Integrated method for production of alkyl- and alkenyl-combustion aromatics (options)

FIELD: petrochemical processes.

SUBSTANCE: simultaneous dehydrogenation of mixture containing alkyl and alkylaromatic hydrocarbons is followed by separating thus obtained dehydrogenated alkyl hydrocarbon and recycling it to alkylation unit. Dehydrogenation reactor-regenerator employs C2-C5-alkyl hydrocarbon as catalyst-transportation carrying medium.

EFFECT: increased process flexibility and extended choice of catalysts.

36 cl

 

The present invention relates to an integrated process for the preparation of alkyl - and alkenylamine aromatic compounds.

More specifically, the present invention relates to an integrated method for producing alkyl substituted aromatic compounds, such as ethylbenzene, and alkenylamine aromatic compounds such as styrene and α-methylsterol (via cumene), derived from aromatic, such as benzene and alkane, such as ethane or propane.

More specifically, the present invention relates to an integrated process for the preparation of ethylbenzene and styrene with simultaneous dehydrogenation of ethylbenzene to form styrene, and ethane - with the formation of ethylene, used as reagent for the synthesis of ethylbenzene.

It is well known that styrene and α-methylsterol are products that are used for the production of thermoplastic polymers, such as polystyrene, copolymers of Acrylonitrile, butadiene and styrene, styrolacrylonitrile resins, styrene-butadiene elastomeric copolymers, and compositions for the manufacture of unsaturated polyester resins.

Styrene is usually produced by the catalytic dehydrogenation of ethylbenzene in the adiabatic or isothermal system and in the presence of catalysts selected from metal oxides or mixtures of oxides of the metal is in, and ethylbenzene is produced by alkylation of benzene, available as a product of oil refining, ethylene, obtained by the cracking or dehydrogenation of ethane.

The alkylation reaction can be carried out in the vapor phase using as catalysts zeolites with a high ratio of SiO2/Al2O3for example, zeolite ZSM-5, or Lewis acids, either in the liquid phase. Details of the synthesis of ethylbenzene and its dehydrogenation to obtain styrene described in the Stanford Research Institute (SRI International) Reports.

In U.S. patent 6031143 describes an integrated method of producing ethylbenzene and styrene, which includes the following stages:

- flow of benzene and the flow re-circulating stream containing ethylene in an alkylation plant;

- mixing stream containing ethylbenzene and leaving the alkylation unit, with a stream comprising ethane;

the supply thus obtained mixture in the installation dehydrogenation containing a catalyst capable of simultaneously carry out dehydration as ethane and ethylbenzene with the formation of ethylene and styrene, respectively;

- the flow of product out of a facility dehydrogenation, in the separating (dividing) part of the installation to obtain a stream essentially consisting of styrene and a stream containing ethylene;

- re is circulatio thread containing the ethylene in the alkylation plant.

Installation dehydrogenation includes a first dehydrogenation reactor in the fluidized bed and the second reactor regeneration of spent catalyst. Last continuously removed from the bottom of the first reactor and serves in the upper part of the second reactor, where the catalyst support in a fluidized state by means of moving up the pre-heated air. Thus, the spent solid catalyst slowly goes down countercurrent with respect to the rising hot air, and during this downward movement occurs, the regeneration of the catalyst, during which burn carbon-containing residues which contaminate the catalyst. Transporting catalyst from one reactor to another is performed with the help of a carrier gas, such as air or nitrogen.

However, the simultaneous dehydrogenation of ethane and ethylbenzene has its disadvantages, because these two products have characteristics that are difficult to obtain an acceptable degree of conversion and selectivity towards ethylene and styrene under the same conditions. For example, to obtain the equilibrium degree of conversion of ethylbenzene to styrene at atmospheric pressure, equal to 50%, the required temperature of about 615°With, while at the same the conditions of equilibrium degree of conversion of ethane to ethylene is only 20%. To achieve the equilibrium degree of conversion of ethane into ethylene, equal to 50%, the required temperature of at least 720°but at this temperature there is a thermal destruction as ethylbenzene and styrene. More details on these processes are described in the book Paul H. Emmett "Catalysis - Hydrogenation and Dehydrogenation" vol. III, 453-471, 1995, Reinhold Publishing Corporation.

Thus, the conditions for the implementation of the method described in the cited above U.S. patent is limited and you need to be most careful control of the operation of the dehydrogenation reactor.

The applicant of this application has developed an integrated method of obtaining alkylsilane aromatic compounds, such as ethylbenzene, and alkenylamine aromatic compounds such as styrene, with greater flexibility and a wider choice of catalysts. The method involves the dehydrogenation reactor in the fluidized bed, the flow in which alkane (ethane) at least partially separated from the ethylbenzene feed, as described below, since the fluidized bed reactor/regenerator with circulating solids have different temperature zones. Indeed, in the installation of fluidized bed system "reactor/regenerator heat required for dehydrogenation, comes from the hot regenerated catalyst which is continuously fed into the dehydrogenation reactor transport pipelines from the regenerator, operating at a higher temperature.

Thus, the present invention is an integrated method for production of alkyl - and alkenylamine aromatic compounds, such as ethylbenzene and styrene, which includes:

(a) filing in the alkylation plant flow consisting of an aromatic hydrocarbon With6-C12and re-circulating stream containing alkanniny hydrocarbon With2-C5;

b) possible mixing of the flow coming from the alkylation unit and containing alkylaromatic compound with a stream consisting of alkyl hydrocarbon With2-C5;

C) flow obtained in stage (b)to the dehydrogenation/regeneration of fluidized bed containing a dehydrogenation catalyst capable of dehydration, and also simultaneously, alkyl hydrocarbon, possibly present in the stream, and alkylaromatic compounds;

g) continuous discharging spent catalyst, which accumulates in the bottom of the dehydrogenation reactor, and the flow in the upper part of the reactor regeneration;

d) continuous discharging regenerated catalyst which accumulates in the lower part of the reactor regeneration, and its flow in the upper part of the dehydrogenation reactor;

(e) flow angle is odorata, effluent from the dehydrogenation reactor, in the separating section for receiving the stream essentially consisting of alkenylsilanes aromatic compounds and a stream containing alkanniny hydrocarbon;

g) recycling the stream containing alkanniny hydrocarbon in the alkylation plant;

with specified integrated method is characterized by the fact that the fluid medium for transporting catalyst which accumulates in the lower part of the regenerator at a temperature of 650-800°With, in the dehydrogenation reactor consists of alkyl hydrocarbon With2-C5.

In accordance with the present invention the alkylation plant serves a first stream comprising an aromatic hydrocarbon, for example, the feed of fresh refined (fresh refinery grade) benzene, i.e. having a purity of at least 95 wt. -%, and the second recycle stream essentially consisting of alkenylphenol hydrocarbon, such as ethylene and unreacted alkyl hydrocarbon, such as ethane. More specifically, this second stream consists of 20-95 mol%, preferably 40-80 mol%. from ethane, and 5-80 mol%, preferably 15-60 mol%. from ethylene, respectively.

In recirculating flow are also present, in quantities of 0.1-2% wt. (based on the total weight of the ethylene+ethane), other light products, such as IU is an hydrogen, formed during alkylation, and at the stage of dehydrogenation.

Both streams enter the installation for alkylation, so that the molar ratio of benzene/ethylene meet the requirements of modern technology, i.e. typically between 1.8 and 50, preferably between 2 and 10. The alkylation reaction is carried out in conventional systems, for example in accordance with the method described in European patent 432814.

In the method corresponding to the present invention, it is possible to use any of the alkylation reactor, such as reactor with a fixed catalyst bed or reactor psevdoozhzhennom layer, a reactor with a layer of the carrier and the catalytic distillation reactor. For example, can be used catalytic distillation reactor operating in the gas-liquid mixed phase, described in U.S. patent 5476978 and in published international patent application WO 98/09929. In the catalytic distillation reactor the reactants and products of the catalytic reaction, in this case the reagents and the products of alkylation, simultaneously separated by distillation using a catalytic reactor as distillation columns.

The preferred alkylation catalysts include synthetic and natural porous crystalline solids, such as acid price is lita in which the atomic ratio of silicon/aluminum ranges from 5/1 to 200/1. In particular, preferred are Y-zeolites, beta zeolites, mordenite, omega-, And-, X - and L-zeolites or porous crystalline materials MCM-22, MCM-36, MCM-49, MCM-56 and ERS-10.

In an alternative embodiment of the present invention, the alkylation reaction can be carried out using the reactor of continuous fixed bed operating in the gas phase, as described, for example, in U.S. patents 4409412 and 5517184. In this case, the catalyst is selected from zeolites of the group ZSM, in which the atomic ratio si/al is in the range of 20/1 to 200/1. Examples of zeolites of type ZSM are ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48. Especially preferred is ZSM-5.

The alkylation reaction is carried out at temperatures and pressures, which are known to experts in the art, depend on the type of reaction and the choice of reagents. In the case of the alkylation of benzene with ethylene, the reaction temperature is usually in the range from 50 to 450°C. More specifically, to processes occurring in the gas phase, the temperature preferably is in the range from 325 to 450°With, while in the case of catalytic distillation reactor operating in a mixed gas-liquid phase, the reaction temperature, varying within a layer kata is Isadora, ranges from 140 to 350°C, preferably from 200 to 300°C.

The pressure in the alkylation reactor is maintained at a level of from 0.5 to 6 MPa, preferably from 2 to 4.5 MPa.

The aromatic hydrocarbon stream leaving the alkylation reactor may be subjected to conventional processing to produce, respectively, essentially pure stream of unreacted aromatic product, such as benzene, essentially pure stream of alkyl substituted aromatic compounds, such as ethylbenzene, and flow more heavy products, essentially consisting of di - or polyalkylene aromatic compounds, for example di - or polietilenovoi.

Separation (separation) system preferably consists of a series of distillation (distillation) columns; the first column remove unreacted benzene, which then enters recycle to the alkylation reactor or install parallelomania, as described below. The benzene extract the second distillation column and sent to the dehydrogenation, while polietileno, such as diethylbenzene and triethylbenzene, remove the third column.

Polyalkylene aromatic compounds, such as polietileno, may enter the reactor parallelomania together with aromatic hydrocarbons -C12in this case - together with benzene, to obtain the corresponding monosubstituted aromatic compounds, such as ethylbenzene, and enhance the yield of the alkylation reaction.

The reactor parallelomania preferably consists of a reactor with a fixed bed of catalyst, operating in liquid phase, in which there is a traditional catalyst parallelomania, such as Y-zeolite, beta zeolite or mordenite, preferably a Y zeolite beta or zeolite. The reaction parallelomania can be carried out as described in U.S. patent 5476978.

If parallelomania of polietilenovoi benzene molar ratio benzene/ethylene, calculated in relation to the total number of moles of benzene, in the form of the actual benzene, and in the form of polietilene, and taking into account the total number of moles of ethylene present in the form of a substituent polietilenovi is from 1.8/1 to 17/1, preferably from 2.4/1 to 10/1. The temperature in the reactor parallelomania maintained within the range of from 50 to 300°C, preferably from 120 to 250°and the pressure is maintained within the range of from 0.02 to 5.5 MPa, preferably from 0.7 to 4.5 MPa.

Alkyl hydrocarbon With2-C5or, in the preferred case, ethane, which can also be mixed with the product of alkylation, is a stream of fresh raw materials, octopuscollective with oil, and, thus, is available as benzene with a purity of at least 95% of the mass. Ethan, loaded at this stage, is usually 0-70% of the mass. of the total number of ethane.

The stream containing the product of alkylation, which can also be mixed with ethane, served in a gaseous state in the basis of the dehydrogenation reactor, which operates at temperatures lying in the range from 450 to 650°and pressures from 0.1 to 3 ATM. abs. (ATA), preferably at atmospheric pressure or a pressure slightly more than atmospheric; the flow rate of reagents, expressed in units of volume of reagent per hour per liter of catalyst (gas hourly space velocity or GHSV) is in the range from 100 to 10000 h-1preferably from 100 to 1000 h-1, and the residence time of the catalyst in the zone of the fluidized bed ranges from 5 to 30 minutes, preferably from 10 to 15 minutes.

For optimal carrying out the dehydrogenation catalyst is loaded into the upper part of the reactor and maintain in the fluidized state by means of a stream of hydrocarbon fed to the base unit, so that the catalyst slowly moves down to the lower part of the machine, countercurrent to the rising gas phase. Advancing the catalyst slowly deactivated and accumulates in the lower part of the apparatus is essentially in the waste form.

Otruba the p catalyst is continuously removed from the bottom of the dehydrogenation reactor and served with the conveying medium, such as air or nitrogen, into the reactor regeneration. The reactor regeneration works essentially the same way as the dehydrogenation reactor. The spent solid catalyst load in the upper part of the reactor and maintain in the fluidized state by means of preheated air, possibly enriched with oxygen, so that the catalyst slowly moves down to the lower part of the machine, countercurrent to the rising hot air. Advancing carbon-containing residues contained in the catalyst, slowly fade, so that in the lower part of the regenerator accumulate essentially the regenerated catalyst. Due to the high selectivity of the dehydrogenation reaction, to supply the heat necessary to maintain thermal balance of the system, the regenerator may also be filed with the fuel gas, the combustion of which is maintaining a specified balance.

Preferably, the regenerator is operated at atmospheric pressure or the pressure a little more atmospheric, with flow rate range from 100 to 1000 h-1and residence time of solid particles in the apparatus in the range from 5 to 60 minutes, preferably from 20 to 40 minutes. The temperature profile in the reactor regeneration is usually from 600 to 800°C.

The regenerated catalyst at a temperature of about 650-800°n is discontinuously removed from the lower part of the reactor regeneration and fed into the dehydrogenation reactor using alkyl hydrocarbon With 2-C5or ethane, which is used as the conveying medium and comprising from 30 to 100% of the mass. of its total used amount, preferably from 50 to 70% of the mass. During transport from the regenerator to the reactor for the dehydrogenation of ethane is converted to ethylene, cooling, therefore, the catalyst, which is then fed to the dehydrogenation reaction, creating the optimal reactor temperature profile for the conversion of ethylbenzene to styrene.

In the method in accordance with the present invention can be any catalyst capable of dehydrogenation, if possible, simultaneously, paraffin such as ethane, and alkylaromatic hydrocarbons, such as ethylbenzene. For example, particularly preferred are the catalysts described in International patent application PCT/EP 00/9196 prepared on the basis of iron and one or more promoters selected from alkali or alkaline earth metals and lanthanides, on a substrate of alumina, located in the Delta or theta phase or in a mixed Delta+theta, theta+alpha or Delta+theta+alpha phase, modified silicon oxide and having a surface area defined by the way BETH, preferably less than 150 m2/, More specifically, this catalyst, which includes:

- 1-60 wt. -%, preferably 1-20% mA is C. iron oxide;

the 0.1 - 20 wt. -%, preferably 0.5 to 10 wt. -%, at least one oxide of an alkaline or alkaline-earth metal, for example potassium;

- 0-15 wt. -%, preferably 0.1 to 7 wt. -%, the second promoter selected from the oxides of lanthanides such as cerium, lanthanum or praseodymium;

and addition to 100% alumina, modified 0.08 to 5% of the mass. silicon oxide.

Other examples of catalysts are catalysts based on gallium and platinum, are described in European patent 637578, or on the basis of chromium and tin, is described in European patent 894781. Other catalysts for the dehydrogenation of paraffins and/or alkylaromatic hydrocarbons is described in European patent 400448 and 335130 and in International patent application WO 96/34843.

The catalyst based on gallium and platinum may be selected from catalysts, including:

- 0.1 to 34 wt. -%, preferably of 0.2 to 3.8% of the mass. Ga2About3;

- 1-99 parts per million (mass.), preferably 3-80 parts per million of platinum;

0.05 to 5 wt. -%, preferably, 0.1 to 3 wt. -%, oxide of alkaline and/or alkaline earth metal, for example potassium;

- 0.08 to 3% of the mass. silicon oxide;

and addition to 100% alumina, located in the Delta or theta phase or in a mixed Delta+theta, theta+alpha or Delta+theta+alpha phases and having a surface area m is it 150 m 2/g, a specific way BET.

The catalyst based on chromium and tin may be selected from catalysts, including:

- 6-30 wt. -%, preferably 13-25% of the mass. Cr2About3;

of 0.1 to 3.5 wt. -%, preferably 0.2 to 2.8% by mass. SnO;

0.4 to 3 wt. -%, preferably of 0.5 to 2.5 wt. -%, oxide of an alkali metal, for example potassium;

- 0.08 to 3% of the mass. silicon oxide;

and addition to 100% alumina, located in the Delta or theta phase or in a mixed Delta+theta, theta+alpha or Delta+theta+alpha phases and having a surface area less than 150 m2/g, a specific way BET.

After dehydrogenation allocate digidrirovanny stream essentially consisting of ethylene and styrene. More specifically, the flow includes: 15-30% of the mass. styrene; 7-15% of the mass. ethylene; 10-50% of the mass. unreacted ethylbenzene and 15-55% of the mass. unreacted ethane, as well as other products such as hydrogen, methane, toluene, benzene, formed during alkylation, and at the stage of dehydrogenation.

Digidrirovanny stream is cooled, filtered and sent to the distillation section for extracting styrene and unreacted ethylbenzene, which serves recycle to the dehydrogenation, as well as to extract stream containing ethylene, which serves recycling to boot in the alkylation plant.

If available cash is chii dehydrogenation catalyst is active enough i.e. for the reaction of dehydrogenation quite short time of contact of the reacting gas with the catalyst, the dehydrogenation reactor may switch with associated flows, wherein the gas transfers the whole of solids up pneumatically (reactor with upward flow). In this case, the rate of gas per unit cross-section of the reactor must be greater than the final velocity of the largest particles present in the fluidized bed. Therefore, the velocity of the gas per unit cross-section of the reactor is of the order of magnitude of at least a few m/s Bulk velocity of the gas (GHSV) for such a reactor exceeds 500 h-1and preferably greater than 1000 hours-1. In this case, the alkyl hydrocarbon is fed into the lower part of the reactor with upward flow, entering into contact with the catalyst at a maximum reaction temperature. A stream containing alkylaromatic compound, on the other hand, is injected into the reactor with upward flow at a suitable height, when it happened dehydrogenation mostly alkyl hydrocarbon, and the temperature decreased to values compatible with the proper course of the reaction is the dehydrogenation of alkylaromatic compounds.

Integrated method of producing ethylbenzene and styrene in accordance with the present invention can additionally explain the using the supplied on the shape of the block diagram, where as a non-limiting example presents one possible implementation.

In accordance with the notation in the diagram (A) represents the alkylation plant, (D) the dehydrogenation reactor, (R) - installation regeneration of the catalyst (C) is a water condenser, (S) - scrubber, (SP) - separation section of the setup presented sequentially connected by means of distillation, (F) - filtration installation; (G1) and (G2) are two of the heat exchanger for heat exchange between gases (K1) and (K2) - compressors (V) - separator for separating gas and liquid, (LT) is a membrane separation system, (T1) and (T2) - pneumatic pipelines for the transport of the catalyst between the reactor and the regenerator, and (ST) - a flue for the discharge of smoke into the atmosphere.

Thus, the present invention is fully illustrated on the basis of the accompanying schematic and the above description. Indeed, the thread (1)consisting of benzene, and the recirculated flow (14), essentially consisting of ethylene and ethane, together with traces of hydrogen and methane, serves as reagents in unit (A) alkylation. Inert products (3), which otherwise would accumulate in the production cycle, is removed from the alkylation unit.

Alkilirovanny stream (4), essentially consisting of setimental and ethane, mixed with the second recirculating flow (16)containing ethylbenzene and coming from the distillation section (S). Part ethane required for the integrated method in accordance with the present invention, may be added through pipe (2) to the stream (4).

Thus obtained compound (5) after preheating in (G1) download via pipeline (7) into the reactor (D) dehydrogenation. The reactor (D) works together with the installation of (R) catalyst regeneration. In particular, the spent catalyst, which accumulates in the lower part (D)is continuously removed and transported by the pneumatic method according pipeline (T1), and by introducing transporting gas, such as air or nitrogen, into the upper part of the regenerator (R). Thread (21) of the air taken from the atmosphere (19), is subjected to compression (K2) with the formation of the stream (20), which is pre-heated in (G2) and served in the regenerator. Air (21)is fed to the base unit using a suitable distribution device, not shown in the drawing, burns carbonaceous deposits (coke deposited on the catalyst surface, and, rising in a counter supports solid particles in fluidized condition. Exhaust gases (22) from the regenerator is cooled in (G2), filtered (F) and throw them through (ST).

Similarly, regenerated kata is isator, which accumulates in the lower part (R), is continuously removed and transported by the pneumatic method according pipeline (T2), entering as a carrier gas ethane (6), in the upper part of the reactor (D) dehydrogenation. In the process of moving ethane thoroughly mixed with the hot catalyst, while it is partially converted into ethylene, reducing the temperature of the catalyst to values acceptable for the dehydrogenation of ethylbenzene.

Digidrirovanny product (8)which is essentially composed of styrene, ethylene, unreacted ethylbenzene and ethane, methane, hydrogen and other products such as toluene and benzene, cooled in (G1), washed from the captured fine particles in (S), then cooled in the condenser (C) and sent to a separator (V). Stream (12) products capable of condensation, essentially consisting of styrene, ethylbenzene and other by-products (benzene, toluene), is removed from the lower part (V), while the stream (11) of light products, essentially consisting of ethylene, ethane, methane and hydrogen are then removed from the upper part of the device.

Stream (12) is sent to a distillation unit (8), for example, the installation comprising one or more distillation columns, from which extract styrene (18) of high purity (>99.5%pure), together with ethylbenzene (16), directed by recycle to the dehydrogenation, and by-products (17), the direction is appropriated for subsequent processing.

Stream (11) is brought into the apparatus (K1) to the working pressure of the alkylation unit, separated from the hydrogen (15) in the membrane separation system (LT) and serves recycle in (A) as the primary raw material for piping (14).

Below for a better understanding of the present invention and variants of its implementation is shown illustrating a non-limiting example.

Example

Describes an integrated system for producing styrene, working within 8400 hours per year with normal annual capacity of 3,500 tonnes of styrene.

The installation is made simultaneous dehydrogenation of ethane and ethylbenzene in a manner analogous to the method described in U.S. patent 6031143. Ethylbenzene necessary for the production of styrene is mixed with ethane so that they are loaded in the reactor stream consisted of 30 mol%. ethylbenzene and 70 mol%. ethane. The reaction is carried out in the fluidized bed at an average pressure of 1.5 atmospheres and a temperature of from 550°in the lower part of the reactor up to 600°in the upper part of the catalytic layer, which load the hot regenerated catalyst leaving the reactor. The volumetric rate of gas (GHSV) is 300 standard liters of gas (reduced to standard conditions) per hour per liter of catalyst. The dehydrogenation catalyst comprises gallium oxide (2,33% mass.), the potassium oxide (0.6% of the mass), platinum (75 parts nmillion), the silicon oxide (1,56% wt.); addition to 100% alumina, and the residence time of solid particles (catalyst) in the apparatus is equal to 12 minutes. The degree of conversion of ethylbenzene is 52 wt. -%, and the selectivity for styrene - 92% of the mass. The degree of conversion of ethane is 10 wt. -%, and the selectivity for ethylene - 90% of the mass. Thus, the molar ratio of reacted with benzene and the resulting ethylene equal to 2.5.

Additional quantities of ethane, equal to 60% of pre-mixed with ethylbenzene, enters the base of the pipeline transporting catalyst from the regenerator to the reactor in which the temperature of the regenerated catalyst to bring the average temperature of 650°and to the mean pressure 2 bar (0.2 MPa).

Ethan acts as a transporting gas and partially reacts with the formation of ethylene. The yield of ethylene is 20 wt. -%, and therefore, after the exhaust gas from the fluidized bed reactor is mixed with transporting gas from the regenerator to the reactor, the molar ratio of reacted with benzene and the resulting ethylene is 0.99. Thus, using dehydrogenation of ethane receive an additional amount of ethylene which is sufficient for use as a reagent in section alkiline the project and to obtain the total ethylbenzene, which reacts in the dehydrogenation reactor.

1. Integrated method for production of alkyl - and alkenylamine aromatic compounds, which includes:

a) a feed stream comprising an aromatic hydrocarbon, C6-C12and re-circulating stream containing alkanniny hydrocarbon With2-C5in the alkylation plant;

b) possible mixing of the flow coming from the alkylation unit and containing alkylaromatic compound with a stream consisting of alkyl hydrocarbon, C2-C5;

C) flow obtained in stage (b)to the dehydrogenation/regeneration of fluidized bed containing a catalyst capable of implementing dehydrogenation, and also simultaneously, alkyl hydrocarbon, possibly present in the stream, and alkylaromatic compounds;

g) continuous discharging spent catalyst, which accumulates in the bottom of the dehydrogenation reactor, and the flow in the upper part of the reactor regeneration;

d) continuous discharging regenerated catalyst which accumulates in the lower part of the reactor regeneration, and its flow in the upper part of the dehydrogenation reactor;

e) feeding the hydrocarbon stream leaving the dehydrogenation reactor, Sep'a the include section for more flow, essentially consisting of alkenylsilanes aromatic compounds and a stream containing alkanniny hydrocarbon;

g) recycling the stream containing alkanniny hydrocarbon in the alkylation plant;

with specified integrated method differs in that the fluid medium for transporting catalyst that is deposited in the lower part of the regenerator at a temperature of 650-800°With, in the dehydrogenation reactor consists of alkyl hydrocarbon With2-C5.

2. An integrated method according to claim 1, in which the aromatic hydrocarbon With6-C12represents benzene.

3. An integrated method according to claim 1, in which the alkyl/alkanniny hydrocarbon With2-C5represents ethane/ethylene.

4. An integrated method according to claim 1, in which the recirculated stream is 20-95 mol.% ethane and 5-80 mol.% from ethylene, respectively.

5. An integrated method according to claim 1, in which the streams fed to the alkylation plant so that the molar ratio of benzene/ethylene ranged from 1.8 to 50.

6. An integrated method according to claim 1 in which the alkylation plant includes a catalytic distillation reactor, which operates in a mixed gas-liquid phase.

7. An integrated method according to claim 1 in which the alkylation plant includes a reactor representatvie with a fixed layer, working in the gas phase.

8. An integrated method according to claim 6, in which the alkylation catalyst is chosen from synthetic and natural porous crystalline solids, such as acidic zeolites, in which the atomic ratio of silicon/aluminum ranges from 5/1 to 200/1.

9. The integrated method of claim 8, in which the alkylation catalyst selected from Y-, beta-zeolites, mordenite, omega-, And-, X - and L-zeolites or porous crystalline solids MCM-22, MCM-36, MCM-49, MCM-56 and ERS-10.

10. An integrated method according to claim 7, in which the alkylation catalyst is selected from zeolites of the group ZSM, in which the atomic ratio si/al is from 20/1 to 200/1.

11. An integrated method according to claim 10, in which the alkylation catalyst selected from zeolite ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48.

12. An integrated method according to claim 11, in which the alkylation catalyst is ZSM-5.

13. An integrated method according to claim 1 in which the alkylation reaction is carried out at a temperature of from 50 to 450°C.

14. An integrated method according to claim 6, in which the temperature of the alkylation, varying within a layer of catalyst is from 140 to 350°C.

15. An integrated method according to claim 7, in which the temperature of the alkylation is from 325 to 450°C.

16. An integrated method according to claim 1, in which the pressure in the reaction is the PR alkylation support level, constituting from 0.5 to 6 MPa.

17. An integrated method according to claim 1 in which the alkylation plant includes a separation system for receiving, respectively, essentially pure stream of unreacted aromatic products (benzene), essentially pure stream of alkyl substituted aromatic compounds (ethylbenzene), and flow more heavy products, essentially consisting of di - or polyalkylene aromatic compounds (di - or polietilenovoi).

18. An integrated method according to 17, in which the separation system consists of a series of distillation columns, the first column remove unreacted benzene, which is then served by recycling to the alkylation reactor or install parallelomania, in the second distillation column remove ethylbenzene and send it to the dehydrogenation, and in the third column, remove polietileno, essentially representing diethylbenzene and triethylbenzene.

19. An integrated method according to claim 1, in which polyalkylene aromatic compound fed into the reactor parallelomania for the implementation of parallelomania with aromatic hydrocarbons6-C12to obtain the corresponding monosubstituted aromatic compounds.

20. An integrated method according to claim 1, in which the reaction peralkaline the ia carried out in a reactor with a fixed catalyst bed, working in the liquid phase which contains the catalyst parallelomania selected from Y-zeolite, beta zeolite or mordenite.

21. An integrated method according to claim 1, in which in the case of parallelomania of polietilenovoi benzene, the molar ratio of benzene/ethylene, calculated taking into account the total number of moles of benzene in the form of the actual benzene, and in the form of polietilene, and taking into account the total number of moles of ethylene present in the form of a substituent polietilenovi is from 1.8/1 to 17/1.

22. An integrated method according to item 21, in which the temperature in the reactor parallelomania maintained within the range of from 50 to 300°and the pressure is maintained within the range of from 0.02 to 5.5 MPa.

23. An integrated method according to claim 1, in which the alkyl hydrocarbon With2-C5supplied to the flow coming from the alkylation unit is 0-70 wt.% of the total number.

24. An integrated method according to claim 1, in which a stream containing the product of alkylation, served in a gaseous state in the basis of the dehydrogenation reactor, which operates at temperatures of components from 450 to 650°and pressures from 0.1 to 3 ATM. abs. (ATA).

25. An integrated method according to claim 1, in which the reactor regeneration serves pre-heated air and possibly fuel gas to supply heat when burning,

p> 26. An integrated method according to claim 1, in which the temperature profile in the reactor regeneration typically ranges from 600 to 800°C.

27. An integrated method according to claim 1, in which the regenerated catalyst is continuously removed from the bottom of the reactor regeneration and fed into the dehydrogenation reactor when used as the conveying medium alkyl hydrocarbon, C2-C5in the amount of 30 to 100 wt.% of its total up the number.

28. An integrated method according to claim 1, wherein the dehydrogenation catalyst is prepared on the basis of iron and one or more promoters selected from alkali or alkaline earth metals and lanthanides, on a substrate of alumina, located in the Delta or theta phase or in a mixed Delta+theta, theta+alpha or Delta+theta+alpha phases, modified with silica, and having a surface area defined by the way BETH, preferably less than 150 m2/year

29. An integrated method according to p, in which the dehydrogenation catalyst includes:

1-60 wt.% iron oxide;

0.1 to 20 wt.% at least one oxide of an alkaline or alkaline-earth metal;

0-15 wt.% the second promoter selected from oxides of the lanthanide;

moreover, the complement to 100% is aluminum oxide, modified 0.0 to 5 wt.% silicon oxide.

30. An integrated method according to claim 1, wherein the dehydrogenation catalyst is selected from catalysts prepared on the basis of gallium and platinum or are made on the basis of chromium and tin.

31. An integrated method according to item 30, in which the catalyst is prepared on the basis of gallium and platinum, includes:

0.1 to 34 wt.% Ga2O3;

1-99 ppm (wt.) platinum;

0.05 to 5 wt.% oxide of alkaline and/or alkaline earth metal;

0.08 to 3 wt.% silicon oxide;

moreover, the complement to 100% is aluminum oxide, which is in the Delta or theta phase or in a mixed Delta+theta, theta+alpha or Delta+theta+alpha phases and having a surface area, a certain way BET, less than 150 m2/year

32. An integrated method according to item 30, in which the catalyst is prepared on the basis of chromium and tin includes:

6-30 wt.% Cr2About3;

0.1 to 3.5 wt.% SnO;

0.4 to 3 wt.% oxide of an alkali metal;

0.08 to 3 wt.% silicon oxide;

moreover, the complement to 100% is aluminum oxide, which is in the Delta or theta phase or in a mixed Delta+theta, theta+alpha or Delta+theta+alpha phases and having a surface area, a certain way BET, less than 150 m2/year

33. An integrated method according to claim 1, in which at the end of the dehydrogenation remove degidi is consistent stream which comprises 15-30 wt.% styrene, 7-15 wt.% ethylene, 10-50 wt.% unreacted ethylbenzene and 15-55 wt.% unreacted ethane.

34. Integrated method for production of alkyl - and alkenylamine aromatic compounds, which includes:

a) a feed stream comprising an aromatic hydrocarbon With6-C12and re-circulating stream containing alkanniny hydrocarbon With2-C5in the alkylation plant;

b) possible mixing of the flow coming from the alkylation unit and containing alkylaromatic compound with a stream consisting of alkyl hydrocarbon With2-C5;

C) flow obtained in stage (b)to the dehydrogenation/regeneration of fluidized bed containing a dehydrogenation catalyst capable of dehydration, and also simultaneously, alkyl hydrocarbon, possibly present in the stream, and alkylaromatic compounds;

g) continuous discharging spent catalyst, which accumulates in the bottom of the dehydrogenation reactor, and the flow in the upper part of the reactor regeneration;

d) continuous discharging regenerated catalyst which accumulates in the lower part of the reactor regeneration, and its flow in the upper part of the reactor digidrirovanny is I;

e) feeding the hydrocarbon stream leaving the dehydrogenation reactor, in the separating section for receiving the stream essentially consisting of alkenylsilanes aromatic compounds and a stream containing alkanniny hydrocarbon;

g) recycling the stream containing alkanniny hydrocarbon in the alkylation plant;

with specified integrated method differs in that the transport medium of a catalyst which is deposited in the lower part of the regenerator at a temperature of 650-800°With, in the dehydrogenation reactor consists of alkyl hydrocarbon, C2-C5and the fact that the dehydrogenation reactor is a reactor with upward flow mode in related threads, in which the gas is fully pneumatically transports the solids up.

35. An integrated method according to clause 34, in which the volumetric rate of gas (GHSV) exceeds 500 h-1and preferably greater than 1000 h-1.

36. An integrated method according to clause 34, in which the alkyl hydrocarbon is fed into the lower part of the reactor with upward flow, entering into contact with the catalyst at a maximum reaction temperature, and a stream containing alkylaromatic compound, is introduced into the reactor with upward flow at medium altitudes, where the temperature decreased to values compatible is valid with the flow corresponding reaction of dehydrogenation.



 

Same patents:

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to production of olefin or diolefin hydrocarbons via dehydrogenation of corresponding paraffinic C3-C5-hydrocarbons carried out in presence of catalyst comprising chromium oxide and alkali metal deposited on composite material including alumina and aluminum wherein percentage of pores larger than 0.1 μm is 10.0-88.5% based on the total volume of open pores equal to 0.10-0.88 cm3/g. Preparation of catalyst involves treatment of carrier with chromium compound solution and solution of modifying metal, preferably sodium or sodium and cerium. Carrier is prepared by from product resulting from thermochemical activation of amorphous hydrargillite depicted by formula Al2O3·nH2O, where 0.25<n<2.0, added to homogenous mass in amount 1.0 to 99.0% using, as additional material, powdered aluminum metal, which is partly oxidized in hydrothermal treatment and calcination stages. Hydrocarbon dehydrogenation process in presence of the above-defined catalyst is also described.

EFFECT: increased activity and selectivity of catalyst.

3 cl, 2 dwg, 4 tbl, 7 ex

The invention relates to catalysts used in the dehydrogenation of hydrocarbons, and to methods of using catalysts

The invention relates to the field of petrochemicals
The invention relates to a method for producing styrene and can be used in the petrochemical industry

The invention relates to a catalytic system and to a corresponding method for oxidative dehydrogenation of alkylaromatic hydrocarbons, in particular benzene, or paraffins to the corresponding alkanolamines hydrocarbons, in particular styrene, or to the corresponding olefins

The invention relates to a method for dehydrogenation of ethylbenzene to styrene in a system containing a reactor with a fluidized bed and the regenerator, in the presence of a catalyst based on iron oxide and promoters selected, for example, metal oxides such as oxides of alkali metals, oxides of alkaline-earth metals and/or metal oxides of the lanthanides group, plotted on the modified alumina

FIELD: petrochemical processes.

SUBSTANCE: alkylation and transalkylation reactions are carried out in one step by charging mixture of two different catalysts into one reactor: first alkylation catalyst EBEMAX-1 and then transalkylation catalyst EBEMAX-2 at their weight ratio (5-1):1. Process is carried out at 380-450°C.

EFFECT: increased yield of ethylbenzene and alkylation selectivity while simultaneously reduced power consumption and process expenses.

1 tbl, 9 ex

FIELD: petrochemical processes.

SUBSTANCE: alkylation and transalkylation reactions are carried out in one step by charging mixture of two different catalysts into one reactor: alkylation catalyst EBEMAX-1 and transalkylation catalyst EBEMAX-2 at their weight ratio (20-1):1. Process is carried out at 380-450°C.

EFFECT: increased yield of ethylbenzene and alkylation selectivity while simultaneously reduced power consumption and process expenses.

1 tbl, 9 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to preparing antioxidants of phenolic type. Method involves using alkylation products of mixture of para- and ortho-isomers of isononylphenol with isobutylene as an antioxidant. Alkylation reaction is carried out at 40-120°C and 0.02-0.4 MPa in the presence of acid catalyst in batch and continuous feeding isobutylene to reactor unit providing maintaining isobutylene concentration in reaction mass 0.8 mole/l, not above, and the total amount of isobutylene feeding to alkylation 1.82-2.0 mole per 1 mole parent alkylphenols. Method provides preparing antioxidant showing good technological properties and high effectiveness of protective effect for rubbers of emulsion polymerization and rubbers based on thereof, and simple method for its synthesis also.

EFFECT: improved method for preparing.

6 cl, 3 tbl, 7 ex

FIELD: petrochemical processes.

SUBSTANCE: alkylation is carried out at 250-425°C, pressure 0.1 to 2.5 MPa, benzene/ethylene molar ratio 1-5, and volume flow rate of raw material 0.5 to 3.5 h-1 in presence of spherical zeolite-containing catalyst having following composition: 5-55 wt % high-silica ZSM-5-type zeolite with silica/alumina molar ratio 20-150 and 45-95 wt % amorphous aluminosilicate carrier. Chemical analysis of catalyst, wt %: aluminum oxide 3.0-9.5, rare-earth element oxides 0.4-5, calcium oxide 1.0-5.0, sodium oxide 0.1-0.6, silicon oxide - the balance.

EFFECT: increased yield of ethylbenzene and alkylation selectivity.

2 cl, 1 tbl, 5 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves carrying out the interaction condensed and polynuclear aromatic hydrocarbons, in particular, naphthalene and biphenyl with polyalkylaromatic hydrocarbons, in particular, with diisopropyl benzene under transalkylation conditions with aim to prepare dialkylated condensed and polynuclear aromatic hydrocarbons. Transalkylation reaction is carried out in the presence of zeolite catalysts comprising 12-membered oxygen rings with diameter of zeolite channels from 5.6 to 7.7 . Invention provides the development of new method for preparing dialkylated polycyclic hydrocarbons.

EFFECT: improved preparing method.

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The invention relates to a method for producing alkyl benzenes interaction of benzene with olefins in the presence of a catalyst complex of aluminum chloride

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