peroxide and concentrated under vacuum by evaporation of water.

The concentration of the hydrogen peroxide solution obtained in this way was 43 wt.% in terms of the total weight of the solution; it contained 250 mg/kg N2About2phosphate, 20 mg/kg of nitrate and 30 mg/kg of sodium.

Examples 2 through 6 and comparative examples 1 to 8

All of the examples used titanosilicate catalyst. From titanosilicates powder using a colloidal solution of silicic acid as a binder in accordance with example 5 in EP 00106671.1 was molded 2 mm extrudates. A solution of N2About2in accordance with example 1 was used after concentration by evaporation of water up to 60 wt.%.

Epoxidation was performed continuously in a reaction tube with a volume of 300 ml, with a diameter of 10 mm and a length of 4 m moreover, the equipment consisted of three containers for liquids and associated pumps, as well as the vessel for separating liquid. Three containers for liquids contained methanol, 60%H2About2and propene. The reaction temperature was controlled by using water ohla is giving liquid, which is circulated in the cooling jacket, so with a thermostat regulating the temperature of the coolant. In the reactor the absolute pressure was 25 bar. The mass flow rate of the supply pump was controlled so that the concentration of propene was equal to 38 wt.%, the initial concentration of methanol was 48.7 wt.%, and the initial concentration of H2About2was equal to 8 wt.%. Furthermore, methanol was added to the original material, containing additional components, or made crude N2About2(250 mg/(kg H2About2) phosphate, 20 mg/(kg H2About2) nitrate, 30 mg/(kg H2O2) sodium), or intentionally made, which are listed in table 1.

When conducting the experiments of these examples and comparative examples, resorted to peritonea method expires, the temperature in the cooling jacket brought up to 35°and the total mass flow was equal to 0.35 kg/h of the Formed stream was analyzed by gas chromatography, and the degree of transformation of H2About2was determined by titration. The selectivity in respect of the H2About2was calculated as the ratio between the number of probenecid and the total number of probenecid and other by-products formed from the N2About2. The determination was carried out after the time of the experiment, asanoha in table 1.

Table 1
No.The number of added components group III) [mg/kg N2O2]The number of components group IV) [mg/kg N2About2]The time of the experiment [h]The transformation of N2About2[%]The selectivity in respect of the H2About2[%]
PR-NH32007329490
PRLi 25NH35009459590
PR-NH31000479789
PR-NH3100011149691
PR-NH3100023569490
SRPNa 1700489890
SRPNa 17006198875
SRPNa 20+Li 5007458276
SRPN 20+Li 50 021842871
SRPNa 20+Li 10008428578
SRPNa 20 + Li 100021344568
SRPMe3N 15003804274
SRPMeNH2100NH3100021422182

Data pkBfor the nitrogenous bases are published in the work H.R.Christen; "Grundlagen der organischen Chemie"; Verlag Sauerländer Aarau, Diesterweg Sall Frankfurt am Main; 1975; p.392 presented in table 2

Table 2
FoundationpkB
NH34,76
Me3N (trimethylamine)4.26 deaths
MeNH2(methylamine)3,36

If we compare the data of example 4 with the data of comparative example 1, it is obvious that at the beginning of a continuous process after 48 h, the values of conversion and selectivity are almost the same. This explains why adding a minor salts as described in EP-A 712852 THE EP AND 757043 described them briefly experiments leads to acceptable results. But with increasing duration of the experiment in comparative examples 1 to 6 demonstrate a significant decrease in the degree of conversion and selectivity, whereas in example 5, even after more than 2300 h, the degree of conversion and selectivity are still acceptable. Comparative examples 7 and 8 show that the addition of amine bases, having a value PKInless than 4.5, over time leads to a very big decrease in the degree of conversion and selectivity.

1. Method for continuous epoxidation of olefins with hydrogen peroxide in the presence of a heterogeneous catalyst for accelerating the reaction of epoxidation, in accordance with which the aqueous reaction mixture includes

I)an olefin;

II) hydrogen peroxide;

III) less than 100 parts per million of alkali metals, alkaline earth metals, regardless of whether those and other ionic or complex form, bases or base cations having a value pkInless than 4.5, or combinations thereof; and

IV) at least 100 parts by weight per million bases or base cations having a value pkInat least 4.5, or combinations thereof,

in accordance with the values in parts by weight per million specified in terms of the total weight of hydrogen peroxide in the reaction mixture.

2. The method according to claim 1, in which the share of the components in group III) in total is less than 80 parts by weight per million, preferably less than 70 parts by weight per million, more preferably less than 60 parts by weight per million, and most preferably less than 50 parts by weight per million, calculated on the total weight of hydrogen peroxide.

3. The method according to claim 1, wherein the reaction mixture includes

IIIa) is less than 50 parts by weight per million of alkali metals, alkaline earth metals or combinations thereof in total, regardless of whether alkaline or alkaline-earth metals in cationic or complex form; and

IIIb) is less than 50 parts by weight per million amines having a pk valueInless than 4.5, or the corresponding protonated compounds in total;

in accordance with the values in parts by weight per million specified in terms of the weight of hydrogen peroxide.

4. The method according to one of the preceding paragraphs, in which the number of components group IV) a total of at most 3000 parts by weight per million, preferably from 150 to 2000 parts by weight per million, more preferably from 200 to 1500 parts by weight per million, most preferably from 300 to 1200 parts by weight per million, calculated on the total weight of hydrogen peroxide.

5. The method according to claim 1, in which the components of group (IV) is chosen from organic amines and amides having a value pkInat least 4,5, organic hydroxylamines having a value pkInat least 4,5, ammonia and hydroxylamine.

6. The method according to claim 1, in which the reaction is ionic mixture further includes

V) at least 100 parts by weight per million anions or compounds that are capable of dissociate with the formation of anions, in total, in terms of the weight of hydrogen peroxide.

7. The method according to claim 1, wherein the reaction is carried out in a reaction system with a continuous flow, where the reaction mixture is passed through a fixed catalyst layer on the principle of flow during the reaction at least partially remove heat of reaction.

8. The method according to claim 7, in which is used a reactor with a fixed bed comprising the cooling means.

9. The method according to claim 8, in which a reactor with a fixed bed is a pipe reactor, and the cooling means is a cooling jacket.

10. The method according to claim 7, in which the reaction mixture is passed through a catalytic layer with a flow rate per unit cross section of the flow from 1 to 100 m/h, preferably from 5 to 50 m/h, most preferably from 5 to 30 m/h

11. The method according to claim 7, in which the reaction mixture is passed through a catalytic layer with an average hourly velocity of the fluid (SCSI) from 1 to 20 h-1preferably from 1.3 to 15 h-1.

12. The method according to claim 7, in which the fixed catalytic layer supported mode "Oceania thin stream".

13. The method according to item 12, in which the mode of Oceania trickle" is supported in the following environments expiration: G/λ< 2000 m/HR and Lψ<50 m/h, where G denotes the flow rate per cross sectional area of the gas flow, defined in a flow reaction system of continuous action as the velocity of the gas flow in m3/h divided by the cross-section of the catalytic layer in m2;

L denotes the flow rate per cross sectional area of fluid flow defined in a flow reaction system of continuous action as the speed of fluid flow in m3/h divided by the cross-section of the catalytic layer in m2;

ρGdenotes the density of the gas phase, g/cm3;

ρLdenotes the density of the liquid phase, g/cm3;

ρWdenotes the water density, g/cm3;

ρAirdenotes the air density, g/cm3;

σWindicates the water surface tension, Dyne/cm;

σLdenotes the surface tension of the liquid phase, Dyne/cm;

μLdenotes the viscosity of the liquid phase, SP;

μWdenotes the viscosity of water, JV.

14. The method according to claim 7, in which the reaction temperature is from 30 to 80°C, preferably from 40 to 60°C.

15. The method according to 14, in which the temperature profile inside the reactor support so that the temperature Oh adusei environment means cooling was at least 40° C, the maximum temperature inside the catalytic layer was equal to 60°C.

16. The method according to claim 1, wherein the reaction mixture further includes:

VI) an organic solvent.

17. The method according to clause 16, in which the reaction is carried out in a multiphase reaction mixture comprising a liquid water-rich by hydrogen peroxide phase containing an organic solvent having at 25°solubility in water of at least 10 wt.%, and rich olefin liquid organic phase.

18. The method according to clause 16, in which the organic solvent is a methanol.

19. The method according to claim 1, in which the catalyst used titanium containing zeolite.

20. The method according to claim 1, wherein the olefin is a propene.



 

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