The method of obtaining aromatic hydrocarbons

 

(57) Abstract:

The invention can be used in the petrochemical industry. Aromatic hydrocarbons are produced by contact regcognition feedstock comprising olefins and paraffins with a zeolite catalyst in an adiabatic reactor with a fixed layer containing a fixed catalyst layer consisting of a zeolite catalyst, thereby making the reaction of catalytic cyclization regcognition raw materials. The reaction of catalytic cyclization is carried out in conditions which satisfy the following requirements: 1) zeolite catalyst has an initial catalytic activity of 0.2 (c-1or more in terms of the rate constants for the initial stage of the first order decomposition of n-hexane catalyzed by zeolite catalyst, measured at a temperature of 500oC and atmospheric pressure; 2) the catalyst bed has a temperature of 450-650oC; 3) a layer of catalyst has a temperature distribution with respect to distance from the entrance to the catalyst bed to the outlet of the catalyst layer, the temperature distribution has at least one maximum value; 4) the outlet temperature of the layer is rolled is about allows to obtain a stable aromatic hydrocarbons with high yield over a long period of time. 32 C. p. F.-ly, 13 tab., 9 Il.

The present invention relates to a method for producing aromatic hydrocarbons from light hydrocarbons. More specifically, the present invention relates to a method for producing aromatic hydrocarbons from light hydrocarbons, which involves feeding regcognition raw material containing at least one component selected from the group comprising olefins and paraffins, in an adiabatic reactor with a fixed layer containing a fixed catalyst layer consisting of a zeolite catalyst, to thereby be brought into contact regcognition feedstock with zeolite catalyst in an adiabatic reactor with a fixed layer and to make the reaction catalytic cyclization regcognition raw materials, where the zeolite catalyst has a specific activity, and the reaction of catalytic cyclization is carried out at a specific temperature conditions in relation to the catalytic layer.

According to the method of the present invention can not only be obtained aromatic hydrocarbons with high yield, but also the loss of catalytic activity is small, so that the extraction of aromatic hydrocarbons can stappen used in the petrochemical industry and in the refining of oil, especially when obtaining aromatic compounds of high-octane gasoline.

Widely known different ways in which the aromatic hydrocarbon is obtained using zeolite, such as ZSM-5 as catalyst. For example, in Japanese patent application, the examined N 56-42639 (corresponding to U.S. patent N 3756942) described the way in which the aromatic hydrocarbon is produced from hydrocarbons consisting of paraffins, olefins and/or naphthenes, each having 5 or more carbon atoms, and which has a content of aromatic hydrocarbons 15% by mass or less, using a zeolite catalyst ZSM-5. In Japanese patent application, the examined N 4-5712 described the method by which aromatic hydrocarbons derived from hydrocarbon containing saturated hydrocarbons having 4 or less carbon atoms, unsaturated hydrocarbons having from 2 to 4 carbon atoms and solid oil in a quantitative sense, using a zeolite catalyst of the ZSM-4.

In addition, U.S. patent N 3845150 described the way in which the hydrocarbon containing from 20 to 65% by weight of saturated hydrocarbons and from 20 to 50% by weight nanasai the cyclization reaction (exothermic) unsaturated hydrocarbons and the cyclization reaction (endothermic) saturated hydrocarbons, can be done in terms of thermal balance, obtaining aromatic hydrocarbons by isothermal reaction.

In the pending application for Japanese patent application (kohyo) N 3-503656 (corresponding to U.S. patent N 4851602) described the way that the fraction of hydrocarbons containing lower alkanes and lower alkenes, is subjected to contact with the liquefied layer acidic zeolite catalyst of the type having average pore sizes in the first conversion zone, thereby inducing the reaction mixture (surface flow), containing aromatic hydrocarbons enriched in aliphatic hydrocarbons, and the resulting reaction mixture is subjected to contact with the liquefied layer acidic zeolite catalyst of the type having an average pore size in the second conversion zone, thereby receiving the product, which is enriched alkylated aromatic hydrocarbons, and which contains gasoline, having 5 or more carbon atoms.

Also posted in the description of the pending application for Japanese patent N 63-69888 (corresponding to U.S. patent N 4720602) described a method by which a hydrocarbon feedstock containing at least 50% by weight of C2-C12aliphatic Ugledar citiessee activity.

In lined with the description of the pending application for Japanese patent N 63-14732 described the way in which aromatic hydrocarbons are obtained from light hydrocarbons using a zeolite catalyst of the ZSM-5 containing zinc and having specific properties.

In lined with the description of the pending application for Japanese patent N 3-182592 (corresponding to U.S. patent N 4885420) described a method by which a hydrocarbon feedstock containing olefins is subjected to hydrogenation reactions using hydrogen and a hydrogenation catalyst, and then the resulting product is subjected to reaction dehydrocyclization in the reactor containing the catalyst dehydrocyclization, thereby obtaining aromatic hydrocarbons.

However, in these known methods when attempting to obtain aromatic hydrocarbons using an adiabatic reactor with a fixed layer (which is commercially more advantageous because it is not only simple, but also has high efficiency), problems arise, such as the yield of the desired product based on aromatic hydrocarbons becomes low or runs intensive gumming, so that it becomes Tr is tsya impossible to stably obtain the desired aromatic hydrocarbons with high yield when using adiabatic reactor with a fixed layer. For obtaining aromatic hydrocarbons with high yield was taken several attempts. For example, in lined with the description of the publication of unexamined application for Japanese patent N 3-182592 method by which the olefins contained in the raw material is first subjected to hydrogenation, and then the fraction is subjected to dehydrocyclization for obtaining aromatic hydrocarbons. This process, however, is disadvantageous, since it must be carried out in two stages. Further, in some of the commonly proposed method for obtaining aromatic hydrocarbons with high yield, is unprofitable but necessary use of reactors with complex structures (such as isothermal reactor, a reactor with a moving bed and the reactor with the liquefied layer).

As discussed above (U.S. patent N 3845150) described the process by which a fraction containing saturated hydrocarbons and unsaturated hydrocarbons in a specific weight ratio, is used so that makes possible the carrying out of the process in terms of heat balance. In this process, although heat from an external source is almost never served, aromatic hydrocarbons get almost the same output as the way to implement is to determine the temperature in the reaction system or, how to maintain stable operation, which suppresses a decrease in catalytic activity caused by coking of the catalyst. In the aforementioned pending patent application of Japan (konyo) N 3-503656 described method, in which a hydrocarbon feedstock containing lower alkanes and lower alkenes in such a weight ratio to maintain near isothermal reaction conditions in a conversion zone, is used to obtain the product, which is enriched alkylated aromatic hydrocarbons and contains gasoline, having 5 or more carbon atoms. In this way the reactor with the liquefied layer (on which the catalytic reaction and regeneration of the catalyst can be continuously) is used to prevent the lowering of catalytic activity caused by coking of the catalyst. However, the reactor with the liquefied layer, used in this way, has a complex structure, so costs are high.

Applicants have conducted extensive and intensive studies to solve the aforementioned problems, known from the prior art. The result was unexpectedly discovered that when obtaining aromatic hydrocarbons from light hydrocarbons, the city of the olefins and paraffins, served in the adiabatic reactor with a fixed layer containing a fixed catalyst bed consisting of a zeolite catalyst, thereby bringing into contact the original product light hydrocarbons with zeolite catalyst in an adiabatic reactor with a fixed layer, and carrying out the reaction of catalytic cyclization regcognition raw materials, in the case when using zeolite catalyst having a specific activity, and when the reaction of catalytic cyclization is carried out in certain temperature conditions with respect to the layer of catalyst, not only can be obtained with a high yield of the desired aromatic hydrocarbons, but also the smaller is the decrease of catalytic activity, therefore, obtaining the desired aromatic hydrocarbons can stably operate for a long period of time. The present invention is made on the basis of the above discovery.

Therefore, the first object of the present invention is a method for aromatic hydrocarbons by bringing into contact regcognition raw material containing at least one component selected from the group comprising olefins and paraffins, with zdrady can be obtained with high yield and stably for a long period of time.

Further and other objects, features and advantages of the present invention will be understood from the subsequent detailed description and the claims, taking into account the accompanying drawings.

In Fig. 1 shows a block diagram representing one mode of the method of the present invention; Fig. 2 is a block diagram representing another mode of the method of the present invention; Fig. 3 is a diagram representing one preferred profile of the temperature distribution in the catalyst layer used in the method of the present invention; Fig. 4 is a diagram representing one preferred profiles homogeneous distribution of temperature during steam treatment of a layer of a catalyst containing a zeolite catalyst, which must be used in the method of the present invention provided with the profile of an inhomogeneous temperature distribution; Fig. 5 is a block diagram representing one mode of separation of the reaction mixture obtained by the method of the present invention; Fig. 6 is a block diagram representing another mode of separation of the reaction mixture obtained by the method of the present invention; Fig. 7 is a block diagram representing one of the modes of regeneration Zolotarenko reactor, which should be used to assess the activity of the zeolite catalyst to be used in the method of the present invention; Fig. 9 is a block diagram representing one mode of recycling of the reaction product obtained by the present invention.

In Fig. 5 and 6, like parts and components denoted by the same numerals or letters.

Essentially the present invention, a method for obtaining aromatic hydrocarbons from light hydrocarbons by catalytic cyclization, which involves feeding regcognition raw materials including at least one component selected from the group comprising olefins and paraffins, in an adiabatic reactor with a fixed catalyst bed containing a fixed catalyst bed consisting of a zeolite catalyst, thereby resulting in contact regcognition feedstock with zeolite catalyst in an adiabatic reactor with a fixed layer, and carrying out the reaction of catalytic cyclization regcognition raw materials, and where the zeolite catalyst is at least one component selected from the group consisting of essentially fresh zeolite catalyst and obrabotannaya, which satisfy the following requirements(1), (2), (3) and (4):

(1) zeolite catalyst has an initial catalytic activity of 0.2 (-1or more in terms of the rate constants for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst, measured at a temperature of 500oC and at atmospheric pressure;

(2) the catalyst bed has a temperature in the range from 450 to 650oC;

(3) a layer of catalyst shows the temperature distribution with respect to distance from the entrance to the catalyst bed to the outlet of the catalyst layer, characterized in that the temperature distribution has at least one maximum value;

(4) the outlet temperature of the catalyst layer is in the range 40oC compared to the temperature at the inlet to the catalyst bed.

In the present invention, the term "essentially fresh zeolite catalyst" is intended to denote not only steamed zeolite catalyst, but also zeolite catalyst, which was treated with steam to such an extent that a significant modification of the zeolite catalyst was achieved. The term "substantial modification" means the mod is lithium catalyst with steam.

For easy understanding of the present invention the main structure and the various preferred embodiments of the present invention are presented below.

1. The method of obtaining aromatic hydrocarbons by catalytic cyclization, which involves feeding regcognition raw material containing at least one component selected from the group comprising olefins and paraffins, in an adiabatic reactor with a fixed layer containing a fixed catalyst bed consisting of a zeolite catalyst, thereby resulting in contact regcognition feedstock with zeolite catalyst in an adiabatic reactor with a fixed layer, and carrying out the reaction of catalytic cyclization regcognition raw materials, and where the zeolite catalyst is at least one component selected from the group consisting essentially of fresh zeolite catalyst and steamed zeolite catalyst, characterized in that the reaction of catalytic cyclization is carried out in conditions which satisfy the following requirements(1), (2), (3) and (4):

(1) zeolite catalyst has an initial catalytic activity of 0.2 (-1or more in terms of the rate constants of n is adopted at a temperature of 500oC at atmospheric pressure;

(2) the catalyst bed has a temperature in the range from 450 to 650oC;

(3) a layer of catalyst shows the temperature distribution with respect to distance from the entrance to the catalyst bed to the outlet of the catalyst layer, characterized in that the temperature distribution has at least one maximum value;

(4) the outlet temperature of the catalyst layer is in the range 40oC compared to the temperature at the inlet to the catalyst bed.

2. The method under item 2 above, wherein the zeolite catalyst consists essentially of zeolite.

3. The method under item 1 above, wherein the zeolite catalyst comprises a mixture of zeolite and at least one component selected from the group comprising a metal belonging to group VIII, IB, IIB or IIIB of the Periodic table and its derivatives.

4. The method under item 3 above, wherein the zeolite catalyst comprises a mixture of zeolite and at least one component selected from the group comprising zinc and its derivatives.

5. The method under item 4 above, wherein the zeolite catalyst comprises a mixture of zeolite, at least one component selected from the group comprising C is the lyst includes a mixture of zeolite and the product, obtained by heat treatment in a pair of a mixture of aluminum oxide and at least one component selected from the group comprising zinc and its derivatives.

7. The method under item 4 above, wherein the zeolite catalyst comprises a mixture of zeolite and zinc aluminate.

8. The method according to any of paragraphs. 4-7 above, wherein the content of at least one component selected from the group comprising zinc and its derivatives, in the zeolite catalyst is from 5 to 25% by weight relative to the amount of zinc.

9. The method under item 1 above, wherein the zeolite in the zeolite catalyst is replaced by a metal belonging to group VIII, IB, IIB or IIIB of the Periodic table.

10. The method according to any of paragraphs. 1-9 above, wherein the zeolite is zeolite catalyst has an atomic ratio Si/Al of at least 12 in its zeolite structure, and has a sodium content of 500 mass ppm or less.

11. The method according to any of paragraphs. 1-10 above, characterized in that the zeolite catalyst contains zeolite ZSM-5.

12. The method according to any of paragraphs. 1-11 above, wherein the zeolite catalyst is substantially fresh zeolite catalyst.

13. Spocom catalyst, which is obtained by steam treatment essentially fresh zeolite catalyst.

14. The method under item 13 above, wherein the zeolite catalyst comprises a mixture of steamed zeolite catalyst, which is obtained by steam treatment essentially fresh zeolite catalyst consisting essentially of zeolite, and at least one component selected from the group comprising a metal belonging to group VIII, IB, IIB or IIIB of the Periodic table and its derivatives.

15. The method according to p. 14 or 15 above, characterized in that the steam treatment is essentially fresh zeolite catalyst produced by the flow of steam flow through the reactor for steam treatment, containing essentially fresh zeolite catalyst with the sequence of the following stages (a) and (b):

(a) a stream of steam having a partial vapor pressure of not less than 0.1 kg/cm2and temperature from 500 to 650oC, passes through the reactor for steam treatment, thus is -+ contact fresh essentially of zeolite catalyst with the steam for 0.1 to 3 hours;

(b) temporary suspension flow through the reactor for steam treatment and removal of steam which remains in the reactor, while PA is eactor for steam treatment provided that the temperature of the steam flowing in stage (b) is higher than the temperature of the steam flowing in the phase (a) phase (b) is performed at least once, so pairs, individually flowing in each stage (b), is subjected to contact with the zeolite catalyst is treated with steam at the stage preceding each stage (b).

16. The method according to any of paragraphs. 1-15 above, characterized in that regcognition raw material contains at least one component selected from the group comprising fraction C4product system high temperature thermal cracking of hydrocarbon material oil, or a fraction obtained by removing butadiene or removal of butadiene and I-butene from fraction C4; fraction C5product system high temperature thermal cracking of hydrocarbon material oil or a fraction obtained by removing dienes from fraction C5; thermally graciously gasoline; a raffinate obtained by extracting aromatic hydrocarbons from thermally recerving gasoline; Zhytomyr cardboard factory-NC; Zhytomyr cardboard factory-graciously gasoline; a raffinate obtained by extracting aromatic hydrocarbons from the reformed; coke NC and whole oil.

18. The method according to any of paragraphs. 1-17 above, characterized in that the internal pressure of the adiabatic reactor during the cyclization reaction is in the range from atmospheric pressure to 30 kg/cm2G, and regcognition raw material is introduced into the adiabatic reactor at a specific clock speed (PSP) from 0.1 to 50 h-1.

19. The method according to any of paragraphs. 1-18 above, which further includes separating the resulting cyclization reaction mixture containing the product of aromatic hydrocarbons to A product consisting essentially of the product of aromatic hydrocarbons, and product B, consisting essentially of hydrogen and product non-aromatic hydrocarbon having 1-5 carbon atoms, and characterized in that the separation produced by the gas-liquid separator and, optionally, distillation columns.

20. The method according to any of paragraphs. 1-18 above, which further includes separating the resulting cyclization reaction mixture containing the product of aromatic hydrocarbons to A product consisting essentially of the product of aromatic carbon, and the product of D consisting essentially of hydrogen and product nonaromatic hydrocarbons having 1-3 carbon atoms, characterized in that the separation produced by the gas-liquid separator and, optionally, distillation columns.

21. The method according to p. 19 or 20 above, wherein the gas-liquid separation is produced using a cooler consisting of propylene or ethylene, and wherein the propylene or ethylene receive and use as a cooler in the process of producing ethylene by high temperature thermal cracking of petroleum hydrocarbons.

22. The method according to p. 19 above, wherein at least a portion of the product B, consisting essentially of hydrogen and product non-aromatic hydrocarbon having 1-5 carbon atoms, recyclart in the adiabatic reactor and used as part of regcognition raw materials.

23. The method according to p. 19 above, wherein at least a portion of the product B, consisting essentially of hydrogen and product non-aromatic hydrocarbon having 1-5 carbon atoms, is fed into the system high temperature thermal cracking of hydrocarbon material oil.

24. The method according to p. 20 above, characterized in that the product of non-aromatic hydrocarbons, having 4-5 carbon atoms, and the product D consisting essentially of hydrogen and product nonaromatic hydrocarbons having 1-3 carbon atoms, recyclart in the adiabatic reactor and used as regcognition raw materials.

25. The method under item 20 above, wherein at least a portion of at least one component selected from the group comprising C, consisting essentially of the product of non-aromatic hydrocarbons having 4-5 carbon atoms, and the product D consisting essentially of hydrogen and product nonaromatic hydrocarbons having 1-3 carbon atoms is introduced into the high temperature thermal cracking of petroleum hydrocarbons.

26. The method according to any of paragraphs. 19-25 above, which further includes processing A product consisting essentially of the product of aromatic hydrocarbons by at least one method selected from the group consisting of the following ways:

the way that the product of A process using the equipment for dealkylation, thus gaining benzene;

the way that the product of A process using the equipment for distillation, extraction equipment or equipment for the extraction distillation, polie to disproportionation or equipment for isomerization;

the way in which the product A is mixed with gasoline.

27. The method according to any of paragraphs. 1-26 above, which further includes a temporary suspension of supply regcognition raw materials in the adiabatic reactor with a fixed layer, and the burning of the coke formed on the zeolite catalyst during the reaction of catalytic cyclization, oxygen-containing inert gas as a fuel gas for the regeneration of the zeolite catalyst in the regeneration zone of the catalytic Converter.

28. The method under item 27 above, wherein the excess fuel gas discharged from the regeneration of the catalyst, recyclart in the area of regeneration of the catalyst through the heater through reciklirawe compressor, thereby forming a circulation system of a combustible gas, comprising a regeneration zone of the catalyst, recyclery compressor and heater, which are connected in this order through the pipeline, and wherein the fresh oxygen-containing inert gas is fed into the circulation system of the fuel gas at the first entrance, located between the exit from the zone of regeneration of the catalyst and the inlet of the heater in an amount of from 0.05 to 50% volume relative to the volume of circulation of the fuel gas discharging from what W to the heater in the quantity which is essentially equal to the amount of fresh oxygen-containing inert gas fed to the first input, where the number and the oxygen content is served fresh, oxygen-containing inert gas is adjusted so that the combustible gas flowing into the regeneration zone catalyst has an oxygen content of from 0.01 to 10 volume%.

29. The method according to p. 28 above, which further includes fresh inert gas not containing oxygen in the circulation system combustible gas to the second input of which is identical to the first input or provided separately from the first input between the output of the zone of regeneration of the catalyst and the inlet of the heater, in the amount of 10 volume% or less with respect to the circulating volume of combustible gas, and the subsequent discharge of the circulation system excess fuel gas fuel gas leaves the zone, the regeneration of the catalyst before it enters the heater in a quantity which is essentially equal to the quantity of fresh inert gas not containing oxygen, fed to the second input, thereby suppressing an increase in the partial pressure of steam in the fuel gas flowing into the regeneration zone of the catalytic Converter.

30. The method according to p. 29 above, which further includes ohlazhdeniya gas before it enters the heater, characterized in that the cooling and heating get through at least one heat exchanger.

31. The method according to any of paragraphs. 13-15, characterized in that the steam treatment is essentially fresh zeolite catalyst produced using the circulation system pair includes a reactor for steam treatment, recyclery compressor, heater and at least one heat exchanger, which are connected by a pipeline.

32. The method according to p. 31 above, wherein the reactor for steam treatment is used as an adiabatic reactor.

33. The method according to p. 31 or 32 above, wherein the circulation system pair is used as the circulation system combustible gas for the regeneration of the zeolite catalyst according to the method of paragraph 30 above, where the reactor for process steam is used as the reactor for regeneration or is replaced by a reactor for regeneration, including the zone of regeneration of the catalyst in the circulation system of a combustible gas, and where a combustible gas circulation system combustible gas is used instead of the steam system steam circulation.

Zeolite to zeolite catalyst to be used in the method of the present invention has an atomic ratio Si/Al from 2 to 60 in up-zeolite, -zeolite, Y-zeolite, L-zeolite, erionite, offretite, mordenite, periera, ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35 and ZSM-38. Among them, crystalline aluminosilicates and crystalline metroselect from the family of ZSM-5, that is, ZSM-5, ZSM-8, ZSM-11, and the like, are preferred. Regarding the details of the zeolite family of ZSM-5, you can specify, for example, U.S. patent N 5268162.

As a zeolite catalyst, which must be used in the present invention, can be used zeolite catalyst consisting essentially of zeolite. However, the zeolite catalyst to be used in the present invention may further contain at least one metal selected from metals belonging to group VIII, IB, IIB or IIIB of the Periodic table. It is preferable that the zeolite catalyst contained a mixture of zeolite and at least one component selected from the group comprising a metal belonging to group VIII, IB, IIB or IIIB of the Periodic table and its derivatives (for example, a metal oxide, such as zinc oxide as the metal oxide can facilitate dehydrogenization zeolite). Among the metals belonging to group VIII, IB, IIB or IIIB of the Periodic table, the metals selected from Zn, Cu, Ag, Ni, Pt, Pd and Ga, I is to be preferred, to zeolite catalyst contained a mixture of zeolite and at least one component selected from the group comprising zinc and its derivatives. More preferably, the zeolite catalyst further contains aluminum oxide and silicon oxide as a binder.

According to the method of the present invention, examples of materials suitable for use as at least one component selected from the group comprising zinc and its derivatives (hereinafter often referred to as "zinc component") include zinc, zinc oxide, zinc hydroxide, and salts such as zinc nitrate, zinc carbonate, zinc sulfate, zinc chloride, zinc acetate and zinc oxalate, and organic zinc compounds such as alkylzinc.

According to the method of the present invention is preferable that the zeolite catalyst contained a mixture of zeolite, a zinc component and aluminum oxide. It is also preferable that the zeolite catalyst contained a mixture of zeolite and the product obtained by heat treatment in a pair of a mixture of aluminum oxide and a zinc component. In the case where the zeolite catalyst is treated with steam, as described in detail below, the zinc component and alumina react with each other and cyclization greatly reduced. In addition, when the zeolite catalyst comprises a mixture of zeolite and zinc aluminate can be achieved the same effects as described above. The zinc aluminate, referred to here as the zinc aluminate, which shows the same structure x-ray diffraction, as shown in JCPDS 5-0669 NBS Circ., 539, Vol. 11, 38 (1953), for measurements in the x-ray diffractometer, such as XD-610, manufactured and sold by Shimadzu Corporation, Japan.

According to the method of the present invention, the alumina may be anhydrous alumina or hydrated alumina. Additionally, there may be used materials, which are able to obtain anhydrous or gidratirovannuyu aluminum oxide by hydrolysis, thermal decomposition, oxidation or the like.

When the zeolite catalyst contains at least one component selected from the group comprising zinc and its derivatives, it is preferred that the content of at least one component selected from the group comprising zinc and its derivatives, in the zeolite catalyst ranged from 5 to 25% by weight relative to the amount of zinc.

When the zeolite catalyst contains aluminum oxide, the aluminum oxide content in kata is su zeolite catalyst. When zinc is contained in addition to the aluminum oxide, the molar ratio of aluminum oxide to zinc (molar ratio of Al2O3/Zn) is 1 or more.

Zeolite, which should be used in the present invention may be in the H form or in metallosalen form. If metallising zeolite metal belonging to group VIII, IB, IIB or IIIB of the Periodic table is preferable as the substituent. Among the metals belonging to group VIII, IB, IIB or IIIB of the Periodic table, the metal is selected from Zn, Cu, Ag, Ni, Pt, Pd and Ga, is preferred. Among these metals Zn, Ag, Ni and Ga are particularly preferred. Further, as discussed above, the zeolite may be used in combination with a binder, such as aluminum oxide and/or metal oxide such as zinc oxide, which metal oxide is capable of facilitating dehydrogenization zeolite. As is known, the activity of the zeolite varies depending on the content of sodium in the zeolite. It is preferable that the sodium content of the zeolite catalyst was relatively low, specifically 500 weight parts per million or less. This low sodium is especially important when the atomic ratio Si/Al denotes the atomic ratio Si/Al, measured by29Si NMR. In the method of measuring atomic relations Si/Al by29Si NMR it is possible to mention "Jikken Called Koza (Lecture On Experimental Chemistry) 5, NMR", 4th edition, p. 232-233, 1992, published by Maruzen Cj., Ltd., Japan.

It is preferable that the zeolite catalyst to be used in the method of the present invention, would be steamed zeolite catalyst, which is obtained by steam treatment essentially fresh zeolite catalyst. When using the steamed zeolite catalyst, the amount of substance of coke accumulated on the surface of the zeolite catalyst during the subsequent reaction of catalytic cyclization, is reduced, thereby suppressing the decrease in catalytic activity with time in the reaction of catalytic cyclization.

For example, the above steam treatment can be carried out at a temperature of 500-800oC for 0.1 to 50 hours at a partial vapor pressure of 0.1-10 kg/cm2. When zeolite catalyst containing a mixture of zeolite, a zinc component and aluminum oxide steamed by the method mentioned above, which are described in the posted description of your pending application for Japanese patent N 2-115134, the reamers ways to get steamed zeolite catalyst, containing a mixture of zeolite and other components such as zinc, include (1) the method by which first create the above-mentioned mixture, and subsequently the resulting mixture is treated with steam, (2) the method by which the steamed zeolite catalyst, which is obtained by steam treatment essentially fresh zeolite catalyst consisting essentially of zeolite, mixed with at least one component selected from the group comprising a metal belonging to group VIII, IB, IIB or IIIB of the Periodic table and its derivatives, and, optionally, with another component (such as aluminum oxide or silicon oxide), and (3) a method in which the mixture obtained by the method (2) above, will become steam.

It is known that stabilization of zeolite by steam treatment is attributed to reaction (hereinafter referred to as "dealumination"), in which the aluminum in the zeolite is released from the zeolite structure by the action of steam. The heat of reaction generated during the steaming of the zeolite, is great and the speed dealumination is strongly temperature dependent.

Therefore, if there is an intention to obtain a partial dealuminated zeolite catalyst stably and uniformly in Promishlena.

It is assumed that steam treatment of the aluminum in the zeolite is zeolite structure according to the following reaction scheme:

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(1) Partial dealumination occurs in accordance with the reactions of the above two stages.

(2) the first stage Reaction is a reversible reaction, and therefore, when the supply of steam (H2O) is terminated, Al in Al(H2O)nas an intermediate product is returned in the zeolite structure.

(3) the reaction Rate of the first stage is extremely high compared with the speed of reaction of the second stage. The heat of reaction generated during the steam treatment, is attributed only to the first reaction stage.

(4) the second stage Reaction is an irreversible reaction, and the speed of reaction is extremely low compared with the speed of reaction of the first stage.

As noted above, the heat of reaction generated in the first reaction stage is large and the reaction of the first stage is very fast. Therefore, when the steam is excessively introduced into the catalyst bed in the reactor, the temperature of the catalyst rises rapidly in all areas of the layer of catalyst. Then raise the temperature more nectar.

Fig. 4 is a diagram representing one preferred profiles homogeneous distribution of temperature during steam treatment of a layer of a catalyst containing a zeolite catalyst to be used in the method of the present invention provided with the profile of an inhomogeneous temperature distribution. By way of steam treatment (Fig. 4) use a single-stage adiabatic reactor with a fixed layer, and the steam treatment is carried out by introducing steam at a temperature T0in the reactor at the top and the flow of steam through the reactor for 60 minutes In Fig. 4 the solid lines show the corresponding temperature distribution in the reactor at specified time points from the beginning of the input pair, and the dashed line represents the distribution of time-averaged temperatures in the respective blocks of the layer of catalyst in relation to the period of time from immediately after the start of injection of steam within 60 min after the start of the input pair. When the steam treatment is carried out at time-averaged temperature distribution, as represented by the dashed line in Fig. 4, a portion of the catalyst layer, which is near to the entrance of the reactor, i.e. the part of the layer CA is Oka activity, what part of the catalyst layer, which is located closer to the exit from the reactor, thereby giving rise to an inhomogeneous distribution of the activity of the catalyst after steam treatment. That is, the average activity of the whole catalyst layer after it steamed when time-averaged temperature distribution, as represented by the dashed line in Fig. 4, is equal to the activity of the catalyst, which shows a layer of the catalyst after it is treated with steam at a uniform temperature distribution [in which the temperature is equal to the average temperature of the catalyst layer (T), as represented by the dash-dotted line in Fig. 4] , but, in the first case, where the steam treatment is carried out at time-averaged temperature distribution, as represented by the dashed line in Fig. 4, the catalyst layer exhibits a non-uniform distribution of catalytic activity. Therefore, when the catalyst layer, which is subjected to treatment with steam at time-averaged temperature distribution, as represented by the dashed line in Fig. 4, using, for example, for the reaction of catalytic cyclization, there is a problem in that the catalyst bed is subjected to intensive coking in casticin to obtain a catalyst layer, which has high and stable catalytic activity in the whole space, it is preferable that the steam treatment was carried out at essentially uniform temperature distribution, as represented by the dash-dotted line in Fig. 4.

When conducting a partial dealumination according to the method by which the flow of steam is carried out in one stage, it is likely that there is a temperature difference between the upper part of the catalyst layer and the bottom layer of the catalyst, as shown by the solid line in Fig. 4, so that a homogeneous partial dealumination becomes complicated.

Therefore, the present invention is the advantage that the flow of the steam occurs in two or more stages under the conditions described below.

Specifically, it is preferable that the steam treatment is essentially fresh zeolite catalyst was carried out by passing steam through the reactor for steam treatment, containing essentially fresh zeolite catalyst in a sequence of the following stages (a) and (b):

(a) flowing steam having a partial vapor pressure of not less than 0.1 kg/cm2and the temperature of 500 - 650oC through the reactor for about temporary suspension of the flow of steam through the reactor for steam treatment and removal of steam, which remains in the reactor, and steam having a partial pressure of 0.1 to 10 kg/cm2and temperature 515 - 700oC, flows through the reactor for steam treatment under the condition that the temperature of the steam flowing in stage (b) is higher than the temperature of steam flowing at the stage of (a) stage (b) is conducted at least once so that pairs individually it runs, or each step (b) is held in contact with zeolite catalyst, which process steam at the stage preceding it, or at each stage (b).

In the present preferred embodiment of the method of the present invention the flow of steam through the reactor is preferably carried out in two or more stages in this way, as described above, so that the temperature difference between the upper part of the catalyst layer can be reduced, thereby enabling the processing ferry stably and uniformly.

When working on the first stage (a) multistage process steam treatment according to the present preferred embodiment of the invention, steam having a partial vapor pressure of not less than 0.1 kg/cm2, preferably 0.5 to 1 kg/cm2and the temperature of 500 - 650oC, preferably 550 to 650o is jego zeolite catalyst with the steam for 0.1 to 3 hours, preferably 0.1 to 1 h

Steam, which should flow through the reactor in stage (a) is the partial vapor pressure of not less than 0.1 kg/cm2. Pairs may be diluted with an inert gas. In this case, the concentration of the diluted vapor is preferably not less than 10 volume%, more preferably 20-80% by volume. As the inert gas can be used gas other than such gases (for example, alcohols and ethers), which will generate H2O in contact with the zeolite, and particularly preferred is nitrogen. Specific clock speed (PSP) pair, which should flow through the reactor, preferably represented as a value such that the partial vapor pressure does not become nonuniform in the layer of catalyst, and other problems such as channeling or unwanted steam flow does not occur. More specifically, it is preferable that the value of the PSP was 0.01 to 10 h-1. When the steam temperature is less than 500oC, the effect of suppressing the generation of heat by the reaction in the second stage of the process steam (and steam processing on any of the following stages) markedly enhanced. When the steam treatment is carried out at temperatures higher than 650owhat problems arise such that for a reactor must, unfortunately, be used a material that has high corrosion resistance at high temperatures. Further, when the processing time of the steam in the first stage is too long, a wide temperature distribution in the catalyst bed due to the heat of reaction generated during the steam treatment, and therefore, due to the heterogeneity in the degree of dealumination catalyst layer, so that the distribution of catalytic activity after steam treatment becomes non-uniform.

When working on the second stage (b) multistage process steam first flow of steam through the reactor is temporarily stopped, and the steam remaining in the reactor is displaced with an inert gas, as described above, having a temperature of 20-700oC, preferably 20-600oC. In this regard, it is preferable that not only the average temperature of the catalyst layer was maintained equal to the steam temperature, which later must be used when working on the second stage of the steam treatment, but also the temperature distribution in the catalyst bed must be maintained uniform to such an extent that the difference between the mahora, not removed after temporary suspension of the steam flow, dealuminated zeolite catalyst continues to be caused by the action of the remaining pair, which is undesirable from the viewpoint of achieving uniform dealuminated zeolite catalyst. After removal of the remaining steam steam having a partial vapor pressure of 0.1 - 10 kg/cm2, preferably 0.5 to 1 kg/cm2and the temperature 515-700oC, preferably a temperature which is within the 10oC with respect to the maximum temperature of the catalyst layer, which is achieved when the steam processing at the first stage, flows through the reactor, to thereby be brought into contact pairs with a zeolite catalyst for 0.1-50 hours, preferably 0.1 to 20 hours

Work on the above stage (b) can also be carried out twice or more. Reaction heat, which is generated when the steam processing at the second stage (b) is 1/4-3/5 heat of reaction generated during the steam treatment in the first stage (a), and therefore, the uniformity of temperature in the catalyst bed with steam processing at the second stage is higher than the steam processing at the first stage, so that homogeneous partial dealumination which can be preferably used zeolite catalyst, which is partially dealuminated according to the method described in the application for the South African patent N 94/7674 (corresponding publication of the application for international patent N WO95/09050).

According to the method of the present invention use an adiabatic reactor with a fixed layer. In relation to the adiabatic reactor may be mentioned description on pages 25-26 ("Kogyo Hanno Sochi (Industrial Reaction Apparatus)", edited by Kenji Hashimoto, (published by Baifukan Co., Ltd, Japan, 1984). As examples of adiabatic reactors can be considered those with a fixed layer, a movable layer and the liquefied layer. Of these adiabatic reactor with a fixed layer used in the method of the present invention. As an adiabatic reactor with a fixed layer is preferred adiabatic reactor with a fixed layer of the one type (which provides a layer of catalyst on only one stage), but can also be used a multi-stage adiabatic reactor with a fixed layer with an intermediate heat exchanger (in which the catalyst bed is divided into several stages, and between adjacent steps is a heat exchanger to supply heat to or remove heat from the respective stages). Pastviny adiabatic reactor with a fixed layer of the two reactor columns, in which the reaction is catalytic cyclization can be carried out continuously by alternating use of columns when performing a burn-in of any coke on the catalyst is held in the off column, which is not used for the reaction of catalytic cyclization.

The term "regcognition raw material containing at least one component selected from the group comprising olefins and paraffins", discussed here, refers to those hydrocarbons that have two or more carbon atoms and have a temperature of 90% distillation 190oC or below. Examples of waxes include ethane, propane, butane, pentane, hexane, heptane, octane and Noonan. Examples of olefins include ethylene, propylene, butene, Panten, hexene, hapten, octene, none. In addition to these olefins and/or paraffins regcognition raw materials that should be used can also contain cycloparaffin, such as cyclopentane, Methylcyclopentane and cyclohexan; cycloolefin, such as cyclopentene, methylcyclopentene and cyclohexene; and/or diene, such as cyclohexadiene, butadiene, pentadiene and cyclopentadiene.

The above hydrocarbons can be used as a mixture. The mixture may contain N2, CO2, CO or one of the others is I effective for suppressing the formation of coke on the zeolite catalyst during the reaction. The diluent in the mixture is preferably 20 volume% or less, more preferably 10 volume% or less. It is particularly preferable that the mass ratio of saturated hydrocarbons to unsaturated hydrocarbons in regcognition raw material was from 0.43 to 2.33. The term "mass ratio of saturated hydrocarbons to unsaturated hydrocarbons" discussed here is intended to denote the mass ratio of saturated hydrocarbons to unsaturated hydrocarbons in regcognition raw materials, which must be introduced to the reactor. When, as described in detail below with reference to Fig. 9, the reaction product is extracted from the reactor (40), is divided into the desired fraction of aromatic hydrocarbons and a fraction of nah (as unreacted original product and/or by-products) by means of purification and separation (41), and the fraction nah reciklirajte, the mass ratio of saturated hydrocarbons to unsaturated hydrocarbons denotes the mass ratio in the mixture (44) fresh feed (43) and recycled fraction (42).

Examples of hydrocarbon mixtures to be used as the outcome is B>4product obtained by subjecting a hydrocarbon oil, such as crude oil, thermal cracking at high temperatures, or a fraction obtained by udaleniya butadiene or butadiene and I-butene from fraction C4; fraction C5product obtained by subjecting a hydrocarbon oil to thermal cracking at high temperatures, or a fraction obtained by removing dienes from fraction C5; thermally graciously gasoline; a raffinate obtained by extracting aromatic hydrocarbons from thermally recerving gasoline; the resulting fluid catalytic cracking (JCK) oil condensate (NC); Zhytomyr cardboard factory-graciously gasoline; a raffinate obtained by extracting aromatic hydrocarbons from the reformed; coke(? ) NC; and crude oil. Particularly preferred mixtures are the fraction of C4and fraction C5product of the high temperature thermal cracking of petroleum hydrocarbons, such as natural oil and fractions obtained by removing at least part of butadiene, isobutene, isoprene and cyclopentadiene fraction C4and C5. The most preferred source products are those in which the mass ratio faction is s individually or in combination. The term "product of the high temperature thermal cracking", as used here, means a product produced by the equipment for thermal cracking, intended for use in the process of thermal cracking with the use of the pipeline, which is called "steam cracking". Steam cracking is described in The Oil and Gas Journal, PP. 220-222, May 12, 1969.

The fraction of hydrocarbons that must be used in the method of the present invention may contain impurities, such as oxygen-containing compounds, for example, TBA (tert-butyl alcohol), methanol, and the like.

In the present invention the speed of the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst (hereinafter often referred to simply as "speed initial stages of the reaction of the first order decomposition of n-hexane"), obtained by the method in which the reaction of the decomposition of n-hexane is carried out using zeolite catalyst on the equipment shown in Fig. 8, and the calculation is performed using the value of the volume of the zeolite catalyst, the value of the flow velocity of the raw product of the fraction of n-hexane and concentrations of n-hexane in Paleogene n-hexane, catalyzed by zeolite catalyst, was obtained as follows. Referring to Fig. 8, a quartz reaction tube (29) (10 mm diameter) covered with quartz glass, a catalyst (35) and ring process (32) in that order, from the lower to the upper part of the quartz reaction tube (29). Quartz reaction tube (29) is heated by an electric stove (33) equipped with a thermocouple (34) for adjusting the temperature of the oven (33) makes it possible to maintain the temperature of the catalyst (35), containing quartz tube (29), constant and equal to 500oC, which is measured using a thermometer (30). Then n-hexane is introduced into the quartz reaction tube (29) through the inlet (31) for the introduction of the original product through the ring process (32) at atmospheric pressure and at a specific clock speed (PSP) 4 h-1. The reaction product obtained in the time period between time points to 0.75 h and 1.0 h, each after the introduction of n-hexane (i.e. for 0.25 h) is cooled by the refrigerator (37), and then cooled by the cooler, consisting of dry ice and ethanol in an oil trap (38). All the separated oil component in the oil trap (38) and the whole of the separated gaseous component in the cell-collector strip (39) is collected. With the FID-TCD gas chromatography (Hp-5890 Series II, manufactured and sold by Hewlett Packard Company, USA) and FID gas chromatography (GC-17A, manufactured and sold Shimadzy Corp. , Japan), thereby obtaining the concentration of n-hexane in the reaction product. Concentrations of n-hexane, the volume value of the zeolite catalyst and the value of the flow velocity of the input n-hexane respectively substituted into the appropriate members of the following formula to obtain the average speed of the initial stages of the reaction of the first order decomposition of n-hexane in relation to time of collection of gas-oil 0.25 hours between the two time points, to 0.75 h and 1 h, each, after the introduction of n-hexane.

< / BR>
In the above formula to determine the [h] the term "volume of the zeolite catalyst" is intended to denote the volume of the zeolite catalyst as such, which does not include the amount of inert substances (such as ring process, glass beads and so on) contained in the catalyst layer. Thus, using the amount of zeolite catalyst as such as the amount of zeolite catalyst of the above formula is obtained the initial rate of reaction of the first order decomposition of n-hexane.

In the present invention the speed of the initial stage of ray in units of (h-1), is used after the value is converted to a value expressed in units (with-1).

According to the method of the present invention, as mentioned above, it is required that the zeolite catalyst satisfies the following requirement (1):

(1) zeolite catalyst has a catalytic activity at the initial stage of 0.2 (-1or more in terms of speed initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst, measured at a temperature of 500oC and at atmospheric pressure.

When the zeolite catalyst has an activity at the initial stage of less than 0.2 (-1in terms of speed initial stages of the reaction of the first order decomposition of n-hexane, the yield of aromatic hydrocarbons becomes unsatisfactory. For the implementation of a product aromatic hydrocarbons stably for a long period of time is preferable that the catalytic activity at the initial stage zeolite catalyst ranged from 0.2 to 2-1in terms of speed initial stages of the reaction of the first order decomposition of n-hexane. The term "yield aromatic angle is related to the number of non-aromatic hydrocarbons, contained in the input source product.

In the present invention, the term "inlet temperature catalyst layer" is intended to indicate the temperature of the catalyst layer in the part which first comes into contact with the stream of injected substances (the term "entrance of the catalytic layer" hereinafter often referred to as "reactor inlet"). The term "temperature catalyst layer" is intended to indicate the temperature of the catalyst layer in the part which latter is in contact with the flow of the reaction mixture (the term "exit catalytic layer" hereinafter often referred to as "output reactor"). The term "temperature of the catalyst layer" is intended to indicate the temperature of the catalyst layer, measured in parts corresponding to the parts of the plane perpendicular to the direction of flow of injected substances which part of the plane is located at a distance of 0 to 0.8 d from the center of the plane, where d represents the distance between the center plane and the surface of the inner wall of the reactor. In this invention, the term "maximum temperature" temperature distribution layer catalyst in relation to the distance from the entrance of the catalyst layer to the output layer of the catalyst is DL the deposits of temperature in the whole area from the entrance of the catalyst layer to the output layer of the catalyst. The term "maximum value", considered here, is intended to indicate the maximum values in the purely mathematical aspect as described on pages 56 - 57 "Kaiseki Gairon (Generalities of Analysis" edited by Yukinari Togi (published in 1983 by Gakujutsu Tosho Shuppan Publishing, Japan).

According to the method of the present invention the lower limit of the temperature of the catalyst layer is 450oC or higher and the upper limit temperature of the catalyst layer is 650oC or below.

In the present invention the lower temperature value on the curve of temperature distribution obtained by measuring the temperature in the whole area from the entrance of the catalyst layer to the output layer of the catalyst is defined as the lowest temperature value of the temperature distribution in the catalyst bed. The highest temperature value on the curve of temperature distribution obtained by measuring the temperature in the whole area from the entrance of the catalyst layer to the output layer of the catalyst is defined as the highest temperature value of the temperature distribution in the catalyst bed.

The temperature of the catalyst layer, including the temperature of the input and output layer of the catalyst, measured by thermoelectric thermome the nergy Control Techniques [Heat Control])" published in 1989 by Energy Saving Center, Japan).

In the present invention receives aromatic hydrocarbons using a zeolite catalyst having a catalytic activity, satisfying the requirement (1) above, under reaction conditions that satisfy the requirements of (2) to (4) below:

(2) the layer of catalyst has a temperature ranging from 450 to 650oC;

(3) a layer of catalyst shows the temperature distribution with respect to distance from the entrance of the catalyst layer, characterized in that the temperature distribution has at least one maximum temperature value;

(4) the outlet temperature of the layer of catalyst is within the 40oC with respect to the temperature of the entrance of the catalyst bed.

According to the method of the present invention aromatic hydrocarbons can be produced with high yield and stably in the adiabatic reactor with a fixed layer. When the zeolite catalyst has an activity that meets the above requirement (1), and, in addition, the temperature conditions of the layer of catalyst in an adiabatic reactor with a fixed layer satisfy the above requirements (2) to (4), obtaining aromatic hydrocarbons can be carried out with high o is ebouaney (2) - (4) requires that, as shown in Fig. 3, the catalyst layer had a temperature in the range of from 450 to 650oC, preferably 490 - 600oC, more preferably 500 to 580oC to the temperature distribution in the catalyst bed had at least one maximum value, and to output the temperature in the catalyst bed was in the range of 40oC with respect to the inlet temperature of the catalyst layer. It is preferred that the catalyst bed had at least one maximum temperature value in position between the input layer of the catalyst and part of the catalyst layer, in which the specific hourly space velocity (PSP) source product is 4 h-1. It is preferable that the catalyst bed had at least one maximum temperature value between the part of the catalyst layer, in which the PSP original product is 80 h-1and part of the catalyst layer, in which the PSP original product is 4.5 h-1. The temperature distribution layer catalyst in an isothermal reactor or similar is not the maximum temperature. When the output temperature of the catalyst layer is lower than -40oC with respect to the input temperarture catalyst layer is greater than +40oC with respect to the inlet temperature of the catalyst layer, the temperature of the reaction zone becomes too high, so increasing the coking and activity of the catalyst begins to rapidly decrease, thereby making difficult the stable reaction. When the temperature of the catalyst layer is less than 450oC, the yield of aromatic hydrocarbons is low. On the other hand, when the temperature of the catalyst layer more than 650oC, coking is increased, and the activity of the catalyst begins to rapidly decrease, thereby making difficult the stable reaction.

When the zeolite catalyst satisfies the above requirement (1) and, in addition, the temperature of the catalyst layer in the adiabatic reactor with a fixed layer satisfies the above requirements (2) to (4), coking can be reduced, and the extraction of aromatic hydrocarbons can be carried out with high yield and stably for a long period of time, compared with the case of the method of the reaction, in which any of the above requirements (1) to (4) is not satisfied.

Further preferred embodiments of the method of the present invention describes the link is at the forefront for obtaining aromatic hydrocarbons from light hydrocarbons. In the adiabatic reactor with a fixed layer 1 enter the thread 3 of the original substance, consisting, for example, from fraction C4system product high temperature thermal cracking of petroleum hydrocarbons, such as oil or a fraction obtained by removing butadiene or butadiene and isobutene of fraction C4. In the adiabatic reactor with a fixed layer 2 enter the stream of the original substance 4 consisting of, for example, fractions of C5system product high temperature thermal cracking of petroleum hydrocarbons, such as oil, or a fraction obtained by removing dienes from fraction C5. The mass ratio of the educt flow 3 and flow of the original substance 4 is not somehow limited. For example, the flow of the educt 3 at a temperature of 450 - 650oC is introduced into the adiabatic reactor with a fixed layer 1 with a specific clock speed (PSP) 0.1 to 50 h-1at a pressure of from atmospheric pressure to a pressure of 30 kg/cm2, Stream educt 4 at the same temperature as the flow of the educt 3, is introduced into the adiabatic reactor with a fixed layer 2 at the same specific time speed (PSP), as in the introduction thread ohodnotila original substance 3 in the adiabatic reactor with a fixed layer 1. The reaction mixture flows 5 and 6, which are respectively formed in the adiabatic reactors 1 and 2, are mixed with each other to form the flow of the reaction mixture 7.

In Fig. 2, the numeral 8 denotes the adiabatic reactor with a fixed layer, which is the same as each of adiabatic reactors 1 and 2, shown in Fig. 1. The flow of the original substance 9 is the same as the flow of the educt 3 shown in Fig. 1, and the flow of the original substance 10 is the same as the flow of the educt 4 shown in Fig. 1. Threads of original substance 9 and 10 are mixed with the same mass ratio, what is used for the introduction of threads of original substance 3 and 4 in the embodiment shown in Fig. 1, thereby forming the flow of the original substance 11. The flow of the original substance 11 is introduced into the adiabatic reactor with a fixed layer 8 at the same temperature of the source materials, at the same specific time speed (PSP) and at the same pressure as in the corresponding introduction of threads of original substance 3 and 4 in adiabatic reactors with a fixed layer 1 and 2 in the embodiment shown in Fig.1.

According to the method of the present invention the yield of aromatic hydrocarbons, the floor is of such hydrocarbons, obtained by the embodiment described above with reference to Fig.1.

The method according to the present invention is not limited to the above embodiments.

In the present invention is preferable that the internal pressure of the adiabatic reactor with a fixed layer during the cyclization reaction was in the range from atmospheric pressure to 30 kg/cm2G, and regcognition raw material was introduced into the adiabatic reactor at a specific clock speed (PSP) 0.1 to 50 h-1.

The above internal pressure of the reactor is intended to denote the average of the corresponding internal pressure at the reactor inlet and the reactor outlet. Measurement of the internal pressure as the inlet and outlet of the reactor can be carried out by means of the pressure sensor described on pages 398-406 "Enerugii Kanri Gijutsu [Netsu Kanri-hen] (Energy Control Techniques [Heat Control] )", published by the publishing Committee "Energy Control Techniques [Heat Control]" (published in 1989 bu Energy Saving Center, Jpan).

The above "specific clock speed (PSP)" is calculated according to the following formula:

PSP (h-1) = the weight rate of the original substance (g/h)/amount of catalyst (g).

The weight flow rate of the source substances of the above "Enerugii Kanri Gijutsu [Netsu Kanri-hen] (Energy Control Techniques [Heat Control])", published by the publishing Committee "Energy Control Techniques [Heat Control]" (published in 1989 by Energy Saving Center, Jpan).

According to the method of the present invention the reaction mixture which is enriched product aromatic hydrocarbons, can be separated into a fraction consisting essentially of the product of aromatic hydrocarbons and a fraction consisting essentially of the product of non-aromatic hydrocarbons by gas-liquid separator and, optionally, distillation columns, as described below. In this case, the first fraction consisting essentially of the product of aromatic hydrocarbons may be used as such or can be subjected to treatments such as dealkylation. In the latter fraction, consisting essentially of the product of non-aromatic hydrocarbons is preferred that the fraction was recycled or fed to other processes.

Below, with reference to figures representing the preferred embodiment of the present invention, the method of the present invention is described in more detail.

Fig.5 is a diagram representing one mode of separation of the reaction mixture obtained by the method of the present invention. Stream ishodnoj the fixed layer 14, containing zeolite catalyst, thereby inducing flow of the reaction mixture 19. The flow of the original substance 17 is the fraction of light hydrocarbons, comprising at least one component selected from the group comprising olefins and paraffins. Specific examples of fractions of light hydrocarbons include the fraction of C4system product high temperature thermal cracking of petroleum hydrocarbons, such as crude oil or a fraction obtained by removing butadiene or butadiene and isobutene, from the above fraction C4; fraction C5system product high temperature thermal cracking of hydrocarbon oil, or a fraction obtained by removing dienes from the above fraction C5; thermally graciously gasoline; a raffinate obtained by extracting aromatic hydrocarbons from thermally recerving gasoline; Zhytomyr cardboard factory-NC; Zhytomyr cardboard factory - graciously gasoline; a raffinate obtained by extracting aromatic hydrocarbons from the reformed; coke NC and natural oil. The heat from the flow of the reaction mixture 19 can be used to pre-heat the flow of the original substance 17.

The flow of the reaction mixture 19 is cooled POSReady essentially of the desired product of aromatic hydrocarbons, and product B as a by-product consisting essentially of hydrogen and product non-aromatic hydrocarbons including paraffins, olefins and/or naphthenes having 1 to 5 carbon atoms), using the difference in boiling points between product a and product B through the separating device 16 that includes a gas-liquid separator and, optionally, distillation column (which can improve product purity, separated by a gas-liquid separator). As described above, for example, the flow of the reaction mixture 19 may be cooled via a heat exchanger 15 for cooling, or may be cooled by flow of the source materials 17 and further cooled via a heat exchanger 15 for cooling.

Fig. 6 is a diagram representing another mode of separation of the reaction mixture obtained by the method of the present invention. As shown in Fig. 6, the flow of the reaction mixture 19 is obtained from the stream source materials 17 in the same way, as shown in Fig. 5. The flow of the reaction mixture 19 is cooled via a heat exchanger 15 for cooling, or it can be cooled by flow of the source materials 17 and further cooled via a heat exchanger 15 for cooling the romantic hydrocarbons, product C as a by-product consisting essentially of the product of nonaromatic hydrocarbons having 4 to 5 carbon atoms, and the product D as a by-product consisting essentially of hydrogen and product nonaromatic hydrocarbons having 1 to 3 carbon atoms, using the difference in boiling points between the products A, C and D, by means of the separating device 16 that includes a gas-liquid separator and, optionally, distillation column. Product composition A, comprising essentially the product of aromatic hydrocarbons, is shown in Fig. 5, may or may not be the same as the composition of A product, consisting essentially of the product of aromatic hydrocarbons, is shown in Fig. 6.

Examples of refrigerants that can be used in the heat exchanger 15 for cooling, is shown in Fig. 5 and 6, include cooling water, propylene, ethylene and compounds of fluorine. To reduce the cost of the necessary equipment and the required energy can be used cooler consisting of propylene or ethylene, which receive and are used as coolant in the process of producing ethylene by high temperature thermal cracking Ugledar the e products of the process of producing ethylene, including fractions of C4and C5can be used as at least part regcognition raw materials.

In the present invention the flow of the educt 17 may be a fraction of C5, which is obtained according to the method by which the product of the system high temperature thermal cracking of petroleum hydrocarbons fed into the separator for thermal recerving gasoline to obtain thermally recerving gasoline, and the resulting thermally graciously gas fed into the separator for fraction C5. In this case, as the separating device 16 to separate the flow of the reaction mixture 19 can be used above the separator for fraction C5.

In the present invention, the term "gas-liquid separator is intended to denote any, which are described on pages 73 - 130 "Purosesu Kiki Kouzou Sekkei Shiriizu 2 Tousou-rui (Structural Design of Process Equipments, Series 2, Columns and Vessels)" edited by Depending Kougaku Kyokai (Societ of Chemical Engineering) published in 1970 by Maruzen Co., Ltd., Japan. The term "distillation column" is intended to refer to such, which is described on pages 2 - 4 "Purosesu Kiki Kouzou Sekkei Shiriizu 2 Tousou-rui (Structural Design of Process Equipments, Series 2, Columns and Vessels)" edited by Depending Kougaku Kyokai (Society of Chemical Engineering) published in 1970 by Maruzen Co., Ltd., Japan. The terminology is Shiriizu 4 Kanetsuro (Structural Design of Process Equipments, Series 4, Heaaters)" edited by Depending Kougaku Kyokai (Society of Chemical Engineering) published in 1970 by Maruzen Co., Ltd., Japan.

According to the method of the present invention at least a portion of the product B, consisting essentially of hydrogen and product nonaromatic hydrocarbons having 1 to 5 carbon atoms, or at least a portion of at least one component selected from the group comprising C, consisting essentially of the product of nonaromatic hydrocarbons having 4 to 5 carbon atoms, and the product D, consisting essentially of the product of non-aromatic hydrocarbons having 1 to 3 carbon atoms (in which the products B, C and D are obtained by purification and separation of the desired product aromatic hydrocarbons), can be recycled in the adiabatic reactor 14 and used as part regcognition raw materials. In this case, the recycled product can be mixed with the flow of the educt 17 or with the flow of the educt 18, which is obtained by heating flow educt 17 through heater 13. Alternatively, the recycled product can be directly injected into the middle part of the layer of catalyst in the reactor 14 instead of the reactor inlet 14 in such a way that the temperature conditions catalyst layer of the reactor 14 satisfies the at least a portion of the product B, or at least part of at least one component, selected from the group including products C and D, recyclart into the reactor in the method of the present invention shown in Fig. 9. As an illustration, referring to Fig. 9 (which is a diagram representing one mode of recycling of the reaction product obtained by the method of the present invention), fresh starting material 43 is served in the reactor 40 to obtain the reaction product, and the resulting reaction product is separated into the desired product of aromatic hydrocarbons and a product of nah (as a new starting material or by-product) through 41 for purification and separation, the Product nah recyclart, and recycled product 42 is mixed with fresh original substance 43, receiving the mixture 44, and the mixture 44 is served in the reactor 40.

Further, in the method of the present invention at least a portion of the product B, consisting essentially of hydrogen and product nonaromatic hydrocarbons having 1 to 5 carbon atoms, or at least a portion of at least one component selected from the group comprising C, consisting essentially of the product of nonaromatic hydrocarbons having 4 to 5 carbon atoms, and the product D consisting essentially of hydrogen and proci and separation of the desired product aromatic hydrocarbons), can be served in the system of high-temperature thermal cracking of hydrocarbons to produce ethylene. In this case, various useful products, such as ethylene, propylene, fraction C4the fraction of C5and the product aromatic hydrocarbons (e.g. benzene, toluene, xylene and the like) can be obtained by the above system high temperature thermal cracking of hydrocarbons to produce ethylene.

According to the method of the present invention a product consisting essentially of the product of aromatic hydrocarbons, can be obtained by at least one method selected from the group consisting of the following ways:

the way that the product of A gain, using the equipment for dealkylation, thus gaining benzene;

the way that the product of A gain, using equipment distillation equipment for the extraction or extraction equipment distillation, thereby obtaining benzene, toluene and xylene (hereinafter these three compounds all together referred to as "BTC");

the way that the product of A gain, using the equipment for disproportionation or equipment for isomerization;

sposoby here is intended to denote a reactor, which is used in a method of catalytic dealkylation or in the method of thermal dealkylation, as described on pages 145 - 155 "Shin Sekiyu Depending Purosesu (New Petrochemical Process)" (published by Saiwai shobo on, Japan in 1986), edited by the Japan Petroleum Institute. The term "equipment for distillation" as used here, is intended to refer to equipment that is used in the distillation system, which is described on pages 183 - 206 "Purosesu Sekki Shiriidzu 3, Bunkai. Kanetsu.Joryu Wo Chushin Ni Suru Sekkei (design of Processes, Series 3, "Designing a system using cracking, heating and distillation as important measuries)" (published by Maruzen Co., Ltd., Japan in 1974), edited by The Society of Chemical Engineers Japan. The term "equipment for the disproportionation", used here, is intended to refer to equipment that is used in the disproportionation reaction, as described on pages 100 - 115 "Skin Sekiyu Depending Purosesu (New Petrochemical Process)" (published by Saiwai shobo on, Japan in 1986), edited by The Japan Petroleum Institute. The term "equipment for isomerization", used here, is intended to refer to equipment that is used in isomerization reactions, as described on pages 69 - 88 "Skin Sekiyu Depending Purosesu (New Petrochemical Process)" (published by Saiwai shobo on, Japan in 1986), edited by The Japan Petroleum Institute. The term "equipment for the extraction and equipment for the extraction distillation" as used ZV the distillation or method of azeotropic distillation, as described on pages 206 - 213 "Purosesu Sekki Shiriidzu 3, Bunkai.Kanetsu.Joryu Wo Chushin Ni Suru Sekkei (design of Processes, Series 3, Designing a system using cracking, heating and distillation as important measuries)" (published by Maruzen Co. Co., Ltd., Japan in 1974), edited by The Society of Chemical Engineers Japan.

According to the method of the present invention the occurrence of carbonaceous material (coke) on the zeolite catalyst during the reaction of catalytic cyclization can be significantly reduced. However, if the zeolite catalyst is gumming, filing regcognition raw materials in the adiabatic reactor with a fixed layer may be temporarily suspended, and the coke formed on the zeolite catalyst during the reaction of catalytic cyclization, can be burned using oxygen-containing inert gas as a fuel gas for the regeneration of the zeolite catalyst in the regeneration zone of the catalytic Converter. Coming when burning gas, resulting from the regeneration of the catalyst may be released into the atmosphere or may be recycled to the regeneration zone of the catalyst through reciklirawe compressor in the manner described below. In one case, it is preferable to reduce the water content of the oxygen-containing inert gas flowing into the regeneration zone by katalizatorom oxygen-containing inert gas is air.

When facing combustible gas resulting from the regeneration of the catalyst, is recycled, it is preferable to facing the combustible gas was recycled to the regeneration zone of the catalyst through reciklirawe compressor, thereby forming a circulation system evolved combustible gas, comprising a regeneration zone of the catalyst, recyclery compressor and heater, which are connected in this order pipeline. In this case, the fresh oxygen-containing inert gas may be supplied into the circulation system combustible gas through the first entrance, located between the output of the zone of regeneration of the catalyst and the inlet of the heater, in the amount of 0.05-50% by volume, preferably 2.5 to 10% by volume relative to the volume of circulation of the fuel gas discharging from the circulating system of the fuel gas exiting the fuel gas flows from the zone of regeneration of the catalyst before it enters the heater, in an amount which is essentially equal to the amount of fresh oxygen-containing inert gas is fed to the first input. In relation to the above supplied oxygen-containing inert gas, the quantity and the oxygen content in which are installed so that combustible gas, protinix. Later in the circulation system, the fuel gas can be fed fresh inert gas not containing oxygen, to the second input of which is identical to the first input or provided separately from the first input between the exit from the zone of regeneration of the catalyst and the inlet of the heater, in the amount of 10 volume% or less, preferably 5 volume% or less, relative to the amount of circulation of the fuel gas, and the subsequent discharge of the circulation system of the fuel gas exiting the fuel gas resulting from the regeneration of the catalyst before it enters the heater in a quantity which is essentially equal to the quantity of fresh inert gas, not containing oxygen which is supplied to the second input. This operation can suppress the increase in the partial pressure of steam in the fuel gas flowing into the regeneration zone of the catalytic Converter. As described above, when the fresh inert gas not containing oxygen, is fed into the circulation system of a combustible gas in addition to the fresh oxygen-containing inert gas, fresh oxygen-containing inert gas and fresh inert gas not containing oxygen, can separately be supplied to the circulation system combustible gas to the first input and second input, respectively. On the other hand, Sven, and then fed into the circulation system of the fuel gas to the same input.

Fig. 7 is a diagram representing one method of regeneration of the zeolite catalyst used in the method of the present invention. In the circulation system of a combustible gas, is shown in Fig. 6, the fresh oxygen-containing inert gas 28 and fresh inert gas not containing oxygen is fed to the circulation system combustible gas to the first input and second input, respectively. In Fig. 7 fresh oxygen-containing inert gas 28 (e.g., air) is heated to 350 to 600oC, preferably up to 390-580oC, more preferably up to 420-480oC by the heater 23, is fed into the circulation system of a combustible gas in a quantity of 0.05-50% by volume, preferably 2.5 to 10% by volume relative to the volume of circulation of the fuel gas so that the oxygen content in the fuel gas 24 flowing into the regeneration zone of the catalyst 21 containing zeolite catalyst having adhered thereto Cox, becomes equal to 0.01 to 10 volume%, preferably 0.5 to 2% by volume. A combustible gas consisting of fed fresh oxygen-containing inert gas 28 and facing the fuel gas 25 arising from the regeneration zone rolled the should build up, reaches reciklirawe compressor 22, or before the compressed combustible gas from reciklirawe compressor 22 reaches the heater 23 (the latter case is not shown), fresh inert gas 27, not containing oxygen, is fed into the circulation system of a combustible gas of 10 volume% or less, preferably 5 volume% or less, relative to the amount of circulation of the fuel gas. In addition, before the combustible gas, which will become more tense, reaches reciklirawe compressor 22, or before the pressurized combustible gas from reciklirawe compressor 22 reaches the heater 23 (the latter case is not shown), the part facing the fuel gas 25 exiting the zone of regeneration of the catalyst 21 (which part facing the fuel gas 25 arising from the regeneration of the catalyst 21, designated by the number 26), is removed from the circulation system combustible gas in an amount which is essentially equal to the total number served fresh oxygen-containing inert gas 28 and fed fresh inert gas 27, not containing oxygen which is supplied, for example, specifically, in the amount of 0.05 to 60% by volume, preferably 0.05 to 20% by volume relative to the volume of circulation of the fuel gas so that the inner Dawley side facing the fuel gas can be provided in a position below the first inlet to supply fresh oxygen-containing inert gas and a second inlet to supply fresh inert gas, not containing oxygen (this embodiment not shown). By the above operations, it is possible to suppress the growth of partial pressure of steam in the fuel gas flowing into the regeneration zone of the catalyst 21, thereby greatly suppressing the decrease of catalytic activity.

It is preferable that the water content of the fuel gas from reciklirawe compressor 22 has been lowered before it is served to the heater 23, by contact of the fuel gas adsorbing water agent. The inert gas is selected from gases, other than those (such as alcohol or ether), which generate H2O, being in contact with the zeolite. Especially desirable as the inert gas is nitrogen.

In the present invention adiabatic reactor can be used not only for the reaction of catalytic cyclization, but also as a regenerative reactor system of circulation of the fuel gas for the regeneration of the zeolite catalyst. In this case, the system for the reaction of catalytic cyclization and circulation system combustible gas together using the same reactor, which acts as an adiabatic reactor for the catalytic cyclization in the first system, and full cyclization adiabatic reactor is used as a regeneration reactor through manipulation of the respective valves, so the adiabatic reactor is disconnected from the system reaction catalytic cyclization and connected, and is included in the system for the regeneration of the zeolite catalyst, forming a closed circulation system, as shown in Fig. 7 (when using two reactors, as in the case of the reactor in a twin column mentioned above, or the like that is used three or more of the reactor, provided appropriate valves so that at least one system reaction catalytic cyclization and at least one circulation system of a combustible gas, such systems include a variety of reactors, can be appropriately formed by switching valves). Alternatively, the zeolite catalyst used in the reaction of catalytic cyclization, can be removed from the adiabatic reactor and transported to a regeneration zone of the catalyst in the circulation system of a combustible gas, is shown in Fig. 7 (which zone to the regeneration of the catalyst is provided separately from the adiabatic reactor for the reaction of catalytic cyclization), and then can be produced by regeneration of the zeolite catalyst. Similarly, the heater used to heat flow ishu system of circulation of the fuel gas for the regeneration of the zeolite catalyst.

Next, the combustible gas which must be introduced through reciklirawe compressor 22 may be cooled and injected combustible gas may be heated before reaching the heater 23, and the cooling and heating can be performed via at least one heat exchanger. Above the cooling gas, which is introduced through reciklirawe compressor 22, is aimed at increasing the efficiency reciklirawe compressor 22, and the above heating of the injected combustible gas before reaching the heater 23 is aimed at lowering the load of the heater 23. The heat exchange may be accomplished in one of two ways. That is, in one way section of pipeline connecting the outlet zone of the regeneration of the catalyst and the entrance reciklirawe compressor, and the section of pipeline connecting the output reciklirawe compressor and the inlet of the heater are located so that both sections are passed through the same heat exchanger (not shown), and cooling and heating produced by the same heat exchanger. Alternatively, in another method the section of the pipeline that connects the output reciklirawe compressor and the inlet of the heater, sootak that cooling and heating get through two separate heat exchangers, respectively.

According to the method of the present invention, the steam treatment is essentially fresh zeolite catalyst can be produced using the system of the circulation of steam, comprising a reactor for processing a pair, recyclery compressor, heater and at least one heat exchanger, which are connected by pipelines. In this case, it is preferable that the reactor for the steam treatment was used as an adiabatic reactor for the reaction of catalytic cyclization. Further, it is preferable that the circulation system pair was used as described above, the circulation system combustible gas for the regeneration of the zeolite catalyst. In this case, the reactor for the steam treatment is used as a regeneration reactor or replace those containing an area of regeneration of the catalyst in the circulation system, combustible gas, combustible gas circulation system combustible gas is used instead of the steam system steam circulation. In the present invention is preferred to the reactor for the steam treatment was also used as an adiabatic reactor and as a regeneration reactor.

The term "recyclery compressor used C, astrobingo fan, axial compressor, axial fan, and the like, which are described on pages 11-46 "Dai 10 Pen Kuuki Kikai (Section 10 Pneumatic machinery)" of "Kikai Kogaku Handobukku, Kaitei Dai 6 Pan (Handbook of Mechanical Engineering, 6threvised edition)" (published by The Japan Society of Mechanical Engineering in 1970 edited by The Japan Society of Mechanical Engineering.

The present invention will now be discussed in more detail with reference to the following examples and comparative examples, which should not be construed as limiting the subject matter of the present invention.

Example 1. 60 wt. including crystalline aluminosilicate ZSM-5 (having the atomic ratio Si/Al equal to 46 in its zeolite structure) in the form of ammonium ion, 15 wt. h-alumina and 25 wt. including zinc nitrate are mixed and the resulting mixture was subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4-6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 10% by weight.

Then single-stage adiabatic reactor with a fixed layer of fill obtained molded zeolite catalyst for the formation of the reactor a gaseous mixture of steam-nitrogen, containing 40 volume% of steam and having a pressure of 1 kg/cm2G and a temperature of 650oC.

For the evaluation of catalytic activity at the initial stage of the molded zeolite catalyst is treated with steam thus produced reaction test conversion of n-hexane, using a sample of zeolite catalyst in the isothermal isothermal conditions in the reactor shown in Fig. 8. As an illustration, in accordance with the above method, the reaction of decomposition of n-hexane is carried out in the reactor at 500oC at atmospheric pressure and at a specific clock speed (PSP) 4 h-1with respect to n-hexane. It was found that the average rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst, during the time of the collection of gas-oil in 0.25 hours amounted to 0.28 (-1).

Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table.1, when the mass ratio of 3:7, so that the resulting source product has a mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 1,54, which is in the range of 0.43-2,33. Received and the fixed layer, thereby carrying out the reaction of catalytic cyclization. The results obtained after 10 h and 5 days after start of the reaction, as well as the conditions of the reaction are shown in table. 3.

Comparative example 1. Repeat basically the same procedure as in example 1, except that use the original product, consisting only of fraction C5(the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 0,37) specified in the table. 3. The results obtained after 10 h and 5 days after start of the reaction, as well as the conditions of the reaction are shown in table. 3.

Comparative example 2. Repeat basically the same procedure as in example 1, except that use the original product, consisting only of fraction C4(the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 3,00) specified in the table. 1. The results obtained after 10 h and 5 days after start of the reaction, as well as the conditions of the reaction are shown in table. 3.

The results of comparative examples 1 and 2, are presented in table. 3, show that, when the reaction conditions do not satisfy all the requirements(1), (2), (3) and (4) defined in the present and what can be stable reaction.

Example 2. Repeat basically the same procedure as in comparative example 2, except that the internal pressure in the single-stage adiabatic reactor with a fixed layer is 1 kg/cm2, The Results obtained after 10 h and 3 days after start of the reaction, as well as the conditions of the reaction are shown in table. 4. The results of the reaction of comparative example 2 obtained after 10 h and 3 days after start of the reaction, also presented in table. 4.

Example 3. Fraction C4(the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 3,00) specified in the table. 1, heated to 530oC and injected into the single-stage adiabatic reactor with a fixed layer, filled with a layer of the catalyst of the zeolite catalyst, which is obtained in the same way as in example 1. The resulting reaction product is separated into A product consisting essentially of the product of aromatic hydrocarbons, the product C, consisting essentially of the products of non-aromatic hydrocarbons having 4-5 carbon atoms, and the product D consisting essentially of hydrogen and product nonaromatic hydrocarbons having 1-3 carbon atoms. The separation produced by gazozhidkostnoi the fixed layer. The reaction conditions satisfy all requirements(1), (2), (3) and (4) defined in the present invention. The results obtained after 10 h and 3 days after start of the reaction, are presented in table. 4 together with the reaction conditions.

Table. 4 shows that, when the reaction conditions satisfy all requirements(1), (2), (3) and (4) defined in the present invention, aromatic hydrocarbons can be obtained with high yield, and can be held stable reaction regardless of composition similar product.

Comparative example 3. 60 wt. including crystalline aluminosilicate ZSM-5 (having the atomic ratio Si/Al equal to 46 in its zeolite structure) in the form of ammonium ion, 15 wt. including gamma-alumina and 25 wt. including zinc nitrate are mixed, and the resulting mixture is subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4-6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 10% by weight.

Then single-stage adiabatic reactor with a fixed layer of fill obtained molded zeolites catalyst is injected and passed through the reactor a gaseous mixture of steam-nitrogen, containing 40% by volume of steam having a pressure of 1 kg/cm2G and a temperature of 650oC.

For the evaluation of catalytic activity at the initial stage of the molded zeolite catalyst is treated with steam thus produced reaction test conversion of n-hexane, using a sample of zeolite catalyst at isothermal conditions in the same way as in example 1. It was found that the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst, is 0.55 (-1).

Then the fraction of C5(the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 0,37, which is beyond the range of 0.43-2,33) specified in the table. 2, is heated to 530oC and injected into the single-stage adiabatic reactor with a fixed layer. The results obtained after 10 h after start of the reaction, are presented in table. 5 together with the reaction conditions.

Comparative example 4. Repeat basically the same procedure as in comparative example 3, except that use a fraction of C4(the mass ratio of unsaturated hydrocarbons/ saturated hydrocarbons : 3,00) found t reaction.

Example 4. Repeat basically the same procedure as in comparative example 3, except that use the original product (the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 1,54), which is produced by mixing fractions of C5presented in table. 2, with the fraction of C4presented in table. 1, in a mass ratio of 3:7. The results obtained after 10 h after start of the reaction, are presented in table. 5 together with the reaction conditions.

Table. 5 shows that under the above conditions, the yield of aromatic hydrocarbons (56,7% by weight) obtained in example 4 by reaction of the raw product, which was obtained by mixing fractions of C5fraction C4in a mass ratio of 3:7, is higher than the yield of aromatic hydrocarbons (54,7% by weight) (hereinafter referred to as the calculated yield of aromatic hydrocarbons) in a mixture of reaction products obtained by mixing the reaction product from the reaction raw product, consisting only of fraction C5(comparative example 3) with the reaction product from the reaction raw product, consisting only of fraction C4(comparative example 4), in massarani: (the yield of aromatic hydrocarbons, obtained in comparative example 3) 0,3 + (yield of aromatic hydrocarbons obtained in comparative example 4) of 0.7.

In respect of each of comparative examples 3 and 4, and example 4, the yield of aromatic hydrocarbons, which was obtained 5 days after start of the reaction, are presented in table. 5. The results show that under the reaction conditions in example 4 aromatic hydrocarbons can be obtained with high yield and can be stable reaction.

Comparative example 5. Single-stage adiabatic reactor with a fixed layer of fill molded zeolite catalyst ZSM-5 obtained in the same manner as in comparative example 3, to form the catalyst layer. The gaseous mixture of steam-nitrogen containing 40 volume% of steam having a pressure of 1 kg/cm2G and a temperature of 650oC, is injected to flow through single-stage adiabatic reactor with a fixed layer for 5 h for the implementation of steaming zeolite catalyst.

For the evaluation of catalytic activity at the initial stage of the molded zeolite catalyst is treated with steam thus produced reaction test conversion of n-hexane using but the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst is 0,28 (-1).

Then the fraction of C5(the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 0,37, which is beyond the range of 0.43-2,33) specified in the table. 2, heated to 500oC and injected into the single-stage adiabatic reactor with a fixed layer. The results obtained after 10 h after start of the reaction, are presented in table. 5 together with the reaction conditions.

Comparative example 6. Repeat basically the same procedure as in comparative example 5, except that they use a fraction of C4(the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 3,00) specified in the table. 1. The results obtained after 10 h after start of the reaction, are presented in table. 5 together with the reaction conditions.

Example 5. Repeat basically the same procedure as in comparative example 5, except that they use the original product (the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 1,54), which is produced by mixing fractions of C5submitted 10 hours after start of the reaction, presented in table. 5 together with the reaction conditions.

As shown in the table. 5, the yield of aromatic hydrocarbons obtained in example 5 (51,2% by weight) is higher than the calculated yield of aromatic hydrocarbons (49,3% by weight), calculated based on the outputs of aromatic hydrocarbons obtained in comparative examples 5 and 6.

Comparative example 7. Molded zeolite catalyst ZSBM-5 obtained in the same manner as in comparative example 3 is treated with steam under the same conditions as in comparative example 5.

For the evaluation of catalytic activity at the initial stage of the molded zeolite catalyst is treated with steam thus produced reaction test conversion of n-hexane, using a sample of zeolite catalyst at isothermal conditions in the same way as example 1. It was found that the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst, during the time of the collection of gas-oil in 0.25 hours amounted to 0.28 (-1).

Then the fraction of C5(the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 0,37) specified in the table. 2, heat, is received after 10 h after start of the reaction, are presented in table. 5 together with the reaction conditions.

Comparative example 8. Repeat basically the same procedure as in comparative example 7, except that they use a fraction of C4(the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 3,00) specified in the table. 1. The results obtained after 10 h after start of the reaction, are presented in table. 5 together with the reaction conditions.

Comparative example 9. Molded zeolite catalyst ZSM-5 obtained in the same manner as in comparative example 3 is treated with steam under the same conditions as in comparative example 5.

Then prepare the initial product mix fraction C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 3:7, so that the resulting source product has a mass ratio of unsaturated hydrocarbons/saturated hydrocarbons : 1,54, which is in the range of 0.43-2,33. The initial product is heated to 450oC and injected into the single-stage adiabatic reactor with a fixed layer. The results obtained after 10 h after start of the reaction, are presented in table.CE), obtained in comparative example 9 by reaction of the initial product, which is prepared by mixing fractions of C5fraction C4in a mass ratio of 3:7, is higher than the calculated yield of aromatic hydrocarbons (44,7% by weight), calculated based on the outputs of aromatic hydrocarbons obtained in comparative examples 7 and 8.

Example 6. 60 wt. including crystalline aluminosilicate ZSM-5 (having the atomic ratio Si/Al equal to 46 in its zeolite structure) in the form of ammonium ion, 15 wt. h-alumina and 25 wt. including zinc nitrate are mixed, and the resulting mixture is subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4-6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 10% by weight.

Then single-stage adiabatic reactor with a fixed layer of fill obtained molded zeolite catalyst for the formation of the catalyst layer. Within 5 h for the implementation of steaming zeolite catalyst is injected and passed through the reactor gaseous smess evaluation of catalytic activity at the initial stage of the molded zeolite catalyst, steamed thus, the test is done on the reaction conversion of n-hexane, in the same way as in example 1. It was found that the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst amounted to 0.28 (-1).

Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 6:4. Received the original product (the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons 0,86), heated to 530oC and injected into the single-stage adiabatic reactor with a fixed layer. The results obtained after 10 h after start of the reaction, are presented in table. 6 together with the reaction conditions.

Comparative example 10. Repeat basically the same procedure as in example 6, except that the molded zeolite catalyst ZSM-5 steamed for 40 h, so that its catalytic activity at the initial stage becomes smaller than 0.2 (-1). The results obtained after 10 hours after start of the reaction, are presented in table. 6 together with the reaction conditions.

Example 7. 46,4 wt. including cristening ion, 11.6 wt. h-alumina and 42 wt.h. the zinc aluminate are mixed, the resulting mixture is subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4 - 6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 20% by weight.

Then single-stage adiabatic reactor with a fixed layer of fill obtained molded zeolite catalyst for the formation of the catalyst layer. Within 5 h for the implementation of steaming zeolite catalyst is injected and passed through the reactor a gaseous mixture of steam-nitrogen containing 40 volume% of steam and having a pressure of 1 kg/cm2G and a temperature of 650oC.

Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 6:4. Received the original product (the mass ratio of unsaturated hydrocarbons/ saturated hydrocarbons 0,86) is heated to 530oC and injected into the single-stage adiabatic reactor with a fixed layer. The results obtained after 10 h after nacalco aluminium silicate (having an atomic ratio Si/Al, 46 in its zeolite structure) in the form of sodium ion is subjected to ion exchange so that the sodium content of the zeolite becomes 3000 weight parts per million, receiving crystalline aluminosilicate in the form of ammonium ion.

60 wt. including the above crystalline aluminosilicate ZSM-5 in the form of ammonium ion, 15 wt. h-alumina and 25 wt. including zinc nitrate are mixed, the resulting mixture is subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4 - 6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 10% by weight.

In this experiment, we measure the content of sodium in the zeolite catalyst according to the method by which the catalyst is added to aqueous solution of 1 N. HCl, the resulting mixture is heated for 5 min, subjected to filtration to obtain a filtrate, and the filtrate is analyzed by atomic absorption spectrometer (AA-640-12, produced and sold Shimadzu Corporation, Japan).

Then single-stage adiabatic reactor with a fixed layer of fill floor is placed the steaming of the zeolite catalyst is injected and passed through the reactor a gaseous mixture of steam-nitrogen, containing 40 volume% of steam and having a pressure of 1 kg/cm2G and a temperature of 650oC.

For the evaluation of catalytic activity at the initial stage of the molded zeolite catalyst, steamed thus, the test is done on the reaction conversion of n-hexane, in the same way as in example 1. It was found that the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by the zeolite catalyst was 0.05 (-1).

Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 6:4. Received the original product (the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons 0,86), heated to 530oC and injected into the single-stage adiabatic reactor with a fixed layer. The results obtained after 10 h after start of the reaction, are presented in table. 7 together with the reaction conditions.

The sodium content of the zeolite catalyst used in example 6, was measured by the same method as described above. It was found that the content of sodium is 110 mass parts per million. For comparison the table. 7.

Example 8. Repeat basically the same procedure as in example 6, except that the reaction product obtained by the reaction of catalytic cyclization, divided into A product consisting essentially of the product of aromatic hydrocarbons, the product C, consisting essentially of the product of nonaromatic hydrocarbons having 4 to 5 carbon atoms, and the product D consisting essentially of hydrogen and product nonaromatic hydrocarbons having 1 to 3 carbon atoms, by means of a gas-liquid separator and distillation columns, and the product C recyclery in single-stage adiabatic reactor with a fixed layer.

As an illustration 60 wt. including crystalline aluminosilicate ZSM-5 (having the atomic ratio Si/Al equal to 46 in its zeolite structure) in the form of ammonium ion, 15 wt. h-alumina and 25 wt.h. of zinc nitrate are mixed, and the resulting mixture is subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4 - 6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 10% by weight.

2G and a temperature of 650oC.

For the evaluation of catalytic activity at the initial stage of the molded zeolite catalyst, steamed thus, the test is done on the reaction conversion of n-hexane, in the same way as in example 1. It was found that the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst amounted to 0.28 (-1).

Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 6:4. Received the original product (the mass ratio of unsaturated hydrocarbons/ saturated hydrocarbons 0,86) is heated to 530oC and injected into the single-stage adiabatic reactor with a fixed layer. The resulting reaction product is separated into A product consisting essentially of the product of aromatic hydrocarbons, the product C, consisting essentially of the product nah, ima is Dov, having 1 to 3 carbon atoms. The separation produced by the gas-liquid separator and distillation columns. When the separation of the reaction product on the products A, C and D use a cooler consisting of propylene, which is produced and used as a cooler in the process of producing ethylene. Then the product C recyclery in single-stage adiabatic reactor with a fixed layer. The results obtained after 10 h after start of the reaction, are presented in table. 8 together with the reaction conditions. As shown in the table. 8, the output of C6-C9aromatic hydrocarbons obtained in example 8, is higher than that for C6-C9aromatic hydrocarbons obtained in example 6.

Example 9. Repeat basically the same procedure as in example 8, except that the resulting product C, consisting essentially of the product of nonaromatic hydrocarbons having 4 to 5 carbon atoms, not recyclery in single-stage adiabatic reactor with a fixed layer, but enter in the equipment for thermal cracking, thereby carrying out thermal cracking product C.

As an illustration, molded zeolite catalyst ZSM-LASS="ptx2">

Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 6:4. Received the original product (the mass ratio of unsaturated hydrocarbons/ saturated hydrocarbons 0,86) is heated to 530oC and injected into the single-stage adiabatic reactor with a fixed layer. The resulting reaction product is separated into product And consisting essentially of the product of aromatic hydrocarbons, the product C, consisting essentially of the product of non-aromatic hydrocarbons having 4-5 carbon atoms, and the product D consisting essentially of hydrogen and product nonaromatic hydrocarbons having 1-3 carbon atoms. The separation produced by the gas-liquid separator and distillation columns for the separation of use cooler, consisting of propylene, which is produced and used as a cooler in the process of producing ethylene. The resulting product C are subjected to thermal cracking in the equipment for thermal cracking under such conditions that the pressure is equal to atmospheric pressure, the degree of dilution of the pair is equal to 0.35, TVZ (outlet temperature of the coil) is equal to 825oC and time to the procedure, as in example 8, except that the resulting product C, consisting essentially of the product of non-aromatic hydrocarbons having 4-5 carbon atoms, not recyclery in single-stage adiabatic reactor with a fixed layer, and that the resulting product A, consisting essentially of the product of aromatic hydrocarbons, is subjected to dialkylamino.

As an illustration of the molded zeolite catalyst ZSM-5 obtained in the same manner as in example 8, is treated with steam under the same conditions as in example 8.

Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 6:4. Received the original product (the mass ratio of unsaturated hydrocarbons/ saturated hydrocarbons 0,86) is heated to 530oC and injected into the single-stage adiabatic reactor with a fixed layer. The resulting reaction product is separated into product And consisting essentially of the product of aromatic hydrocarbons, the product C, consisting essentially of the product of non-aromatic hydrocarbons having 4-5 carbon atoms, and the product D consisting essentially of hydrogen and product neuromotor and distillation columns, when used to split use a cooler consisting of propylene, which is produced and used as a cooler in the process of producing ethylene. Received the product And are dialkylamino under such conditions that the total conversion of aromatic hydrocarbons is 70%. The results are presented in table. 10.

Example 11. (I) 60 wt. including crystalline aluminosilicate ZSM-5 (having the atomic ratio Si/Al equal to 46 in its zeolite structure) in the form of ammonium ion, 15 wt.h. -alumina and 25 wt.h. of zinc nitrate are mixed, the resulting mixture is subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4-6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 10% by weight.

(II) When carrying out the steam treatment in the first stage single-stage adiabatic reactor with a fixed layer of fill obtained molded zeolite catalyst for the formation of the catalyst layer, the catalyst layer is heated to 600oC in flowing nitrogen. The gaseous mixture of steam-nitrogen containing 40% obamnator 600oC enter and pass through the reactor at a specific clock speed (PSP) 0,08 h-1within 10 minutes compared to 7 blocks of the catalyst layer of the same length, which are arranged along the direction of the steam flow measured temperature change of each block with time during the steam treatment. Then in the second stage input and the flow of steam first, temporarily suspend, and then pairs remaining in the reactor to displace the gaseous nitrogen. The temperature of the catalyst layer is lifted and fixed at 640oC in flowing nitrogen. Subsequently, the gaseous mixture of steam-nitrogen containing 40 volume% of steam having a pressure of 1 kg/cm2G (in which the partial vapour pressure is equal to 0.8 kg/cm2and the temperature of 640oC enter and pass through the reactor at PSP 0,08 h-1within 14 minutes of temperature Change of each of the blocks over time during the steam treatment are measured.

Above the steam treatment is carried out with the use of reciklirawe compressor, heat exchanger, heater and piping, which should be used for regeneration of the catalyst by burning.

(III) To assess the degree of dealumination molded zeolite catalysis is the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane, catalyzed by zeolite catalyst is proportional to the atomic ratio Si/Al zeolite in the zeolite catalyst. Respectively selected part of each of the 7 blocks of equal length layer of the catalyst obtained above partially dealuminated zeolite catalyst, and, with respect to each of the 7 blocks of equal length steamed catalyst layer, the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane receive the same manner as in example 1.

The activity of the zeolite catalyst and the average temperature of each of the top and the bottom layer of the catalyst during the steam treatment are presented in table. 11 together with the reaction conditions of partial dealuminated zeolite catalyst. The rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst, are presented in table. 11, proportional to the degree of dealuminated zeolite. In table. 11 the upper part of the catalyst layer is at the top block of 7 blocks of equal length catalyst layer, and the lower part of the catalyst layer is at the bottom of the block 7 blocks from the same DLU temperature obtained with respect to the upper and lower parts of the catalyst layer, and the average temperature of the lower part of the catalyst layer means an average temperature obtained with respect to the upper and lower parts of the lower part of the catalyst layer.

Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 6:4. Received the original product (the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons 0,86) is heated to 530oC and injected into the single-stage adiabatic reactor with a fixed layer. The results obtained after 10 h after start of the reaction, are presented in table. 11 together with the reaction conditions.

After the reaction remove the upper part of the catalyst layer, and the amount of coke which is formed on the zeolite catalyst during the reaction, determined by CHN CORDER MODEL MT-5, produced and sold by Yanaco Co., Ltd., Japan.

Example 12. Molded zeolite catalyst ZSM-5 receive in the same way as in stage (I) of example 11. Essentially the same method as in example 11, hold steaming molded zeolite catalyst, except that the operation of the second stage to stage (II) do not produce. In kochavim catalyst ZSM-5, which obtained in the same manner as in stage (I) of example 11, to form the catalyst layer and the catalyst layer is heated to 600oC, during the flow of nitrogen. The gaseous mixture of steam-nitrogen containing 40 volume% of steam and having a pressure of 1 kg/cm2G (in which the partial vapour pressure is equal to 0.8 kg/cm2) and a temperature of 600oC, is injected to flow through the reactor at PSP 0,08 h-2within 1 h In relation to the 7 blocks of equal length catalyst layer, which are located along the direction of the steam flow measured temperature change of each block with time during the steam treatment. The activity of the steamed zeolite catalyst was evaluated in the same way as in stage (III) of example 11. The relative activity of the upper part, middle part and lower part of the catalyst layer of partially dealuminated zeolite catalyst, and the average temperature of each of the top and bottom of the layer of catalyst during steam treatment is presented in table. 11.

Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 6:4. Received the original product (mass from the first adiabatic reactor with a fixed layer. The results obtained after 10 h after start of the reaction are shown in table. 11 together with the reaction conditions.

The upper part of the catalyst layer is removed, and the amount of coke formed on the catalyst layer during the reaction, determined in the same manner as in example 11. The results are presented in table. 11 as the relative amount of coke relative to the amount of coke that is defined in example 11.

Table. 11 shows that, when the steam treatment of the zeolite catalyst is carried out in two stages, the formation of coke on the zeolite catalyst during the reaction can be effectively suppressed.

Example 13. 60 wt. including crystalline aluminosilicate ZSM-5 (having the atomic ratio Si/Al equal to 46 in its zeolite structure) in the form of ammonium ion, 15 wt.h. - 3 alumina and 25 wt.h. of zinc nitrate are mixed, and the resulting mixture is subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4-6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 10% by weight.

Then one ª the formation of the catalyst layer. Within 5 h for the implementation of steaming zeolite catalyst is injected and passed through the reactor a gaseous mixture of steam-nitrogen containing 40 volume% of steam having a pressure of 1 kg/cm2G and a temperature of 650oC.

(I) Then prepare the original product by mixing fractions of C5specified in the table. 2, with the fraction of C4specified in the table. 1, when the mass ratio of 6: 4. Received the original product (the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons 0,86) is heated to 530-550oC and injected to flow in a single-stage adiabatic reactor with a fixed layer in two days.

(II) Then the introduction of the original product stop and produce the burning of the coke, which was formed on zeolite catalyst, for about 2 days under the conditions discussed below, through the circulation system of a combustible gas, as shown in Fig. 7, thereby regenera catalyst

The amount of circulation - 5000 m3/h (measured at 0oC, at atmospheric pressure)

The oxygen concentration of 0.8 - 1.2% of the volume

The amount of excess fuel gas, are removed from the circulation system combustible gas - 7.3 to 9.2% of volume

UCSG - 530 h-1< / BR>
Dawny gas), marked on Fig. 7 (hereinafter referred to as "gas-filler"), used in the amount of 3.5% by volume relative to the volume of circulation of the fuel gas, and the gas 28 (oxygen-containing inert gas) is used in the amount of 3.8 to 5.7% by volume relative to the volume of circulation of the fuel gas.

After the above operations (II) catalyst regeneration repeat alternately the reaction of catalytic cyclization regcognition raw materials in the same way as the above operation (I), and regeneration of the catalyst by the same method as in the above operation (II).

The results obtained in the first cyclization reaction in the catalytic cyclization reaction using a catalyst which is regenerated 75 times, are presented in table. 12 together with the reaction conditions.

The term "USSG" (specific clock speed gas) means the amount of which is determined by the following formula:

< / BR>
Example 14. Repeat basically the same procedure as in example 13, except that the gas-filler 27 for use in the regeneration of the catalyst is used in an amount of 0.1% by volume relative to the volume of circulation of the fuel gas, and the amount of excess fuel is ablation of combustible gas. The results obtained in the first reaction catalytic cyclization in the reaction of catalytic cyclization using a catalyst which is regenerated 75 times, are presented in table. 13 together with the reaction conditions.

Comparative example 12. 60 wt.h. crystalline aluminosilicate ZSM-5 (having the atomic ratio Si/Al equal to 46 in its zeolite structure) in the form of ammonium ion, 15 wt.h. -alumina and 25 wt.h. of zinc nitrate are mixed, the resulting mixture is subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4-6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 10% by weight.

Then single-stage adiabatic reactor with a fixed layer of fill obtained molded zeolite catalyst for the formation of the catalyst layer. The gaseous mixture of steam-nitrogen containing 80% by volume of steam having a pressure of 1 kg/cm2G and a temperature of 550oC, is injected to flow through the reactor for 1 h for the implementation of steaming zeolite catalyst.

To estimate the ω thus, produce a reaction test conversion of n-hexane, using a sample of zeolite catalyst at isothermal conditions, in the same way as in example 1. It was found that the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst is 3 (-1).

Then the quartz reaction tube with a diameter of 10 mm (isothermal reactor), which is the same as the one used in the test on the reaction conversion of n-hexane, fill obtained molded zeolite catalyst for the formation of the catalyst layer, and a quartz reaction tube heated by an electric stove so as to set the temperature of the catalyst layer on the whole possible to 538oC.

Then prepare the original product by mixing n-puntata with n-pentanol when the mass ratio of 60:40. Received the original product (the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons 0,66) is heated to 538oC and injected to flow through the above-mentioned isothermal reactor, thereby carrying out the reaction of catalytic cyclization. The results of the reaction, the obtained 5 h after start of the reaction, PR quartz reaction tube and electric stove, presented on Fig. 8.

As shown in the table. 13, in comparative example 12, the yield of aromatic hydrocarbons through 5 h after the start of the reaction is high, but the yield of aromatic hydrocarbons through 5 days after the start of the reaction is low. Thus, in comparative example 12, the yield of aromatic hydrocarbons can not be maintained at a high level for a long period of time.

Comparative examples 13-15. 60 wt.h. crystalline aluminosilicate ZSM-5 (having the atomic ratio Si/Al equal to 46 in its zeolite structure) in the form of ammonium ion, 15 wt.h-alumina and 25 wt.h. of zinc nitrate are mixed, the resulting mixture is subjected to extrusion molding, obtaining a molded product having a diameter of 1.6 mm and a length of 4-6 mm Molded product is dried at 120oC for 4 h, and then calicivirus at 500oC for 3 h to obtain a molded zeolite catalyst ZSM-5 having a zinc content of 10% by weight.

Then single-stage adiabatic reactor with a fixed layer of fill obtained molded zeolite catalyst for the formation of the catalyst layer. Within 2 h for the implementation of steaming realitively a pressure of 1 kg/cm2G and a temperature of 700oC.

For the evaluation of catalytic activity at the initial stage of the molded zeolite catalyst is treated with steam thus produced reaction test conversion of n-hexane, using a sample of zeolite catalyst at isothermal conditions in the same way as in example 1. It was found that the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst is 0.3 (-1).

Then the original product, consisting of fractions of C5(the mass ratio of unsaturated hydrocarbons/saturated hydrocarbons 0,37) specified in the table. 2, is heated to 530oC and injected to flow through the above-mentioned single-stage adiabatic reactor with a fixed layer at atmospheric pressure and PSP 0.8 h-1, thereby carrying out the reaction of catalytic cyclization (comparative example 13). The results obtained after 5 h after start of the reaction, are presented in table. 13 together with the reaction conditions.

Repeat basically the same procedure as in comparative example 13, except that the original product, consisting only of saturated uglev is 14). The results are presented in table. 13.

As shown in the table. 13, the yield of aromatic hydrocarbons (22,9% by weight) obtained in comparative example 13, is less than the calculated yield of aromatic hydrocarbons (29,8% by weight), which is calculated based on the yield of aromatic hydrocarbons in comparative example 14, and the yield of aromatic hydrocarbons in comparative example 15. Above the calculated yield of aromatic hydrocarbons can be obtained as follows.

(I) the Amount of each component in the fraction of C5(hydrocarbons having 5 or less carbon atoms), are presented in table. 2 (listed at the end of this table).

(II) Thus, the total number of saturated hydrocarbons is 72.9% by weight, and the number of unsaturated hydrocarbons is 27,1% by mass.

(III) As shown in table. 13, in comparative example 14 (used only saturated hydrocarbons) the yield of aromatic hydrocarbons is 19.7% by weight, and in comparative example 15 (used only unsaturated hydrocarbons) the yield of aromatic hydrocarbons is 56,8% by mass.

(IV) Respectively calculated output aromatically method of the present invention not only aromatic hydrocarbons can be obtained with a high yield of light hydrocarbons, containing olefins and/or paraffins, but also a small decrease in catalytic activity, so that the extraction of aromatic hydrocarbons can be produced stably for a long period of time, using the adiabatic reactor with a fixed layer, which can be conveniently used in industry because of its simple design and high efficiency.

The method of the present invention can be widely and conveniently used in the petrochemical industry and in the refining of oil, especially in the production of aromatic compounds and high-octane gasoline.

1. The method of obtaining aromatic hydrocarbons by catalytic cyclization, including filing regcognition raw material containing at least one component selected from the group comprising olefins and paraffins, in an adiabatic reactor with a fixed layer containing a fixed catalyst bed consisting of a zeolite catalyst, thereby resulting in contact regcognition feedstock with zeolite catalyst in an adiabatic reactor with a fixed layer, and carrying out the reaction of catalytic cyclization regcognition raw materials, where zolotoyabko catalyst and steamed zeolite catalyst, characterized in that the reaction of catalytic cyclization is carried out in conditions which satisfy the following requirements(1), (2), (3) and (4):

(1) zeolite catalyst has an initial catalytic activity of 0.2 s-1or more, corresponding to the rate constant for the initial stages of the reaction of the first order decomposition of n-hexane catalyzed by zeolite catalyst, measured at a temperature of 500oC, at atmospheric pressure;

(2) the catalyst bed has a temperature in the range 450 - 650oC;

(3) a layer of catalyst shows the temperature distribution with respect to distance from the entrance to the catalyst bed to the outlet of the catalyst layer, in which the temperature distribution has at least one maximum value, and

(4) the outlet temperature of the catalyst layer is in the range 40oWith respect to the temperature at the inlet to the catalyst bed.

2. The method according to p. 1, characterized in that the zeolite catalyst consists essentially of a zeolite.

3. The method according to p. 1, wherein the zeolite catalyst comprises a mixture of zeolite and at least one component selected from the group comprising a metal belonging to group VIII, IB, IIB or IIIB P is a torus contains a mixture of zeolite and at least one component, selected from the group comprising zinc and its derivatives.

5. The method according to p. 4, wherein the zeolite catalyst comprises a mixture of zeolite and at least one component selected from the group comprising zinc and its derivatives and aluminum oxide.

6. The method according to p. 4, wherein the zeolite catalyst comprises a mixture of zeolite and the product obtained by thermal steam treatment of the mixture of aluminum oxide and at least one component selected from the group comprising zinc and its derivatives.

7. The method according to p. 4, wherein the zeolite catalyst comprises a mixture of zeolite and zinc aluminate.

8. The method according to PP.4 to 7, characterized in that the content of at least one component selected from the group comprising zinc and its derivatives, in the zeolite catalyst is 5-25% by weight relative to the amount of zinc.

9. The method according to p. 1, characterized in that the zeolite in the zeolite catalyst is replaced by a metal belonging to group VIII, IB, IIB or IIIB of the Periodic table.

10. The method according to PP.1 to 9, characterized in that the zeolite is zeolite catalyst has an atomic ratio Si/Al of at least 12 in its zeolite structure and the sodium content is 50 the ATOR contains zeolite ZSM-5.

12. The method according to PP.1 - 11, characterized in that the zeolite catalyst is essentially fresh zeolite catalyst.

13. The method according to PP.1 - 11, characterized in that the zeolite catalyst is steamed zeolite catalyst, which is obtained by steam treatment, essentially fresh zeolite catalyst.

14. The method according to p. 1, wherein the zeolite catalyst comprises a mixture of steamed zeolite catalyst, which is obtained by steam treatment, essentially fresh zeolite catalyst consisting essentially of a zeolite and at least one component selected from the group comprising a metal belonging to group VIII, IB, IIB or IIIB of the Periodic table and its derivatives.

15. The method according to p. 13 or 14, characterized in that the steam processing, essentially, a fresh zeolite catalyst produced by the flow of steam flow through the reactor for steam treatment, containing essentially fresh zeolite catalyst with the sequence of the following stages (a) and (b):

(a) a stream of steam having a partial vapor pressure of not less than 0.1 kg/cm2and the temperature of 500-650oWith, fed through the reactor for processing BR> (b) carry out temporary suspension flow through the reactor for steam treatment and removal of steam that remains in the reactor, steam having a partial vapor pressure of 0.1-10 kg/cm2and temperature 515-700oWith, fed through the reactor for steam treatment under the condition that the temperature of the steam flowing in stage (b) is higher than the temperature of the steam flowing in the phase (a) phase (b) carry out at least once, so that the steam flowing in each stage (b), is subjected to contact with the zeolite catalyst is treated with steam at the stage preceding each stage (b).

16. The method according to PP.1 - 15, characterized in that regcognition raw material contains at least one component selected from the group comprising fraction WITH4product system high temperature thermal cracking of hydrocarbon material oil or a fraction obtained by removing butadiene or removal of butadiene and I-butene from the faction WITH4; fraction5product system high temperature thermal cracking of hydrocarbon material oil or a fraction obtained by removing dienes from the faction WITH5; thermally graciously gasoline; the raffinate obtained potm catalytic cracking of petroleum condensate; received fluid catalytic cracking graciously gasoline; a raffinate obtained by extracting aromatic hydrocarbons from the reformed; liquefied petroleum gas installation for cracking and crude oil.

17. The method according to PP.1 to 16, characterized in that regcognition raw material contains a fraction of saturated hydrocarbons and a fraction of unsaturated hydrocarbons, where the mass ratio of the fraction of saturated hydrocarbons and fractions of unsaturated hydrocarbons is 0.43 - 2,33.

18. The method according to PP. 1 to 17, characterized in that the internal pressure of the adiabatic reactor during the cyclization reaction is in the range from atmospheric pressure to 30 kg/cm2and regcognition raw material is introduced into the adiabatic reactor at a specific clock speed (PSP) 0.1 to 50 h-1.

19. The method according to PP. 1 to 18, characterized in that carry out the separation of the resulting cyclization reaction mixtures containing aromatic hydrocarbons, product And consisting essentially of aromatic hydrocarbons and a product consisting essentially of hydrogen and non-aromatic hydrocarbons having 1 to 5 carbon atoms, with the division performed by hesoid who eat what carry out the separation of the resulting cyclization reaction mixtures containing aromatic hydrocarbons, product And consisting essentially of aromatic hydrocarbons, the product consisting essentially of nonaromatic hydrocarbons having 4 to 5 carbon atoms, and the product D consisting essentially of hydrogen and non-aromatic hydrocarbons having 1 to 3 carbon atoms, and the separation is conducted through a gas-liquid separator and, optionally, distillation columns.

21. The method according to p. 19 or 20, characterized in that the gas-liquid separation is conducted using a cooler consisting of propylene or ethylene, obtained by high temperature thermal cracking of petroleum hydrocarbons.

22. The method according to p. 19, characterized in that at least part of the product, consisting essentially of hydrogen and non-aromatic hydrocarbons having 1 to 5 carbon atoms, recyclart in the adiabatic reactor and used as part of regcognition raw materials.

23. The method according to p. 19, characterized in that at least part of the product, consisting essentially of hydrogen and non-aromatic hydrocarbons having 1 to 5 carbon atoms, is fed into the system becauseshe fact, that at least a portion of at least one component selected from the group comprising a product consisting essentially of nonaromatic hydrocarbons having 4 to 5 carbon atoms, and the product D consisting essentially of hydrogen and non-aromatic hydrocarbons having 1 to 3 carbon atoms, recyclart in the adiabatic reactor and used as part of regcognition raw materials.

25. The method according to p. 20, characterized in that at least a portion of at least one component selected from the group comprising a product consisting essentially of nonaromatic hydrocarbons having 4 to 5 carbon atoms, and the product D consisting essentially of hydrogen and non-aromatic hydrocarbons having 1 to 3 carbon atoms, is introduced into the system high temperature thermal cracking of petroleum hydrocarbons.

26. The method according to PP.19 to 25, characterized in that the product And consisting essentially of aromatic hydrocarbons, is subjected to processing by at least one method selected from the group consisting of the following methods: method by which the product And process, using the equipment for dealkylation, obtaining benzene; the way in which the product And process, using equipment Zola, toluene and xylene; the way in which the product And process, using equipment for disproportionation or equipment for isomerization, and the way in which the product And mix with gasoline.

27. The method according to PP.1 to 26, characterized in that the carry out suspension filing regcognition raw materials in the adiabatic reactor with a fixed layer and the burning of the coke formed on the zeolite catalyst during the reaction of catalytic cyclization oxygen-containing inert gas as a fuel gas for the regeneration of the zeolite catalyst in the regeneration zone of the catalytic Converter.

28. The method according to p. 27, characterized in that the excess fuel gas discharged from the regeneration of the catalyst, recyclart in the area of regeneration of the catalyst through the heater through reciklirawe compressor, thereby forming a circulation system of a combustible gas, comprising a regeneration zone of the catalyst, recyclery compressor and heater connected in this order through the pipeline, with fresh, oxygen-containing inert gas is fed into the circulation system of the fuel gas at the first entrance, located between the exit from the zone of regeneration of the catalyst istemi circulation excess fuel gas fuel gas is removed from the zone of regeneration of the catalyst before it enters the heater in number, which is essentially equal to the amount of fresh oxygen-containing inert gas fed to the first input, where the number and the content of oxygen, the supply of fresh oxygen-containing inert gas is adjusted so that the combustible gas flowing into the regeneration zone catalyst has an oxygen content of 0.01 - 10 vol.%.

29. The method according to p. 28, characterized in that conduct a fresh inert gas not containing oxygen in the circulation system combustible gas to the second input of which is identical to the first input or provided separately from the first input between the output of the zone of regeneration of the catalyst and the inlet of the heater, in the amount of 10 vol.% or less with respect to the circulating volume of combustible gas, and the subsequent discharge of the circulation system fuel gas excess fuel gas is removed from the zone of regeneration of the catalyst before it enters the heater in a quantity which is essentially equal to the quantity of fresh inert gas not containing oxygen is supplied to the second input, thereby suppressing an increase in the partial pressure of steam in the fuel gas supplied to the regeneration zone of the catalytic Converter.

30. The method according to p. 29, characterized in that the conducting cooling the fuel gutreuter, this cooling and heating is performed using at least one heat exchanger.

31. The method according to PP. 13 to 15, characterized in that the steam processing, essentially, a fresh zeolite catalyst is done using the circulation system pair includes a reactor for steam treatment, recyclery compressor, heater and at least one heat exchanger, which are connected by a pipeline.

32. The method according to p. 31, characterized in that the reactor for steam treatment is used as an adiabatic reactor.

33. The method according to p. 31 or 32, characterized in that the circulation system pair is used as the circulation system combustible gas for the regeneration of zeolite catalyst under item 28, where the reactor for process steam is used as the reactor for regeneration or replace the reactor for regeneration, including the zone of regeneration of the catalyst in the system of circulation of the fuel gas and where a combustible gas circulation system combustible gas is used instead of the steam system steam circulation.

 

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