Method of production of oxirane, installation for its realization and a combined method of production of hydrogen peroxide and oxirane

FIELD: chemical industry; production of hydrogen peroxide and oxiranes.

SUBSTANCE: the invention is dealt with a method of production of hydrogen peroxides and oxiranes. The invention provides for conductance of reaction of olefin with hydrogen peroxide at the presence of a catalyst and organic thinner. At that hydrogen peroxide is present as a water solution of hydrogen peroxide extracted mainly with the help of purified water out of a mixture produced as a result of oxidation at least of one alkylanthrahydroquinone without aftertreatment with a cleansing water and-or purification. The technical result is an increase of an output and selectivity of oxirane.

EFFECT: the invention ensures increased output and selectivity of oxirane.

17 cl, 5 tbl, 10 ex

 

The present invention concerns a method of obtaining oxirane by reaction of olefin with hydrogen peroxide in the presence of a catalyst and diluent. More specifically the invention relates to a method for producing 1,2-epoxypropane (or propylene oxide) by reaction of propylene with hydrogen peroxide.

A known method of producing propylene oxide by epoxidation of propylene with hydrogen peroxide in the presence of a catalyst of the type TS-1, as described, for example, in patent application EP 0230949.

Apply hydrogen peroxide, usually well cleaned from organic impurities. Thus, the initial solutions of hydrogen peroxide (H2About2), obtained by extraction from a mixture obtained by oxidation of at least one alkylanthraquinones, usually one or more stages of washing, extraction and/or distillation prior to sale and/or use in the methods of synthesis. This applies, in particular, to the solutions of H2About2used to obtain oxiranes.

Patent application EP 549013 applies to United way of the oxidation of organic substances and obtain H2O2way using alkylanthraquinones (AO), in which the solvent, extracting the H2O2from quinone catcher, CA is both a mixture of water/alcohol, used in the oxidation of organic matter. The applicant stated that this method has several disadvantages:

- lack of flexibility of the method in General, related to the fact that each stage of the synthesis (AO and oxidation depends on another stage;

limit the alcohol content with mixtures of water/alcohol, due to the extraction conditions, which adversely affects the output of the H2O2in the method of the epoxidation reaction;

- difficulties arising from the separation of phases in the method of extracting a mixture of water/alcohol;

- the passage of a significant amount of methanol in the quinone catcher, as a result, given the low flash point of methanol, there is a real danger of explosion vapour phase oxidation steps in the synthesis of H2O2;

- extracted significant number of quinones in a mixture of water/alcohol, which reduces the profitability of the industrial plant; and

- pollution quinone catcher byproducts of the oxidation reaction.

In addition, in the known epoxidation reactions are usually applied propylene, having a relatively high degree of purity, in particular, to avoid side reactions of the oxidation of impurities, mainly in order to improve the efficiency and security. Indeed, propane are the two which is the main impurity propylene, and the patent BE 1001884 indicated that hydrogen peroxide can oxidize alkane in the presence of TS-1.

In addition, the product of the oxidation of propane is isopropanol. After reviewing the patent BE 1001884, a specialist in this area can come to the conclusion that in the continuous method of producing propylene oxide with recirculation of the organic solvent used in the reaction (usually methanol)and/or continuous or periodic method using a source of propylene, rich in propane, isopropanol accumulates in the solvent, and finally turns into acetone, which is difficult to separate from the specified diluent. In the presence of hydrogen peroxide that acetone may form explosive and, in addition, insoluble in the organic medium peroxides, which further increases the risk of explosion as a result of their deposition. Such a conclusion can be made for any oxidized alkane in the presence peroxidizing connection and TS-1 and, consequently, to any source of olefin (recycled or precirculation), rich alkanol (alkanes), which can be used in the epoxidation reaction.

So, in patents US 5599955 and 5599956 described using mainly purified propylene, i.e. with a degree of purity of at least 90% and preferably at least 98%, in which the main clause is imasu is propane.

However, various methods of synthesis of propylene (and olefins in General) usually lead to a significant content of propane (or, more generally, alkane(s)), which is even higher than the content of propylene, which involves the implementation of appropriate methods of separation and/or purification. The above-mentioned US patents 5599955 and 5599956 illustrate this problem.

In addition, in various industrial ways in which olefin is used, carry out the recycling of the unconverted fraction of the latter, usually enriched with alkanol(alkanes). In such methods, therefore, may require a separation of the components prior to the specified recycling. Examples of such methods include the polymerization of olefins and epoxidation.

The object of the present invention is a method of obtaining oxirane, which eliminated at least one of the above disadvantages and produce higher output, improved selectivity compared to the one obtained using purified extract.

Thus, the invention concerns a method of obtaining oxirane by reacting the olefin with hydrogen peroxide in the presence of a catalyst and an organic diluent in which hydrogen peroxide is an aqueous hydrogen peroxide solution, extracted with OS is the RAM purified water from the mixture, obtained by oxidation of at least one alkylanthraquinones without further processing by washing and/or cleaning.

The applicant really has been unexpectedly found that the use in the epoxidation reaction solution of N2About2obtained by extraction using water, instead of a mixture of water/alcohol, allows to increase the output of the specified H2O2. In addition, the use of the crude extract allows you to win in selectivity compared to the use of purified extract.

Methods for producing hydrogen peroxide using alkylanthraquinones(s) or methods of JSC well known and widely described in the literature (see, for example, Ullmann Encyclopedia of Industrial Chemistry, Fifth Edition, 1989, vol. 3, pp. 447-57"). They are to be subjected to the hydrogenation of a working solution of at least one alkylanthraquinones and/or at least one tetrahydrogestrinone in diluent to obtain one or more alkylanthraquinones and/or alkylmethacrylamide. The working solution, the last stage of hydrogenation, then subjected to oxidation with oxygen, air or air enriched with oxygen, to obtain hydrogen peroxide and re-education of alkylanthraquinones and/or alkyldiethanolamine. The resulting hydrogen peroxide then from Aleut from the working solution at the stage of extraction. According to the present invention the Department is using mostly purified water. Obtained at the stage of extracting the working solution is directed to a stage of hydrogenation for the renewal of the cycle of obtaining hydrogen peroxide.

Under alkylanthraquinones mean, for example, 9,10-anthraquinones, substituted by at least one alkyl side chain, linear or branched, aliphatic type, containing at least one carbon atom. Typically, these alkyl chains containing less than 9 carbon atoms and preferably less than 6 carbon atoms. Examples of such alkylanthraquinones are 2-ethylanthraquinone, 2-isopropylaniline, - 2-second - and 2-tert-butylanthraquinone, 1,3-, 2,3-, 1,4 - and 2,7-dimethylanthracene, 2-ISO - and 2-tert-milintachinda and mixtures of these quinones.

Under mostly purified water mean water containing less than 3 wt.% organic diluents, in particular, alcohol(s), preferably less than 0.1%, even less than 0.001% of the above-mentioned diluents. Water used for extraction may, however, mainly to contain inorganic substances at a minimum of about 0.001 wt.%, preferably 0.005%or even a minimum of 0.01%. The content of inorganic substances does not exceed, however, 1 wt.%, preferably of 0.5%, or even 0.1 percent. These inorganic substances are predominantly in the society, regulating pH, such as acids and, in particular, a strong acid such as nitric acid, phosphoric acid or salts of these acids. These inorganic substances may also primarily be substances, stabilizing H2O2such as salts of alkaline or alkaline earth metals and, in particular, sodium, such as sodium pyrophosphate. Extracting solution may, therefore, contain cations of metals such as alkali or alkaline earth metals, for example sodium and/or anions, such as phosphates, nitrates... in small quantities, usually less than 10 g/l, but greater than 0.01 g/L.

A solution of N2O2resulting from the extraction or the original solution of H2O2usually contains less than 50 wt.% H2About2more often less than 40% H2O2. It typically contains more than 5 wt.% H2About2often more than 10%, in particular more than 20%, or even 30%. Prior to use in epoxidation reaction he not been further processed by washing and/or cleaning. Therefore, it contains organic impurities (degradation products of quinone catcher) and inorganic particles (cations and anions introduced extracting water, as well as those that are already present in the mixture resulting from the oxidation of one or more alkylanthraquinones the ones). Extracted solution may contain organic impurities, expressed HUNDRED (concentration of total organic carbon), determined in accordance with ISO 8245 based at least 0.001 g/l, even at least 0.01 g/l, or even at least 0.1 g/l, but not more than 10 g/l, 1 g/l or even 0.2 g/L. It may also contain cations of metals such as alkali or alkaline earth metals, for example sodium and/or anions, such as phosphates, nitrates... in small quantities, usually less than or equal to 10 g/l but greater than or equal to 0.01 g/L.

The original solution of N2About2before its use in the epoxidation reaction can be diluted with water or any other liquid solvent or diluent which does not adversely influence the reaction of epoxidation. Typically, the aqueous solution used for epoxidation, contains at least 5 wt.%, most often at least 10 wt.% H2O2in particular at least 20 wt.%. It often contains a maximum of 50 wt.% peroxidizing compounds, in particular 40 wt.%.

Oxiran, which can be obtained by the process according to the invention is an organic compound that contains a group of General formula

Oxiran usually contains from 3 to 10 carbon atoms, suppose the equipment from 3 to 6 carbon atoms. Oxiran, which can mainly be obtained by the process according to the invention is 1,2-epoxypropanol.

The olefins that are acceptable for the method according to the invention usually contain from 3 to 10 carbon atoms and preferably from 3 to 6 carbon atoms. Particularly suitable propylene and butylene. Propylene is preferred.

The catalysts used in the method according to the invention, predominantly contain zeolite, namely, solid substance containing silicon dioxide having a crystalline microporous structure. Zeolite is mainly free from aluminum. Preferably it contains titanium.

The zeolite used in the method according to the invention, may have a crystalline structure of ZSM-5, ZSM-11, MCM-41 or type beta zeolite. Suitable zeolites of type ZSM-5. Preferred are those infrared absorption band which is around 950-960 cm-1.

Particularly suitable zeolites are silicalite containing titanium. Effective are those that have the formula xTiO2(1-x)SiO2where the value of x is from 0.0001 to 0.5, preferably from 0.001 to 0.05. Substances of this type, known as TS-1 and having a crystal structure of ZSM-5, give particularly good results.

The reaction medium according to the invention usually contains the separated liquid phase and gaseous phase.

Organic solvents used in the method according to the invention can be an organic derivative such as aliphatic alcohols containing from 1 to 4 carbon atoms. As example can be mentioned methanol. The diluent in the liquid phase reaction medium mainly more than 35 wt.%, preferably more than 60%, even 75%. The diluent in the liquid phase reaction medium usually nevertheless less than 99 wt.%, preferably less than 95%.

In a preferred embodiment of the method according to the invention oxirane obtained in the reaction medium can be separated liquid phase extraction using a solvent, as described in patent application WO 99/14208 the present applicant.

The method according to the invention may be continuous or periodic. In the continuous method, unreacted olefin may be recycled to the reactor.

In the reactor, in which the method according to the invention, may be the solution obtained in stage water extraction method JSC. In this case, the installation for implementing the method according to the invention also includes a system for producing a solution of N2About2by the way AO. Such installation and the way for which it is intended, are also the subject of the crust is asego of the invention.

Alternatively, you can store and/or transport of the solution prior to its introduction into the reactor, as in the case of purified solutions currently used.

In the method according to the invention a gas that does not have a negative impact on the epoxidation reaction can also be introduced into the reactor. Indeed, in the patent application WO 99/48883 the applicant stated that the introduction of gaseous compounds in the reaction medium with a flow rate sufficient to move the received oxiran and out of the reactor simultaneously with gaseous connection, you can reduce the duration of the contact obtained oxirane with the reaction medium epoxidation. This eliminates the possibility of formation of by-products and improving the selectivity of the epoxidation.

In a preferred embodiment of the method according to the invention the gaseous phase is introduced into the reactor in such a flow that it allows you not only to move at least a portion of oxirane, but also contribute to the circulation of the liquid phase in the reactor, especially if the reactor is a circulating type. In this case, the gaseous phase is normally introduced into the reactor in such amounts that the molar ratio of the flow rate specified gaseous phase to flow input H2O2 is at least 5, in particular at least 8, with normal values are equal to at least 10. The molar ratio of such costs typically less than or equal to 100, in particular 60, with normal values are less than or equal to 40 or even 20.

In the method according to the invention can be used reactor of any type, in particular the reactor of the circulating type. Good circulation reactors, bubble trap, in which the circulation fluid, and possibly the catalyst is achieved by bubbling the gas in one of the knees. This type of reactor described in the above-mentioned patent application WO 99/48883.

In the method according to the invention should maintain the pH value of the liquid phase during the interaction of the olefin with N2O2equal to at least 4,8, in particular at least 5. Mainly the pH value is less than or equal to 6.5, in particular 6. Good results are obtained when the pH is equal to 4.8 to 6.5, preferably 5-6. To adjust the pH of the liquid phase during the reaction of epoxidation is possible through the introduction of the Foundation. Such a basis can be chosen among water-soluble bases. It could be on a strong footing. As examples of a strong base, NaOH and KOH. It can also go on weak grounds. The weak base may be inorganic. As the examples of weak inorganic bases NH 4OH, PA2CO3, Panso3, Na2HPO4To2CO3, Li2CO3Knso3, Li3To2NRA4. The weak base may also be organic. Acceptable weak organic bases may be salts of alkali and alkaline earth metals with carboxylic acids containing preferably from 1 to 10 carbon atoms. As an example, can be called sodium acetate. Weak bases give good results. Preferred are weak organic bases. Most preferred is sodium acetate.

The molar ratio between the amount of olefin used and the number of H2O2usually greater than or equal to 0.1, in particular greater than or equal to 1 and preferably greater than 5. This molar ratio is often less than or equal to 100, in particular less than or equal to 50 and preferably less than or equal to 25.

In the method according to the invention, when it is carried out continuously and in the presence of zeolite used, the number of N2About2is usually at least 0,005 mol per hour and per gram of zeolite, in particular at least 0.01 mol per hour and per gram of zeolite. Usually the number of N2About2less than or equal to 2.5 mol per hour and per gram of zeolite and, in particular, less than or equal to 1 mol per hour and per gram C is the Olite. Preferred is the number of H2O2that is greater than or equal to 0.03 mol per hour and per gram of zeolite and less than or equal to 0.1 mol per hour and per gram of zeolite.

The interaction between the olefin and N2About2can be carried out in the presence of salts, such as metal salt or ammonium salt. The metal may be selected from among alkali or alkaline earth metals such as lithium, sodium, potassium, cesium, magnesium, calcium, strontium and barium. Metal salts are preferably the halides, oxides, hydroxides, carbonates, sulfates, phosphates and salts of organic acids such as acetates. Halides are usually fluorides, chlorides, bromides and iodides. Preferred are the chlorides. Salt, mainly used in the method according to the present invention, is preferably a halide of an alkali metal and preferably sodium chloride. The used amount of the metal salt is expressed as the content of metal ions or ammonium originating from salt relative to the amount of catalyst, expressed in mmol (mmol) metal or ammonium per gram of zeolite. Such content may be greater than or equal to 10-4mmol/g of zeolite and less than or equal to 10 mmol/g of zeolite. Mainly the content of the metal salt is greater than or equal to 10-3mmol/g of zeolite and less than or RA is but 1 mmol/g of zeolite. It is preferable for the content that is greater than or equal to 10-2mmol/g of zeolite and less than or equal to 0.5 mmol/g of zeolite.

The temperature of the reaction between the olefin and N2About2mostly above 35°that prevents the gradual deactivation of the catalyst. Preferred is a reaction temperature above or equal to 40°and preferably above or equal to 45°C. the Most preferred temperature is higher than or equal to 50°C. However, the reaction temperature is usually below 100°and preferably below 80°C. the Temperature at which the olefin interacts with H2O2usually ranges from 40°to 100°and preferably from 45°C to 80°C.

In the method according to the invention, the interaction between the olefin and N2About2can occur at atmospheric pressure. It can also occur under pressure. Typically, such pressure does not exceed 40 bar. In practice, acceptable pressure is 20 bar.

In accordance with a preferred method according to the invention the olefin interacts with hydrogen peroxide in the presence of a catalyst and an organic diluent in the liquid phase in the reactor, into which enter peroxid of hydrogen and an organic diluent, and a fluid substance containing olefin and alkane(s), the content of which SOS is to place at least 10% of the volume. Preferably the alkane content in the fluid substance is above 10% of the volume.

This option is preferred because it uses different sources of olefins, crude from alkanes to obtain oxiranes and because it was the way of the reaction of alkane oxidation by hydrogen peroxide unexpectedly decreases the amount of alcohol and ketone in the presence of the olefin, and it takes into account the dilution factor. Therefore, the danger of deposition of explosive peroxides is much less than might have been expected theoretically, and can thus be easily controlled in the installation of industrial level.

One of the main benefits of the preferred option is that the reactor is injected fluid substance, the content of one or more alkanes in which at least 10% of the volume. The content of the alkane(s) in the specified fluid substance may in some cases be at least equal to 20%, even 30%. You can also use the fluent substance, the content of the alkane(s) which is at least 50% of the volume. It is not recommended, on the contrary, to use a flowable substance, the content of the alkane(s) in greater than 95% of the volume, and even preferable to use a fluid substance, the content of the alkane(s) that do not exceed 85%.

<> The content of the olefin in the liquid substance is usually more than 50% of the volume, in particular at least 60% of the volume and preferably at least 70% of the volume. The amount of hydrogen introduced into the epoxidation reactor, usually less than 5% of the volume of fluid substances and preferably 0%. The amount of oxygen introduced into the epoxidation reactor, typically less than 10% of the volume of fluid substances.

One or more alkanes contained in the flowable substance according to the present invention typically contain from 3 to 10 carbon atoms and preferably from 3 to 6 carbon atoms. Preferably alkane is linear and does not contain, in particular, aromatic substances. In that case, if the olefin according to the invention is propylene, one or more alkanes consist primarily of propane. Preferably alkane is not used as the organic solvent in the epoxidation reaction and is different from the organic diluent.

The method according to the preferred variant may be continuous or periodic. If it is continuous, fluid substance can be recycled to the reactor after the interaction of the olefin with hydrogen peroxide.

In the first case, the implementation of the preferred variant of the method according to the invention the method is carried out continuously, and the fluid substance introduced into the reactor at the beginning of the process, contains alkane(s) in an amount comprising less than 10% of the volume. In the process of implementation of the method, the fluid substance is recycled to the reactor after the interaction of the olefin with hydrogen peroxide so that the recirculated fluid substance is gradually enriched by alkanol. The alkane content in the fluid substance then reaches at least 10% of the volume.

In the second case, the implementation of the preferred variant of the method according to the invention the method is continuous or intermittent, and fluid substance introduced into the reactor at the beginning of the method, already contains a number of alkane(s)constituting at least 10% of the volume.

Preferably flowable substance (containing olefin and one or more alkanes)introduced into the reactor is a gas. In this case, a special form of implementation of the preferred variant of the method according to the invention is that the flow of the specified gas introduced into the reactor, such that not only allows you to move at least a portion of oxirane, but also to cause circulation of the liquid phase in the reactor, in particular if the latter is the reactor of the circulating type. In this case, the flow rate of the injected gas is usually such that the molar ratio of the flow of the specified gas to the flow rate input peroxidizing connection is at least 5, particularly at least 8, the standard values are equal to 10. The molar ratio of such costs typically less than or equal to 100, in particular 60, with normal values are less than or equal to 40 or even 20.

In a preferred variant of the method according to the invention in its continuous implementation is preferable amount of hydrogen peroxide that is greater than or equal to 0.03 mol per hour and per gram of zeolite and less than or equal to 0.25 mol per hour and per gram of zeolite.

In a preferred variant of the method according to the invention an aqueous solution of hydrogen peroxide most often contains 70 wt.% peroxidizing compounds, in particular 50 wt.%.

The invention also concerns another method of obtaining oxirane, according to which in the reactor in the liquid phase is the interaction of the olefin with hydrogen peroxide in the presence of a catalyst and an organic diluent, and in accordance with which the reactor is injected hydrogen peroxide and an organic diluent, and a fluid substance containing olefin and at least 10% of the volume of alkane(s).

This is another method according to the invention corresponds to the preferred option described above, when it is carried out as such, not combining with the first method according to the invention, in which use an aqueous solution of hydrogen peroxide, extra is computerized using mostly purified water from the mixture, obtained by oxidation of at least one alkylanthraquinones, without further processing by washing and/or cleaning.

Conditions, which can be done this another way, identical to the first method except for the use of the initial hydrogen peroxide solution.

Example 1 (according to the invention) and 2C (comparative)

In the reactor of continuous action, containing a 5.25 g of TS-1, supported 35°at atmospheric pressure, and in it enter 0,57 mol H2About2per hour in the form of a 40 wt.% aqueous solution, 475 ml of methanol/h and 250 IN/I (or 11.2 mol/h) of propylene. Facing the liquid and the gaseous phase is subjected to analysis to determine the proportions of various organic substances, as well as the output of H2About2.

The table below shows the results of the experiments, which used fresh catalyst TS-1 obtained by methods known from the literature.

Example No.1 (invention)2C (comparison)
 source extracted N2O2purified H2O2
The output of the H2O2after 2 hours76,776,0
The same after 6 hours5453
Selectivity* after 6 hours90,585,4
* selectivity is expressed by the ratio mol/mol obtained PR (propylene oxide) to the total number of formed organic products.

See known gradual decrease in the activity of the catalyst, which does not affect the quality of H2About2. The presence of the original H2O2a positive effect only on the selectivity.

It should be noted the content of anions and cations in these solutions N2About2(table):

Content in mg/lsource H2O2purified H2O2
Na262,3
other cations (except H+)<0,3<0,3
NO3343,7
Phosphates, expressed in R281,4
TOC17269

Examples 3 (according to the invention) and 4C (comparative)

The table shows the results of experiments, similar in all respects to the one described in examples 1 and 2C during the cycle following the recovery of the catalyst. The catalyst in ustanavlivaetsya for 7 hours with passing through it of air, heated to 300°C.

Example No.3 (invention)4C (comparison)
 source H2O2purified H2O2
The output of the H2O2after 2 hours75,475,6
The same after 6 hours53,554,3
Selectivity** after 6 hoursto 91.185,7

Confirmed that the activity was identical, taking into account errors that are valid for measurements, and that the deviation selectivity is preserved.

Examples 5C (comparative) and 6 (according to the invention)

Solution synthesis of N2O2obtained after oxidation of quinone catcher/hydrochinone, were extracted with methanol/water, in which the methanol content is 52 wt.%. This aqueous extract is then used in the experiment epoxydecane propylene (example 5C) and the results were compared with results of a similar experiment, conducted with the original H2About2in the amount of 40 wt.% in water, obtained by extraction from the same catcher using mostly purified water (example 6). This catcher contains 11,8 g/kg H2O2.

Extra is tion with a mixture of water/alcohol was carried out in 4 stages. The first extraction was carried out by processing 14331 g catcher (containing generally 169,1 g H2About2with the help 1511 methanol/water. Phase methanol-water has a higher density than the original organic solution, and deposited relatively quickly (within approximately 15 min), forming 1085 g of extract. The concentration of H2About2it defined Lodomeria is 3,18 mol H2About2/kg, which corresponds to 3.45 mol or 117,4 g H2O2(=69% of the whole).

A second extraction was carried out using 1522 g of the same methanol/water. The Department was less obvious. The deposition took place very slowly: it took more than 1 hour in order to proceed with the separation of the phases. In contrast to the first extract phase of methanol-water at this time was less dense and contained 1215 g of extract. The concentration of H2About2it is equal to 0,833 mol/kg, which corresponds 1,012 mol or 34.4 g H2O2. Thus, two stages of extraction were collected 90% of the total H2About2.

A third extraction was carried out using 1511 g of the same methanol/water. The Department was also difficult, and were collected 1446 g phase methanol-water. The concentration of H2O2it is equal to 0,244 mol/kg, which corresponds to 0,353 mol or 12.0 g H2O2(i.e. the 3 stages of extraction was the elected to 96.9% N 2O2).

Finally, the fourth stage extraction was carried out using 1517 g of the same methanol/water. The Department was also difficult, and were collected 1497 phase methanol-water. The concentration of H2About2it is equal to 0,071 mol/kg, which corresponds to 0,106 mol or 3.6 g H2About2(i.e. the 4 stages of extraction were collected 99,0% H2O2).

All four of the extract is then mixed, obtaining a solution of methanol/water containing 0,94 mol H2About2/kg (control was carried out by titration). The methanol content determined using CPV is about 437 g/kg

The content of "useful" quinones (= which can be used to obtain the H2About2), lost in this phase, is 0,020 g/kg of the extract.

In addition, there is a clear transition of methanol in quinone catcher, as it shows the difference between the mass of the used mixtures of methanol/water and the collected extracts (in particular, on the 1st and 2nd stages of extraction). The methanol content of the quinone catcher determined using CPV, really close to 6 wt.%.

Experiments on epoxydecane propylene (PE) was carried out on the installation with bubbling siphon under the following conditions: T: 55°s; ow Re: 75 l/h under normal conditions; H2O2: to 0.17 mol H2About2/h; the concentration of H2O2in the circuit is zero ri conversions: 1.0 mol/kg; catalyst: 0,53 g TS-1.

With regard to example 5, the introduction of the mixture of all four extracts methanol/water containing H2O2in the installation with bubbling siphon would after the distillation to the education environment, "poor" methanol (concentration <440 g/kg). It was therefore introduced an additional amount of methanol so as to maintain its concentration in the contour of approximately 440 g/kg, which corresponds to the methanol content in the original H2O2used in the reference experiment (example 6).

The results obtained are set forth in the table below.

 The output of the H2O2(%)
 2 hours3 hours4 hours5 hours6 hours7 h24 hour25th hour26 hour
Ave. 5C30,420,718,615,312,610,48,78,48,1
Ave. 633,325,524,420,420,119,6of 17.518,417,2

Examples 7-9

The propylene oxide was obtained in the reactor with bubble trap, such as described is an in the application WO 99/48883, the interaction of propylene with hydrogen peroxide in the presence of methanol and catalyst TS-1 used in the form of balls with a diameter of 0.5 mm.

The experiments were conducted at a temperature of 55°with a continuous flow of 0.17 mol/HR of hydrogen peroxide. The total gas flow rate of 75 l/h under normal conditions (or 3.3 mol/hour). The initial concentration of H2O2in the circuit in the absence of conversion was 1.5 mol/kg, the number of the used catalyst was 4.5 g of beads containing 1.5 g of TS-1.

Example 1 used a mixture containing 75% of propylene "polymer grade" (98% propylene, and 0.3% propane) and 25% propane (molar %); in example 2 was used 100% propylene "polymer grade" and in example 3 used a mixture containing 75% of propylene "polymer grade" and 25% nitrogen.

The results obtained are shown below in the table.

The selectivity towards propylene oxide are given in molar ratio, expressed in percentage, between the amount of propylene oxide, divided by the sum of all organic substances obtained in the experiment of example C3.

 The output of the H2O2(%)Selectivity
 5 hours6 hours7 h5 hours
Example 7 57,455,352,685,8
Example 867,264,061,784,5
Example 959,153,351,285,9

The amount of isopropanol obtained in experiment 1 measured after 5 hours, is to 0.007 mmol/hour. In experiments 2 and 3 traces of isopropanol was not found.

Example 10

Experience in conditions identical to the conditions described above in examples 7 to 9 was carried out using pure propane. The amount of isopropanol, measured after 5 hours, is 0.11 mmol/hour, i.e. has a factor of 16 relative to the number of the example 1. Also received 0,04 mmol/h of acetone. Conversion of H2O2very small, i.e. there is a 1% after 5 hours.

1. The method of receiving oxirane by reacting the olefin with hydrogen peroxide in the presence of a catalyst and an organic diluent, according to which hydrogen peroxide is an aqueous hydrogen peroxide solution, extracted with mostly purified water from the mixture resulting from the oxidation of at least one alkylanthraquinones without further processing by washing and/or cleaning.

2. The method according to claim 1, in which oxiran is 1,2-epoxypropane, and ol the fin is propylene.

3. The method according to claim 1 or 2, wherein extracting water contains less than 3 wt.% organic solvents, in particular alcohol(s).

4. The method according to one of the preceding paragraphs, in which a solution of N2O2obtained by extraction comprises at least 0.001 g/l and not more than 10 g/l of organic impurities, expressed in CELLS, the concentration of organic carbon).

5. The method according to one of the preceding paragraphs, in which a solution of N2O2obtained by extraction, contains cations of metals such as alkali or alkaline earth metals, e.g. sodium) and anions (such as phosphates, nitrates) in quantities greater than or equal to 0.01 g/l and less than or equal to 10 g/L.

6. The method according to one of the preceding paragraphs, in which a solution of H2O2obtained by extraction, contains at least 5 wt.% and most 50 wt.% peroxide of hydrogen.

7. The method according to one of the preceding paragraphs, in which the catalyst is a titanium silicate, preferably of the type TS-1 having a crystalline structure of ZSM-5, and the diluent is methanol.

8. The method according to one of the preceding paragraphs, in which the reaction medium contains a liquid phase and a gaseous phase, and in which the content of organic solvent in the liquid phase more than 35 wt.%.

9. The method according to one of the preceding paragraphs, with the Convention in the reactor in the liquid phase is the interaction of the olefin with hydrogen peroxide in the presence of a catalyst and an organic diluent, and in accordance with which the reactor is injected hydrogen peroxide and an organic diluent, and a fluid substance containing olefin and at least 10 vol.% alkane(s).

10. The method according to claim 9, in which the content of the alkane(s) in the fluid substance is at least 20% of the volume, preferably 30%.

11. The method according to claim 9 or 10, in which the content of the alkane(s) in the fluid substance is less than or equal to 95% of the volume, preferably less than or equal to 85%.

12. The method according to one of p-11, which is a continuous process, in which the fluid substance is introduced into the reactor at the beginning of the process contains less than 10% of the volume of alkane(s), but the result is recirculated to the reactor after the interaction of the olefin with peroxidebased connection, it is gradually enriched by alkanol(s)until the content reaches at least 10% of the volume.

13. The method according to one of PP-11, in which the fluid substance is introduced into the reactor at the beginning of the process contains at least 10% of the volume of alkane(s).

14. The method according to one of PP-13, in which the reactor is a circulating reactor, a fluid substance containing olefin and alkane or alkanes, is a gas, and the molar ratio of the flow rate of this gas to flow peroxidizing connection greater than or equal to 5, preferably greater than or equal to 10.

15. The method according to one of PP-14, in which oxiran is 1,2-what epoxypropanol, olefin is propylene, the alkane is propane.

16. Installation for implementing the method according to claims 1-15, which includes the installation to obtain a solution of N2About2by way of oxidation alkylanthraquinones.

17. United way of getting H2About2by way of oxidation alkylanthraquinones and get oxirane by reacting the olefin with N2About2, for which is used to install on item 16.



 

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FIELD: chemical industry; production of hydrogen peroxide and oxiranes.

SUBSTANCE: the invention is dealt with a method of production of hydrogen peroxides and oxiranes. The invention provides for conductance of reaction of olefin with hydrogen peroxide at the presence of a catalyst and organic thinner. At that hydrogen peroxide is present as a water solution of hydrogen peroxide extracted mainly with the help of purified water out of a mixture produced as a result of oxidation at least of one alkylanthrahydroquinone without aftertreatment with a cleansing water and-or purification. The technical result is an increase of an output and selectivity of oxirane.

EFFECT: the invention ensures increased output and selectivity of oxirane.

17 cl, 5 tbl, 10 ex

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