The method of producing accelerated

 

(57) Abstract:

The method of producing accelerated, which includes the transmission source of a mixture containing an organic hydroperoxide and alkene, through a series of at least two serially connected reactors, each of which contains a layer of particles of heterogeneous epoxidation catalyst and operates in a cyclic mode; in this way a first reactor of the series, operating in cyclic mode is switched to the position for this next in the process, when the activity of the epoxidation catalyst contained in the first reactor is reduced to an undesirable low level; (b) in this position, the catalyst with low activity contact with the mixture of products, coming out of the reactor, in the same position before him, at a temperature which is at least 5°C higher end of the temperature at which the catalyst was used in the first position in the series of reactors, and for a time sufficient to restore the activity to the desired level. For a number of epoxidation reactors operating in cyclic mode, can be located one or more additional epoxidation reactor with a fixed catalyst bed, the efficacy, increase service life of the catalyst, reducing the formation of side reaction products. 2 N. and 11 C.p. f-crystals, 2 PL.

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 present invention also relates to a method of reactivating at least partially deactivated heterogeneous epoxidation catalyst.

Epoxidation of the alkene in alkalinized by reacting the alkene with an organic hydroperoxide is known in the technique.

For example, in the well-known method for simultaneous obtaining of propylene oxide and styrene from ethylbenzene, apply the above epoxidation reaction. Normally, this kind of joint production includes the following stages: (i) interaction of ethylbenzene with oxygen or air to form ethylbenzene hydroperoxide, (ii) interaction of the resulting hydroperoxide, ethyl benzene with propene in the presence of an epoxidation catalyst to obtain propylene oxide and 1-phenylethanol, and (iii) build the P CLASS="ptx2">Another way of obtaining accelerated is a joint production of propylene oxide and methyl tert-butyl ether (TMVE) based on isobutene and propene. This method is well known in the art and includes the same stages of the reaction, as a method of producing styrene and propylene oxide described in the previous paragraph. Under epoxidation tert-butylhydroperoxide reacts with propene, forming propylene oxide and tert-butanol, in the presence of a heterogeneous catalyst for the epoxidation. Tert-butanol is then atrificial methanol, receiving MTBE, which is then used as additives to motor fuels.

The present invention relates to the epoxidation reaction between an alkene and an organic hydroperoxide, and more particularly to the epoxidation reaction, for which is used a number of series-connected reactor with a fixed catalyst bed, each of which is filled with at least one layer of heterogeneous epoxidation catalyst, with special attention paid to the decontamination specified heterogeneous epoxidation catalyst.

Heterogeneous epoxidation catalysts known in the art. Such produce is vanadium, molybdenum, tungsten, titanium and zirconium. One particularly suitable class of heterogeneous epoxidation catalysts are catalysts based on titanium. Examples of such catalysts are the catalysts described, for example, in U.S. patent 4367342 and in the European patent EP-A-0345856. In U.S. patent 4367342 described the use of inorganic oxygen compounds of silicon in chemical composition containing at least 0.1% of the mass. oxide or hydroxide of titanium, while in the patent EP-A-0345856 described heterogeneous catalyst the titanium oxide on the silicon dioxide. According to EP-A-0345856 this catalyst was prepared by impregnation of a silicon compound in a stream of gaseous titanium tetrachloride with subsequent stages of annealing and hydrolysis and, optionally, stage of sililirovanie.

When such heterogeneous epoxidation catalysts used to catalyze the epoxidation of alkene may deactivation of the catalyst. Without taking measures to prevent deactivation of the catalyst in the epoxidation, which is in contact with the stream containing alkene and an organic hydroperoxide with the previous stage of oxidation, will have a limited lifetime due to decontamination and str method, described in the international application WO 98/18555 and/or by the method described in international application WO 99/01445.

Increase service life of the catalyst, it would be advantageous, as it would lead to increased productivity and economic efficiency in the production of accelerated. Increase service life of the catalyst can reduce the costs associated with consumption of catalyst, and the time and cost of congestion reactors. In addition, increased service life of the catalyst is desirable because in this case, you can maintain a lower reaction temperature and thus reduce the formation of by-products.

The present invention in its first aspect provides a method of producing accelerated including cyclic operation of the series connected in series of the epoxidation reactor with a fixed catalyst bed, working in certain conditions, which was found to significantly increase the service life of the catalyst. The method according to the present invention leads to the reactivation of the deactivated catalyst and, consequently, to increase the service life of the catalyst. This, in turn, leads to higher economic efficiency and produces the Yes, this method involves passing the mixture containing organic hydroperoxide and alkene, through a series of at least two serially connected reactors, each of which contains a layer of particles of heterogeneous epoxidation catalyst, operating in cyclic mode, after which, optionally, is at least one additional epoxidation reactor containing a layer of particles of heterogeneous epoxidation catalyst, and continuous removal of the product stream from the last of the epoxidation reactor containing the reaction products of accelerated and alcohol, and from the specified stream products extract the final product - accelerated, and in a specified way:

(a) a first reactor of the series of operating in a cyclic mode, set at the position distant from this, a number of reactors in the process or immediately after any of the additional reactors, when the activity of the epoxidation catalyst contained in the reactor is reduced to an undesirable low level;

(b) in this position, the catalyst with low activity is in contact with the products leaving the reactor, which is re is used in the first position, a number of reactors, and for a time sufficient to restore the activity of the catalyst to the desired level.

The main advantage of the method according to the present invention is that the reactor containing the deactivated catalyst, we do not need to work every time, when the degree of decontamination becomes undesirable high, so there is no need to interrupt the process each time an epoxidation catalyst in the first reactor epoxidation deactivated. In addition, while the deactivated catalyst is in the new position, he may still continue to contribute to the final output of accelerated. That is, when its activity is increased, the amount of alkene, turned into accelerated on this particular layer of the catalyst, may also increase. The cyclic operation mode of the number of series-connected reactors epoxidation known in the art. For example, in U.S. patent 5849937 described by way of a number of serially connected reactors epoxidation, designed to get accelerated, in which the reactor, containing most of the deactivated catalyst is either in the first or last position in the row, and when what erom position, containing fresh catalyst. Accordingly, in this way is continuously under construction fixed number of reactors epoxidation in a while one reactor is in reserve. To have one reactor in reserve is not desirable, considering in the future possible costs.

In industrial processes the epoxidation reaction is usually carried out at temperatures from 50 to 135°C., more acceptable from 70 to 125°C., and at pressures up to 80 bar, more acceptable from 10 to 60 bar, and the reaction medium is a liquid phase. Usually during the epoxidation temperature in the reactor increases. So between every two consecutive epoxidation reactors should be located means for cooling. In order to compensate for loss of catalyst activity due to decontamination, the temperature in the reactor can be increased, for example, by regulating the amount of cooling, so that the conversion in each reactor can be maintained at a desired level. The temperature was raised until, until it reaches the temperature above which, as you might expect, negative side effects (for example, the formation of by-products) stanovitsyadusha, which can be reached during the epoxidation, to compensate for loss of catalyst activity, called "final temperature". This final temperature is usually achieved by the end of the epoxidation cycle, i.e. the period of time between the last two switching reactors in the series of reactors epoxidation plus possible additional epoxidation reactors.

Thus, in the method of the present invention, at least partially deactivated catalyst in the first reactor of the series is subjected to the action of temperature, which is at least 5°C higher than the previously mentioned final temperature. This is achieved by the fact that the first reactor is placed in position after the specified number of reactors or, if you use one or more additional reactors epoxidation, in the position immediately after any of the additional reactors, and shall contacting the deactivated catalyst with a mixture emerging from the previous reactor at the required temperature.

Accordingly, at the stage (a) of the present method, the first reactor of the series, operating in cyclic mode is set to a position beyond that is near or if ispalindrome after any such additional reactors when the activity of the contained catalyst for the epoxidation reduced to an undesirable low level. However, in the most preferred embodiment of the invention, the first reactor of the series is placed in final position in a series of reactors operating in cyclic mode at stage (a), regardless of whether any additional reactor.

The number connected in series and operating in cyclic mode epoxidation reactor consists of at least two of the epoxidation reactor with a fixed catalyst bed. However, it is preferable that this series contained at least three of the reactor, while the preferred maximum number of reactors that make up a number, equal to seven. Most preferably, the specified range is from three to five reactors.

For the next series connected reactors epoxidation, described above, may be one or more additional epoxidation reactor with a fixed catalyst bed. If there is more than one such additional reactors, these reactors are connected in series and, preferably, do not operate in a cyclic mode. The number of additional reactors,e is the number of additional reactors ranges from one to three.

The switching of the reactor in stage (a) is carried out when the activity of the epoxidation catalyst contained in the reactor is reduced to an undesirable low level. This usually takes place in the case when the catalyst is maintained 20% or less of its initial activity. The term "initial activity" means the activity of the catalyst at the beginning of the cycle epoxidation, i.e. immediately after the previous switching of the reactor, when considering the catalyst is used and is in the first reactor of the series of reactors operating in cyclic mode. Preferably, the switching reactor conducted when the catalyst retains only 10% or less of the initial activity, more preferably less than 5% and most preferably less than 1%. However, the degree of deactivation of the catalyst may vary, and may even go beyond the specified limits, depending on such factors as the cooling capacity, the number of reactors in series, the presence of additional reactors, the rate of deactivation and composition of raw materials.

In practice, the switching of the reactor can be any suitable means known to the experienced operator and valves located in suitable positions so that the threads coming and going from the various reactors could be directed in the desired location in the course of the process.

At the stage (b) of this method the catalyst with low activity contacts being in its new position (position), with the mixture leaving the reactor, in a previous position at a temperature that is at least 5°C higher than the final temperature at which the catalyst used in the first position in the series of reactors, and in sufficient time to restore its activity to the desired level. It has been found that particularly favorable results are obtained if the temperature at least 10°C and preferably at least 15°C higher than the final temperature at which the catalyst used in the first position in the series of reactors. More preferably, the temperature at which heat the at least partially deactivated catalyst is not more than 50°C higher and, more preferably, not more than 30°C above the specified target temperature. The period of time during which (partially deactivated catalyst VTL activity of the catalyst to the desired level. This is usually not less than 20 hours, because otherwise reactivation would be insufficient. The time required for reactivation, does not have a fixed maximum, because the reactor containing the catalyst, which must be re-activated, continues to work. Thus, the more reactivated catalyst, the more this catalyst is able to convert the alkene in accelerated. If the reactor containing reactivity the catalyst remains in the work, the time during which it remains in this position is determined by the rate of deactivation of the catalyst layer in the reactor, which is located at the first position of the number, as it is a catalyst, following the course of the process that you want to reactivate. If the reactor containing the reactivated catalyst, is placed back on the first position in the series of reactors operating in cyclic mode, the time during which it remains in the new position may be at most 10 days, preferably at most 6 days.

The thread that is in contact with reactivity catalyst is a flow of product coming out of the preceding epoxidation reactor. This goes the receipt of propylene oxide, constituting a part of the process for the joint production of styrene and propylene oxide). During the joint production of styrene and propylene oxide such emerging from the reactor stream will also contain ethylbenzene and will usually contain the ethylbenzene hydroperoxide (INR). However EVNR can almost completely absent if the reactor containing the deactivated catalyst is in the final position in the series of reactors operating in cyclic mode, and if there are no additional epoxidation reactor. Such a variant embodiment of the invention will be discussed in more detail below.

Accordingly, in one preferred embodiment of the present invention stage (a) and (b) of this method is repeated as long as the activity rectivirgula catalyst cannot much longer be restored to the desired level. In addition, if the reactivation is no longer sufficiently effective, it would be preferable to bring the reactor containing the catalyst, which is largely deactivated from the process to replace the deactivated catalyst in the reactor with fresh catalyst and enter the reactor back into operation end position is located, the method includes, in addition to stages (a) and (b) the following stages:

(C) after the catalyst is restored to the desired level, the reactor set back to the first position in the series of reactors;

(d) optionally, step (a) to (C) is repeated at least one time;

(e) the first reactor is removed from the work, when the activity of the epoxidation catalyst within it is reduced to unacceptably low levels, and it can no longer be restored to the desired level, and the deactivated catalyst is replaced with fresh catalyst;

(f) the reactor is injected back into working on the final position in the series of reactors operating in cyclic mode; and

(g) stage (a) to (f) is repeated, and at the same time, the product stream containing alkylenes and alcohol, continuously take away from the last reactor. In this embodiment of the invention, at least partially deactivated catalyst is recycled back into the first position in the series of reactors, as soon as his activity will be sufficiently restored.

If you do not use any additional epoxidation reactors in addition to a number of epoxidation reactors operating in cyclic mode, a particularly preferred method aswar, want to reactivate, in the final position in the series of reactors at the stage of (a) and increase the degree of conversion in the other reactors in General, at least 95% and most preferably up to almost 100% per INR. Therefore, the reactor containing the catalyst that you want to reactivate, and then contact with the mixture leaving the reactor, located on the second end position; such a mixture contains at most 5% INR and, preferably, contains almost no INR. Through at least 20 hours and preferably at most 10 days, more preferably within 6 hours, the catalyst is sufficiently reactivated, and the reactor will be placed back on the first position (stage (C)). Conditions of transformation, especially temperature, can be changed so as to achieve at least 95% conversion INR and, preferably, 100% conversion INR again in all reactors. Stage (d) to (g) then can be performed in a production line by the above method.

The method according to the present invention is applicable to heterogeneous catalysts for epoxidation all epoxidation reactions, including the reaction of the alkene with an organic hydroperoxide. svodnyy aliphatic hydrocarbons4-C20and kalkilya hydrocarbons WITH7-C10or mixtures thereof. Examples of suitable organic hydroperoxides are t-butylhydroperoxide, tert-AMYLPEROXY, tert-activedatabase, ethylbenzene hydroperoxide, cyclohexylpropionic and diethylbenzimidazolium. Of them the most widely used are the ethylbenzene hydroperoxide and tert-butylhydroperoxide.

As alkene can be used any organic compound having at least one aliphatic double bond carbon-carbon. This connection can be a connection, typically containing from 2 to 25 carbon atoms and preferably from 3 to 12 carbon atoms, such as propene, 1-butene, 2-butene, 1-penten, 1-octene, 1-dodecene, styrene and methylsterol. However, most preferably, as alkene using propene, of which the propylene oxide according to the method of the present invention.

As a heterogeneous catalyst for the epoxidation you can use any catalyst known in the art, which is suitable for catalysis of the reaction between an alkene and an organic hydroperoxide to obtain the corresponding accelerated and EP, apply the catalysts described in U.S. patent 4367342 and EP-A-0345856 discussed above. However, it was found that particularly favorable to use all the epoxidation reactors for the purposes of the present invention the catalysts of titanium dioxide on the silicon dioxide described in the patent EP-A-0345856. When these catalysts are used, this method gives very good results.

The composition of the initial mixture supplied to the epoxidation reactor, is not decisive for the method of the present invention in the sense that the initial mixture may be of any composition, which is usually used in industrial processes. Accordingly, in case the joint production of styrene and propylene oxide source mixture supplied to the plant epoxidation, contains at least some amount of ethylbenzene hydroperoxide (INR) and usually also a significant amount of ethylbenzene. Propene or injected into the reactor as a separate commodity flow, or it can be added to the flow of raw materials containing EVNR, before entering the reactor (reactors) epoxidation. The flow of raw material may also contain a number of methylvinylketone and/or 1-phenylethanol formed before wirausaha product. The typical flow of the original mixture (raw material) coming into the epoxidation reactor, which is the first in the process after the previous stage of the oxidation, including the stage of processing of the product leaving the reactor oxidation (such as washing and distillation) contains 15-25% of the mass. EVNR, 30-50% of the mass. ethylbenzene, 30-50% of the mass. of propene, 0-5 wt%.1-phenylethanol and 0-5% of the mass. methylvinylketone, up to 100% of the mass.

During the joint production of MTBE and propylene oxide source mixture flowing in the epoxidation reactor contains at least some amount of tert-butylhydroperoxide (TNR) in solution tert-butanol. Like the joint production of styrene and propylene oxide, propene or injected into the reactor as a separate stream, or it can be added to the flow of raw materials containing TNR, before entering into the epoxidation reactor.

The following aspect of the present invention also relates to a method of reactivating at least partially deactivated heterogeneous epoxidation catalyst that can promote the epoxidation reaction between an alkene and an organic hydroperoxide with getting accelerated and alcohol.

Such methods reatogo type, which includes contacting the used catalyst with a specific solvent at a temperature of from 20 to 400°C. the Main disadvantage of this method is that the reactor containing the used catalyst, should be put out of operation in order to carry out the regeneration. In addition, during regeneration of the catalyst does not contribute to increase the yield of the final product.

In U.S. patent 5798313 described method of regeneration of such heterogeneous catalysts for the epoxidation of olefins, which used the epoxidation catalyst is heated at a temperature of at least 700°C in the presence of oxygen. This method also requires that the reactor containing the deactivated catalyst was withdrawn from work and due to the high temperature of the catalyst must be unloaded from the reactor to give the opportunity to perform the regeneration. In addition, such processing with the aim of regeneration is very energy-consuming, which is undesirable from both an environmental and an economic point of view.

The purpose of the present invention is to overcome these disadvantages of the known methods of regeneration.

In accordance with this present and tertogennogo epoxidation catalyst, capable of promote the epoxidation reaction between an alkene and an organic hydroperoxide with the formation of accelerated and alcohol, and this method includes the following stages:

(1) communicating at least a certain amount of organic hydroperoxide with an alkene to form accelerated and alcohol in the presence of a suitable heterogeneous epoxidation catalyst under suitable conditions, the epoxidation;

(2) contacting the at least partially deactivated catalyst from the reaction mixture formed during the epoxidation stage (1) containing an organic hydroperoxide, alkene, accelerated and alcohol, at a temperature which is at least 5°C higher than the final temperature at which at least partially deactivated catalyst was used immediately prior to reactivation.

The advantages described above of the method consist in the fact that

(i) a reactor containing the deactivated catalyst is not required to work every time, when the degree of decontamination becomes undesirable high, and that

(ii) deactivated catalyst during regeneration prodoljitionam.rektalno, to stage (1) of the above-described method, the initial mixture containing organic hydroperoxide and alkene, passed at least two of the reactor, which both contain a layer of particles of heterogeneous epoxidation catalyst, before the thus obtained reaction mixture will be in contact with the at least partially deactivated catalyst in stage (2).

It is preferable to carry out stage (2) at a temperature which is at least 10°C. and, more preferably, at least 15°C higher than the final temperature at which at least partially deactivated catalyst was in operation immediately prior to reactivation. However, a suitable temperature during reactivation will be a temperature which is not more than 50°C higher and more appropriate - not more than 30°C above the specified target temperature. It was found that to achieve an effective reactivation of the catalyst in the epoxidation particularly suitable is the length of contact between the at least partially deactivated catalyst and reaction mixture in stage (2) equal to at least 20 hours, preferably, at least. what, however, as explained here above, the time of contact, there is no fixed maximum because the reactor containing reactivity catalyst, during reactivation continues to work.

It was found that reactivation is particularly effective for neoreality epoxidation catalysts, and more specifically for titanium containing catalysts for epoxidation. Of them the most widely used are catalysts of titanium dioxide on the silicon dioxide. However, other neoreality heterogeneous epoxidation catalysts also can be re-activated by the method of the present invention.

Used alkene and an organic hydroperoxide are the same as described previously in connection with the method of producing propylene oxide. Accordingly, the most preferable to use the alkene is propylene, while the organic hydroperoxide is an ethylbenzene hydroperoxide. These reagents leads to the formation of propylene oxide and 1-phenylethanol.

The invention is further illustrated by the following examples without limiting the scope of the invention to these specific choices of its implementation.

Example 1

The initial substance was applied to the reactor in two high-pressure pumps and mixed with each other before entering into the reactor. The reactor worked, filled with fluid under pressure 50 bar (absolute). The reactor was supported by a significant flow of recirculating the mixture to ensure isothermal operation mode of the layer of catalyst in the reactor and to ensure that reactivity the catalyst is contacted with the reaction products of the epoxidation. Fed to the reactor alkene and 35% (by weight) solution of INR in benzene was mixed with recirculating flow before entering them into the reactor.

Analysis of the composition of the reaction mixture is carried out by supercritical fluid chromatography (SFC).

Supported the following process conditions:

the amount of solution Inductance 18 g/hour

the recirculated flow of 2.5 kg/h

The catalyst used in the reactor is a partially deactivated catalyst titanium/silicon dioxide derived from section epoxidation of an industrial process for the joint production of styrene and accelerated.

The catalyst activity was expressed by the value "C" showing the reaction rate constant in kg2fluid per kg of catalyst per mole per hour (kg2/(kg·mol·h)), reduced to 85°C, suggesting that INR and propene applicable reaction kinetics of the first order.

Laboratory installation for the continuous epoxidation containing partially deactivated catalyst titanium/silicon dioxide, started at time 0 hours at 90°C To the final temperature at which the catalyst is a titanium/silicon dioxide used before this section epoxidation of an industrial process for the joint production of styrene and accelerated. Then the installation worked under the conditions specified above. When time experience 5 hours the reaction rate, expressed as C, was equal to 0.2 mg2/(mg·mol·h). This reaction rate constant, although it is low, indicates that formed P10°C.

The increase in the activity of the catalyst is a titanium/silicon dioxide shown in table 1. Constant K expressed in kg2/(kg·mol.h).

From table 1 we can see that the contacting the deactivated catalyst with the reaction product of epoxidation and the temperature increase of 20°C from 90 to 110°C over 30 hours after the start of the experiment ultimately increases the activity of 15 times compared to the initial activity of the deactivated catalyst.

Comparative example 1

Repeating example 1 except that maintained a temperature of 90°C for 150 hours.

It was found that after 50, 100 and 150 hours after the start of the experiment K was equal to 0.2 kg2/(kg·mol·h). Thus, the activity of the deactivated catalyst remained consistently low.

Example 2

In this experiment, in order to illustrate the invention, used a series of four series-connected reactors epoxidation, each of which had a volume of 9.2 m3and contained 4000 kg of catalyst for the epoxidation of titanium dioxide on the silicon dioxide.

In this experiment, within 36 hours of reactivation number EVNR (35% is accounted for, accordingly, 100 and 90 tons/hour. Thus, the transformation INR and propene to propylene oxide and 1-phenylethanol continued during decontamination.

A number of reactors were in operation within a few weeks, and the activity of the catalyst in the first reactor was reduced to less than 1% of its initial activity, which represents the activity of fresh catalyst immediately after it is loaded into the reactor. The temperature at the outlet of the first reactor was equal to about 90°C.

The first reactor was then switched into its final position. In this position, the mixture leaving the third reactor was passed through a layer of the deactivated catalyst within 36 hours, and the mixture had a temperature of 120°C.

The rate constant of first order reaction of epoxidation (k0) defined for the conversion INR flowing through first order in the reactor containing the catalyst, which it was necessary to reactivate, was determined as a function of time, and the results are shown in table 2.

The switching of the reactor was carried out at t=0 hours the Activity of the deactivated catalyst at the time, expressed in the form ln(k0), is indicated in the table.

<) increases as a result of processing according to the present invention.

Example 3

The number of series-connected reactors epoxidation as described in Example 2, were exploited in a few weeks.

The rate constant of first order reaction of epoxidation (k0the first reactor, which was in contact with the raw material supplied, determined at time t=0 hours Was found that ln(k0) is equal to 8.2. The temperature of the reactor is equal to 85°C.

At t=18 hours, the reactor containing the reactivated catalyst, became the first reactor, which is in contact with supplied raw materials, and investigated the reactor becomes the second reactor, which is in contact with the raw material supplied.

At t=36 hours, the temperature of the investigated reactor (the second reactor) was equal to 91°C and ln(k0) is equal to 8.8.

1. The method of producing accelerated, including the transmission source of a mixture containing an organic hydroperoxide and alkene, through a series of at least two serially connected reactors, each of which contains a layer of particles of heterogeneous epoxidation catalyst, operating in cyclic mode, after which is optional, at least one additional reactor epoxidation, stereoselective epoxidation, containing as the reaction products of accelerated and alcohol, and from the specified stream product produce the final product - accelerated, and in the specified manner: (a) a first reactor of the series, operating in cyclic mode is set to the position after a series of reactors or immediately after any of the additional reactors, when the activity of the epoxidation catalyst contained therein is reduced to an undesirable low level; (b) in this position the catalyst with low activity is in contact with the mixture leaving the reactor, which is located in the preceding provision, at a temperature which at least 5°C higher than the final temperature at which the catalyst used in the first position in the series of reactors, and in sufficient time to restore its activity to the desired level.

2. The method according to p. 1, in which operating in cyclic mode, the number of reactors consists of at least three series-connected reactors epoxidation.

3. The method according to p. 1 or 2, in which stage (a) and (b) to repeat until the catalyst activity, which should be re-activated, you can no longer restore to Yo, which is mostly deactivated, removed from the work, the deactivated catalyst is replaced with fresh catalyst, after which the reactor is injected again in the final position of a number of reactors.

5. The method according to p. 1, which includes additional stages: (c) after the catalyst is restored to the desired level, the reactor set back in the first position, a number of reactors; (d) optionally, step (a) to (C) is repeated at least once; (e) the first reactor is removed from the work, when the activity of the epoxidation catalyst contained therein is reduced to an unacceptably low level and can no longer be restored to the desired level, and the deactivated catalyst is replaced with fresh catalyst; (f) this reactor is injected back into work in the end position, the number of reactors operating in cyclic mode; (g) stage (a) to (f) are repeated at that time, as a stream of product containing alkylenes and alcohol, continuously take away from the last reactor.

6. The method according to any of paragraphs.1-5, in which heterogeneous epoxidation catalyst used in the epoxidation reactor is a titanium containing catalyst, the site is ispolzuemyi alkene is a propene, and used organic hydroperoxide is an ethylbenzene hydroperoxide or tert-butylhydroperoxide.

8. The method of reactivation of the at least partially deactivated heterogeneous epoxidation catalyst capable of promote the epoxidation reaction between an alkene and an organic hydroperoxide with the formation of accelerated and alcohol, comprising the following stages: (1) the reaction of at least a certain amount of organic hydroperoxide with an alkene to form accelerated and alcohol in the presence of a suitable heterogeneous epoxidation catalyst under suitable conditions, the epoxidation; (2) contacting the at least partially deactivated catalyst from the reaction mixture epoxidation formed in stage (1) containing an organic hydroperoxide, alkene, accelerated and alcohol, at a temperature which is at least 5°C higher end of the temperature at which at least partially deactivated catalyst was used immediately prior to reactivation.

9. The method according to p. 8, in which at the stage of (1) the initial mixture containing organic hydroperoxide and alkene, miss cereste, as the reaction mixture, thus obtained, is in contact with the at least partially deactivated catalyst in stage (2).

10. The method according to p. 8 or 9, in which stage (2) is carried out at a temperature at least 10°C higher than the final temperature at which at least partially deactivated catalyst was in operation immediately prior to reactivation.

11. The method according to any of paragraphs.8-10, in which the engagement between the at least partially deactivated catalyst and reaction mixture in stage (2) continues for at least 20 h, preferably at least 30 am

12. The method according to any of paragraphs.8-11, in which the at least partially deactivated catalyst in the epoxidation is a titanium containing catalyst, preferably a catalyst of titanium dioxide on the silicon dioxide.

13. The method according to any of paragraphs.8-12, in which the organic hydroperoxide is a hydroperoxide, ethyl benzene and the resulting alcohol is a 1-phenylethanol.



 

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FIELD: chemical industry; production of a catalyst carrier material and the catalyst.

SUBSTANCE: the invention is dealt with the field of chemical industry. The method of production of a catalyst carrier material includes the following stages: (a) treatment of the utilized catalyst of titanium dioxide-on-silicon dioxide to clear from coke; (Ь) washing of the catalyst cleared from the coke by a flushing fluid chosen from a water solution of an inorganic acid, a water solution of an ammonium salt and their combinations; (c) drying and calcination of the catalyst washed out and cleared from the coke with production of the catalyst carrier material. The technical effect - the material produced this way is fit for use as the carrying agent material for titanium dioxide in a heterogeneous catalyst for epoxidation of olefines in alkylene oxide.

EFFECT: the invention ensures production of the material fit for use as the carrying agent material for titanium dioxide in a heterogeneous catalyst for epoxidation of olefines in alkylene oxide.

12 cl, 4 ex, 1 tbl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention describes a method for preparing oxirane in reactor comprising a liquid reaction medium. Method involves carrying out reaction between olefin and peroxide compound in liquid reaction medium in the presence of a solid catalyst and a solvent. Solid catalyst comprises zeolite as an active component and it is used in form of particles wherein at least part of particles present in reactor in the fluidized state. Invention provides increasing rate of the process that results to the enhanced output.

EFFECT: improved preparing method.

1 ex

FIELD: petrochemical industry; methods of reactivation of the alumina catalyzer of dehydration of methylphenylcarbinol (MPhC).

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular , to the method of reactivation of the catalyzer of the vapor-phase dehydration of methylphenylcarbinol. The offered method of the reactivation of the catalyzer of dehydration of methylphenylcarbinol is realized with the help of the carbon-containing compounds and coke burning-off by the air oxygen in the flow of the water steam and the subsequent wash by the acid water solution capable to give back hydrogen in the form of the proton. The volumetric ratio of the acid solution to the catalyzer at the wash is kept equal to 1÷10:1. In the process of the catalyzer wash the water solution of the acid having the temperature of 5-90°C is used. The technical result of the invention is reduction of the water consumption at realization of the reactivation of the alumina catalyzer of dehydration of methylphenylcarbinol.

EFFECT: the invention ensures reduction of the water consumption at realization of the reactivation of the alumina catalyzer of dehydration of methylphenylcarbinol.

9 ex, 1 tbl

FIELD: chemical industry; environmental protection technologies and methods of utilization of the waste mercury-containing catalyzer.

SUBSTANCE: the invention is pertaining to the field of environmental protection technologies, in particular, to the processes of utilization of the waste mercury-containing catalyzer for the process of hydrochlorination of the ethine. The invention presents the method of utilization of the mercury-containing catalyzer by its heating in the medium of the reducing gas, in the capacity of which use the residual gas of the high-temperature homogeneous pyrolysis of hydrocarbons. The heating is conducted at the temperature of 400-700°C within 4-7 hours. The technical result of the invention is the complete extraction (99.99 %) of mercury from the waste catalyzer, that transforms the mercury into the non-toxic substance.

EFFECT: the invention ensures the complete extraction of mercury from the waste catalyzer, that transforms the mercury into the non-toxic substance.

5 tbl, 6 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to field of oil processing, in particular CO oxidation catalysts, used as additive to cracking catalyst for oxidising oxygen into carbon dioxide in process of cracking catalyst regeneration. Claimed catalyst for CO oxidation in process of cracking catalyst regeneration contains manganese compounds, aluminium oxide and natural bentonite clay, with the following component content, wt %: manganese in terms of MnO2 6-20, bentonite clay - 24-44, Al2O3 - the remaining part, and has microspherical form of particles with average size 70 mc, wear resistance 92-97%, bulk density 0.7-0.8 g/cm3. Described is method of preparing catalyst for CO oxidation in process of cracking catalyst regeneration, which includes mixing manganese (IV) hydroxide, obtained by precipitation of manganese nitrate from water solution with ammonium, with composition, which consists of aluminium hydroxide and bentonite clay, preliminarily processed with concentrated nitric acid (12.78 mole/l), composition drying and burning, which is carried out step by step: at temperature 500°C during 4-6 hours, and then at temperature 950-970°C during 4 hours.

EFFECT: increase of catalyst activity and wear-resistance.

2 cl, 1 tbl, 12 ex

FIELD: technological processes.

SUBSTANCE: invention relates to sorption equipment and may be used to restore protective properties of chemical adsorbents-catalysts and filtering-absorbing canisters equipped with them that have expired shelf life. A method is described to regenerate a carbon-based sorbent-catalyst that lost activity during storage, including treatment with a chemical reagent containing ammonia, and further thermal treatment, where a reagent is an ammonium-air mixture with ammonia concentration (40±5) vol.%, which for (15±1)s is passed through a layer of a chemical adsorbent-catalyst arranged in an equipped filtering-absorbing canister, at the temperature of (22±3)°C and flow of (30±1.5) dm3/min with subsequent soaking for (5-6) min and thermal treatment for (5-6) min, by air heated up to (150±5)°C and flow of (200±20) dm3/min. (40±5) vol.%, which for (15±1)s is passed through a layer of a chemical adsorbent-catalyst arranged in an equipped filtering-absorbing canister, at the temperature of (22±3)°C and flow of (30±1.5) dm3/min with subsequent soaking for (5-6) min and thermal treatment for (5-6) min, by air heated up to (150±5)°C and flow of (200±20) dm3/min.

EFFECT: restoration of protective properties of a chemical adsorbent-catalyst in composition of filtering-absorbing canisters with expired shelf life without their disassembly.

1 tbl

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