Method of hydrogenation of aromatic compounds by reaction distillation

FIELD: chemistry of aromatic compounds.

SUBSTANCE: proposed method includes bringing the non-substituted mononuclear aromatic compound in contact with gaseous hydrogen in presence of at least one catalyst in reaction column at passing the reaction components through catalyst (catalysts) fixed in reaction column; hydrogenation is performed in such way that cyclo-aliphatic compounds escape through side outlet or lower part of column or from side outlet and lower parts of column.

EFFECT: enhanced selectivity of hydrogenation and increased yield of products.

11 cl, 2 dwg, 1 tbl, 1 ex

 

The present invention relates to a method for hydrogenation of unsubstituted or substituted by at least one alkyl group, amino group or hydroxyl group, or a combination of two or more such groups, one - or polynuclear aromatic compounds to the corresponding cycloaliphatic compounds. The present invention particularly relates to a method for hydrogenation of benzene to cyclohexane by reactive distillation in the reaction column by passing the components of the reaction countercurrent through a fixed (fixed) in the reaction column of catalyst (catalysts).

There are many ways to hydrogenation, for example, benzene to cyclohexane. These methods hydrogenation in the vast majority carried out in the gas or liquid phase using justiciarship Nickel and platinum catalysts (see, among others, U.S. patent 3597489, respectively, the United Kingdom patent 1444499, respectively, the United Kingdom patent 992104). Usually first in the main reactor, the maximum portion of the benzene hydronaut to cyclohexane and then in one or more reactors is brought to a complete transformation in cyclohexane.

In the case of strongly exothermic hydrogenation reactions required careful control of pressure, temperature and time, p is byvania to achieve full conversion at high selectivity. In particular the need to suppress a significant formation of Methylcyclopentane, which preferably occurs at higher temperatures. According to the typical characteristics of the residual cyclohexane benzene content should be below 100 ppm, and the content of Methylcyclopentane below 200 h/million the content of n-paraffins (as n-hexane, n-pentane and others) is critical. These undesirable compounds are also preferably formed at higher temperatures hydrogenation and exactly the same as Methylcyclopentane, they can be separated from the cyclohexane only by expensive operations division. Separation can be accomplished, for example, by extraction, distillation or through the use of molecular sieves as described in UK patent 1341057. Used for the hydrogenation catalyst also has a strong influence on the resultant unwanted Methylcyclopentane.

For this reason, it is desirable to carry out the hydrogenation is possible at low temperatures. This, however, is limited by the fact that depending on the type of hydrogenation catalyst, only since higher temperatures reach high enough to achieve cost-effective output per unit time per unit volume activity of the hydrogenation catalyst.

IP is alzhemier for the hydrogenation of benzene Nickel and platinum catalysts have a number of disadvantages. Nickel catalysts are very sensitive to sulfur-containing impurities in benzene, so either you want to use for the hydrogenation of benzene to a very high degree of purity, or, as described in UK patent 1104275, in the main reactor using a platinum catalyst which is resistant to high levels of sulfur and thus protects additional reactor filled with a Nickel catalyst. Another possibility consists in doping the catalyst with rhenium (patent UK 1155539) or in the preparation of the catalyst when using ion exchangers (patent UK 1144499). The preparation of such catalysts, however, is expensive. The hydrogenation can also be carried out using Raney Nickel (U.S. patent 3202723), however, the disadvantage is easy Flammability of the catalyst. For the hydrogenation can also be used homogeneous Nickel catalysts (application for European patent A-0668257). These catalysts, however, are very sensitive to water, so used benzene before hydrogenation must first be dried in a drying column to a residual moisture content below 1 h/million Another disadvantage of the homogeneous catalyst is the inability of its regeneration at acceptable costs.

Platinum rolled atory have fewer disadvantages, than Nickel catalysts, but their preparation is much more expensive. As with the application of platinum, and Nickel catalysts require a very high temperature hydrogenation, which can lead to significant formation of undesirable by-products.

When using ruthenium catalysts for the hydrogenation of benzene to cyclohexane is technically impossible, however, in patent literature there are references to the application containing ruthenium catalysts for this application.

According to the patent of the USSR 319582 to obtain cyclohexane from benzene using ruthenium suspension catalysts doped with palladium, platinum or rhodium. Catalysts, however, due to the use of palladium, platinum or rhodium, are very expensive. Further, in the case of suspension of catalysts preparation and regeneration of the catalyst is expensive.

According to the patent of the USSR 403658 to obtain cyclohexane using doped with chromium ruthenium catalyst. The hydrogenation is carried out at a temperature of 180°; this produces a significant amount of undesirable by-products.

In U.S. patent 3917540 describes deposited on alumina as the material of the carrier of the catalysts for cyclohexane. As the active metal they contain a noble metal of the VIII side of the subgroups of the periodic system of elements, next, an alkaline metal, and technetium or rhenium. The native aluminum oxide are in the form of beads, pellets or the like. The disadvantage of such catalysts is that only achieve selectivity of 99.5%.

Finally, in U.S. patent 3244644 describes deposited on η-Al2About3as the material of the carrier ruthenium hydrogenation catalysts, which should also be suitable for the hydrogenation of benzene. The molded catalysts in the form of particles with a size of maximum 0,635 cm (1/4 inch), and they contain at least 5% of the active metal; cooking η-Al2O3is expensive.

In the prior art, along with the above justiciarship catalysts or suspension catalysts, known monolithic catalysts on a carrier in the form of having an ordered structure of the nozzles with a catalytically active layers, which can be used for hydrogenation reactions.

In the European patent In-0564830 described, for example, a monolithic catalyst on the carrier, which as the active components may include elements of group VIII of the periodic system of elements.

In the application for a European patent A-0803488 reveals the way to turn, for example, hydrogenation, aromatic compounds, which, as the substituent of the aromatic ring which contains at least one hydroxyl group, or amino group. The transformation is carried out in the presence of a catalyst comprising a homogeneous compound of ruthenium, which is precipitated in situ on the carrier, for example on the monolith. The hydrogenation is carried out at pressures above 50 bar and temperatures preferably 150-220°C.

In the International application WO-96/27580 describes a method of hydrogenation of unsaturated cyclic and polycyclic compounds via catalytic distillation, in which the reactor operates at a pressure at which the reaction mixture boils at a low partial pressure of hydrogen.

In the International application WO-98/09930 disclosed process for the selective hydrogenation of aromatic compounds in a mixed hydrocarbon stream through a catalytic distillation in the presence of a catalyst.

In ways, according to both listed last, patent applications required pressure of 13.8-17.2 bar and temperature 135-190°to achieve sufficient output per unit time per unit volume. Under both proposals, the desired product is always output, respectively, obtained from the head of the column.

If all described in the literature methods hydrogenation of aromatic compounds in common is that for strongly exothermic hydrogenation reactions requires careful control of temperature and residence time to achieve is to achieve full conversion at high selectivity. In particular the need to suppress a significant formation of Methylcyclopentane, which is formed preferably at high temperatures. Formed during hydrogenation by-products, such as, for example, Methylcyclopentane, in the case of the above-mentioned methods of the prior art lead to contamination of the product. To obtain, for example, cyclohexane high purity therefore, if necessary, require subsequent distillation, which is associated with the investment costs.

The present invention is therefore based on the task of developing a cost-effective method of obtaining cycloaliphatic compounds by hydrogenation of the corresponding aromatic compounds, in particular the hydrogenation of benzene to obtain cyclohexane, allowing you to get cycloaliphatic compounds of high purity with high selectivity, high yield and under mild reaction conditions.

This problem is solved by the proposed in the invention method of hydrogenation of unsubstituted or substituted by at least one alkyl group, amino group or hydroxyl group, or a combination of two or more such groups, one - or polynuclear aromatic compounds to the corresponding cycloaliphatic compounds with gaseous hydrogen in the presence of at least one to whom telesfora in the reaction column by passing the components of the reaction through a fixed (fixed) in the reaction column of catalyst (catalysts), moreover, the hydrogenation carried out so that the cycloaliphatic compounds is brought out through the side lumen or the lower part of the column or through the side outlet and the lower part of the column.

Components of the reaction preferably is passed countercurrent through a fixed (fixed) in the reaction column of catalyst (catalysts).

If desirable as a product cycloaliphatic compounds is brought out through the side lumen, more easily boiling (low-boiling components are removed from the head of the column. Accordingly, the boiling higher than cycloaliphatic compounds, components (high-boiling components) is obtained from the bottom of the column. According to this mode of operation tailored to the respective side products, which are contained in aromatic compounds or formed during the reaction. For example, low-boiling components out through the head of the column and, accordingly, the high-boiling components are removed from the bottom of the column, while the cycloaliphatic compound is brought out through the side lumen.

If not formed any high-boiling by-products or side components, valuable product is removed from the bottom of the column.

Needless to say, according to the invention it is also possible mode of operation in which cycloaliphatic with the unity as valuable products brought out through the side lumen and from the bottom of the column.

Thus according to the invention the regulation of conduct through the reflux in the column and/or power consumption in the column, remove cycloaliphatic compounds through the side outlet or from the bottom of the column. Through the side exhaust product is preferably extracted in liquid form.

In this surprisingly found that aromatic compounds, of which as a non-exhaustive list can be called as benzene, toluene, xylene and aniline, you can gidrirovanii to the corresponding cycloaliphatic compounds on offer in the invention method with clearly lower compared with the methods of the prior art pressures and temperatures selectively and with high yield per unit time per unit volume and get them with a high degree of cleanliness of the installation.

Under the proposed according to the invention method, the hydrogenation preferably carried out at pressures below 20 bar and at a temperature below 200°C.

According to a particularly preferred variant of implementation, the hydrogenation is carried out at pressures below the bar 13 and at a temperature below 150°C.

Even more preferably the hydrogenation is carried out at a pressure in the region of 1-20 bar, preferably 5-13 bar, and/or at a temperature in the region of 50-200°C, preferably 80-150°C.

Since the system is in a state of boiling, when the learn of proposed according to the invention method, the temperature of the reaction mixture can be adjusted in a simple way through the pressure.

The invention method, the pressure is set so that when the hydrogenation of the partial pressure of hydrogen is the largest in the area of 0.1 to 20 bar and preferably in the field 5-13 bar.

In the case of proposed according to the invention of a method of catalytic hydrogenation is carried out in a reaction column in the presence of a heterogeneous catalyst, and, in principle, it is possible to use all suitable for this application, the catalysts.

In particular, it should for example be mentioned: the molded products of the catalytically active ion exchangers, as described in Chem. Eng. Technol., 16, 279-289 (1993), which are made in the form of Raschig rings, saddle-shaped bodies and the other, known from the technique of distillation of forms. Another example of a catalytically active moulded products, which are similar in form, separating the built-in elements known from the technique of distillation, are manufactured by Sulzer catalysts CATARAC and carriers of catalysts, as well as manufactured by Montz catalysts MULTIPAK. In their structure they correspond to the common technique of distillation structures with cross-channels, such as the design firm Sulzer BX, CY, DX, MELAPAK or company Montz A3, BSH. Such patterns, however, in the form of metallic fabrics, which is additionally attached to erkovtsi, described in the patent application Germany And 19624130.8.

Further, the catalysts, as, for example, ion exchangers, which are introduced into the cells of the mesh, you can pull up in the rolls with a diameter of approximately 0.2-0.6 m, and the height of the roll is approximately 0.3 m These rolls by one or several load in distillation columns. Further information regarding such catalysts can be obtained from U.S. patent 4215011, as well as from the publication in Ind. Eng. Chem. Res., 36, 3821-3832 (1997), the relevant contents of which are fully included in the context of this application by reference.

Further, it is possible to use heterogeneous catalysts with active metals. As the active metal, in principle, you can use all the metals of the VIII side of the subgroups of the periodic system of elements. As the active metal is preferably used platinum, rhodium, palladium, cobalt, Nickel or ruthenium or a mixture of two or more of these metals, and as an active metal in particular is used ruthenium.

Of the applicable metals I and VII side of the subgroups of the periodic system of elements, which are also, in principle, all applicable, it is preferable to use copper and/or rhenium.

Especially preferably use one ruthenium. The advantage of using ruthenium as the metal for the hydrogenation zaklyuche the Xia is thus, compared with a distinctly more expensive metals for hydrogenation with platinum, palladium or rhodium can reduce the considerable costs of the preparation of the catalyst.

Preferably used in the present according to the invention method, the ruthenium catalyst is placed in a column or in the form of a granular mass, either in the form of catalytically active distillation nozzles, or a combination of both forms. The form of this kind of bulk material or distillation nozzles known to the expert from the prior art.

Examples of metallic materials as materials carriers are the technical purity metals as iron, copper, Nickel, silver, aluminum, zirconium, tantalum and titanium, or alloys like steel or stainless steel, such as Nickel, chromium and/or molybdenum steel. Next, you can use brass, phosphor bronze, Monel and/or Nickel silver or a combination of two or more of the above materials.

Examples of ceramic materials include aluminum oxide (Al2O3), silicon dioxide (SiO2), zirconium dioxide (ZrO2), cordierite and/or steatite.

Examples of synthetic materials carriers are, for example, polymers such as polyamides, polyesters, polyethers, polyvinyl, polyolefins, as polyeth the flax, polypropylene, polytetrafluoroethylene, polyketone, simple poliafito-ketones, simple polyethersulfone, epoxy resins, aldehyde resins, urea - and/or melamine-aldehyde resin. Further, as a carrier you can use carbon.

Preferably use structured storage in the form of metal fabrics, metallic knitted fabric, knitted metal products, metal sheets or metal felts, fabrics or felts of carbon fiber or fabrics or knitted fabrics of polymers. As metal fabrics are used woven fabrics suitable for the production of fabric of metal wires, derived from iron, spring steel, brass, phosphor bronze, Nickel technical purity, Manila, aluminum, silver, Nickel silver, Nickel, chromium-Nickel alloy, chrome steel, stainless, acid-resistant and highly temperature-resistant chromium-Nickel steels, and titanium.

You can also use fabric from inorganic materials, such as fabrics made of ceramic materials such as aluminum oxide and/or silicon dioxide.

According to one variant embodiment of the invention it is also possible to use synthetic wire and fabric of polymers.

Particularly preferred monoliths from tissue attachments, as they withstand the high priest is Ichnya load of gas and liquid and undergo only minor wear.

According to a further particularly preferred variant implementation, apply metal structured media or monoliths consisting of stainless steel, which is preferably at annealing in air and subsequent cooling acquires the surface roughness. These properties are particularly high-quality steel, in which case the above specific temperature stratification one component of the alloy is concentrated on the surface and in the presence of oxygen due to oxidation forms processreply rough surface of the oxide layer. This component of the alloy may be, for example, aluminum or chromium, which forms the surface layer, respectively, of Al2About3or Cr2About3. Examples of high-quality steels are those with material number 1.4767, 1.4401, 1.4301, 2.4610, 1.4765, 1.4847 and 1.4571. These steels can be roughened thermally, preferably by annealing in air at a temperature of 400-1100°during the period of time from 1 hour to 20 hours and subsequent cooling to room temperature.

According to a preferred variant implementation of the heterogeneous catalyst is a coated ruthenium fabric, which simultaneously serves as a distillation attachment.

According to another D. Lenasia preferred option proposed in the invention method, distillation attachment consists of coated ruthenium metal thread, especially preferable to use stainless steel number 1.4301 or 1.4767.

As is known to the expert from the prior art, it is possible to apply the promoter or several promoters of the catalyst. Promoters may be, for example, alkaline and/or alkaline earth metals, such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium; metals for coin alloys, such as copper, silver and/or gold; zinc, tin, bismuth, antimony, molybdenum, tungsten, and/or other promoters as sulfur and/or selenium.

Before application of the active metal and, if necessary, promoters structured or solid carriers, if necessary, coated with one, two or more oxides. This can be done physically, for example by spraying. In oxidizing atmosphere under conditions of high vacuum elements and/or compounds of elements of the sprayed on material media. As element can be called, for example, titanium, silicon, zirconium, aluminum, and zinc. Further information can be obtained from the European patent In-0564830, relevant content of which is fully incorporated in the context of this application by reference.

In some cases you can also apply also described in the European patent In-0564830 high-vacuum deposition (e.g., cathode ray napile the s).

Structured media either before or after application of the active metals, respectively, promoters, it is possible to deform, respectively, together laminating, for example, by rolling gears, to obtain a monolithic catalytic element.

Used according to the invention catalysts can prepare technically by applying at least one metal VIII the side of the subgroups of the periodic system of elements and, if necessary, at least one promoter for one of the above media.

The application of active metals and, if necessary, promoters on the above media can be performed so that the active metal is evaporated in a vacuum and continuously condense on the media. Another possibility consists of applying to the native active metals by impregnation with solutions that contain active metals and, if necessary, the promoters. The next opportunity is to apply to the native active metal and, if necessary, promoters by chemical methods, such as chemical vapor deposition.

Thus, the prepared catalysts can be used immediately or prior to their application to be subjected to annealing and/or calcination and can be used both in pre-vosstanovlenie is m, and also in unrestored condition.

Before application of the active metal and, if necessary, promoters carrier can be subjected to pre-treatment. Pre-treatment is preferable, for example, when you want to improve the adhesion of the active ingredients with the carrier. Examples of pre-processing are coating media which increases the adhesion means or Cherkovna mechanical (e.g. grinding, sandblasting) or thermal methods, such as heat, usually in air, plasma etching or machining using glow discharge.

According to a preferred variant implementation of the present invention relates to such a method, and as an active metal catalyst contains at least one metal VIII the side of the subgroups of the periodic system of the elements individually or together with at least one metal I or VII side of the subgroups of the periodic system of the elements, supported on a carrier, and the carrier has an average pore diameter of at least 50 nm and a specific surface area determined by BET method, at most 30 m2/g, and the amount of active metal is from 0.01 to 30 wt.%, calculated on the total weight of the catalyst (catalyst 1). Further, the average diameter of the pores of the support that can produce the RA is at least 0.1 microns and specific surface area, determined by BET method is at most 15 m2/g (catalyst 1A).

Further, the invention relates to such a method, and as an active metal catalyst contains at least one metal VIII the side of the subgroups of the periodic system of the elements individually or together with at least one metal I or VII side of the subgroups of the periodic system of elements in an amount of 0.01-30 wt.%, calculated on the total weight of the catalyst supported on a carrier, and 10-50% of the pore volume of the carrier to form macropores with a pore diameter in the area of 50-10000 nm and 50-90% of the pore volume of the carrier to form the mesopores with pore size in the field of 2-50 nm, and the sum of the proportions of the volumes of pores is 100% (catalyst 2).

As carriers, in principle, can be used with all carriers who have macropores, i.e. the media, which have exclusively macropores, as well as along with also contain macropores mesopores and/or micropores.

The term "macropores and mesopores in the framework of the present invention is used in the sense in which they are defined in Pure Appl. Chem., 45, 79 (1976), namely as pores whose diameter is above 50 nm (macropores) or the diameter of which ranges from 2 nm to 50 nm (mesopores). "Micropore" is defined in accordance with the above literature and the meaning of the pores of the diameter below 2 nm.

The content of the active metal is, in General, from about 0.01 wt.% to about 30 wt.%, preferably from about 0.01 wt.% to about 5 wt.% and especially from about 0.1 wt.% to about 5 wt.% accordingly, calculated on the total weight of the used catalyst, and the content of the active metal is preferably used in these, preferably used catalysts 1 and 2, again indicated when discussing these catalysts separately.

Now below will be described in detail preferably used catalysts 1 and 2. However, the description is carried out, for example, referring to the use of ruthenium as active metal. The following instructions can also be extended to other active metals, as specified in the present context.

Catalyst 1

Used according to the invention catalysts 1 technically you can do by applying at least one metal VIII the side of the subgroups of the periodic system of elements and, if necessary, at least one metal I or VII side of the subgroups of the periodic system of the elements on suitable media.

Application can be achieved by impregnation of the carrier with aqueous solutions of salts of metals, such as, for example, aqueous solutions of salts of ruthenium, by spraying the carrier with the corresponding metal salt solutions or other suitable means. As salts of the metals I, VII or VIII side of the subgroups of the periodic system of elements suitable nitrates, nitrosylated, halides, carbonates, carboxylates, acetylacetonates, chlorine-containing complexes, nitrite complexes or complexes with amines of the respective metals, preferably nitrates and nitrosylated.

In the case of catalysts, which along with VIII metal side of the subgroups of the periodic system of elements contain other metals as the active metal on the carrier, metal salts, respectively, solutions of metal salts, can be applied simultaneously or sequentially.

Covered, respectively, impregnated with a solution of metal salt media is then dried, preferably at temperatures of 100-150°and possibly calcined at temperatures between 200 and 600°C, preferably 350-450°C. In the case of separate impregnation of the catalyst after each impregnation stage, dried and possibly calcined as described above. The sequence in which the impregnation of the active components, choose in any way.

Coated and dried, and calcined media then activated by treatment in a gas stream containing free hydrogen, at temperatures from about 30°With up to approximately 600°C, preferably from p is IMEMO 150° With up to 450°C. the Gas stream preferably consists of 50 to 100 vol.% hydrogen and 0-50% vol. of nitrogen.

The solution of metal salt or metal salt solutions applied to the carrier or carriers in such amount that the total content of the active metal, respectively, based on the total weight of the catalyst ranges from about 0.01 wt.% to about 30 wt.%, preferably from about 0.01 wt.% to about 5 wt.%, more preferably from about 0.01 wt.% to about 1 wt.% and in particular from approximately 0.05 wt.% to about 1 wt.%.

Specific surface area of metal in the catalyst 1 is in General preferably from about 0.01 m2/g to about 10 m2/g, more preferably from about 0.05 m2/g to about 5 m2/g and in particular from about 0.05 m2/g to about 3 m2/g of catalyst. The specific surface of the metal is determined according to the method of chemisorption described by J. Lemaitre and others in the book, "Characterization of Heterogeneous Catalysts", edited by Francis Delanney, ed. Marcel Dekker, new York, s-324, 1984

In applied according to the invention the catalyst 1 to the ratio of the surfaces of the active metal of the active metal and the catalyst carrier is preferably less than approximately 0.05, and the lower limit value is about 0,0005.

Used for cooking used coz the ACLs to the invention catalysts materials media represent such which are macroporous and have an average pore diameter of at least about 50 nm, preferably at least about 100 nm, particularly of at least about 500 nm, and specific surface area determined by BET method is at most about 30 m2/g, preferably at most about 15 m2/g, more preferably at most about 10 m2/g, in particular at most about 5 m2/g and even more preferably at most about 3 m2/the Average pore diameter of the carrier is preferably from about 100 nm to about 200 μm, more preferably from about 500 nm to about 50 μm. The specific surface of the carrier determined by BET method, is preferably from about 0.2 m2/g to about 15 m2/g, more preferably from about 0.5 m2/g to about 10 m2/g, in particular from about 0.5 m2/g to about 5 m2/g and even more preferably from about 0.5 m2/g to about 3 m2/year

The specific surface of the carrier is determined by the BET method by nitrogen adsorption, in particular according to DIN 66131. Determination of the average diameter of pores and the pore size is carried out by porometry, in particular according to DIN 66133.

The pore distribution of the largest media before occhialino may be approximately bimodal, moreover, the distribution of the pore diameter with maxima at about 600 nm and about 20 microns, with a bimodal distribution is a special variant embodiment of the invention.

Further, preferred is a carrier with a specific surface area of 1.75 m2/g, which has this bimodal distribution of the pore diameters. The pore volume of this preferred carrier is preferably approximately of 0.53 ml/year

As a macroporous material of the carrier is applicable, for example, with macropores activated carbon, silicon carbide, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide or mixtures of two or more of these oxides, preferably using aluminum oxide and zirconium dioxide.

Further detailed information regarding the catalyst 1, respectively, its preparation can be obtained from the patent application Germany And 19624484.6, relevant content of which is fully incorporated in the context of this application by reference.

Used for preparation used according to the invention catalyst 1A, which represents the preferred form of the catalyst 1, materials carriers are those which are macroporous and have an average pore diameter of at least 0.1 microns, before occhialino at least 0.5 micron, and have a specific surface area of at most 15 m2/g, preferably at most 10 m2/g, particularly preferably at most 5 m2/g, in particular at most 3 m2/the Average diameter of the pores used in this case, the media is in the area of 0.1-200 μm, particularly 0.5 to 50 μm. The specific surface of the carrier is preferably 0.2 to 15 m2/g, particularly preferably 0.5 to 10 m2/g, in particular 0.5-5 m2/g, in particular 0.5 to 3 m2/Also, this catalyst has, relative to the distribution of pore diameters, already above bimodality with similar distributions and the corresponding preferred pore volume. Further details regarding catalyst 1A can be obtained from the patent application Germany And 19604791.9, relevant content of which is fully incorporated in the context of this application by reference.

Catalyst 2

Used according to the invention catalysts 2 contain one or more metals of the VIII side of the subgroups of the periodic system of the elements as active component (active component) on the media, as specified in the present context. As active component (active component) is preferably used ruthenium, palladium and/or rhodium.

Used according to the invention the cat is the catalysts 2 technically you can do by applying at least one active metal VIII the side of the subgroups of the periodic system of elements and, if necessary, at least one metal I or VII side of the subgroups of the periodic system of the elements on suitable media. Application can be achieved by impregnation of the carrier with aqueous solutions of salts of metals, such as, for example, aqueous solutions of salts of ruthenium, by spraying the carrier corresponding metal salt solutions or other suitable means. As metal salts for the preparation of solutions of metal salts suitable nitrates, nitrosylated, halides, carbonates, carboxylates, acetylacetonates, chlorine-containing complexes, nitrite complexes or complexes with amines of the respective metals, preferably nitrates and nitrosylated.

In the case of catalysts which contain supported on a carrier multiple active metals, metal salts, respectively, the metal salt solutions can be applied simultaneously or sequentially.

Covered, respectively, impregnated with a solution of metal salt media is then dried, preferably the temperature of 100-150°C. These carriers can be ignited at temperatures between 200 and 600°C, preferably 350-450°C. Then the carriers coated activated by treatment in a gas stream containing free hydrogen, at temperatures of 30-600°C, preferably 100-450°and in particular 10-300° C. the Gas stream preferably consists of 50 to 100 vol.% hydrogen and 0-50% vol. of nitrogen.

If the media put a few of the active metals and the application of exercise consistently, then the media after each application, respectively, impregnation can be dried at temperatures of 100-150°and it is possible to carry out the calcination at temperatures between 200 and 600°C. the sequence in which the coating or impregnation with a solution of metal salt, choose in any way.

The metal salt solution is applied to the carrier, respectively, the media, in such a quantity that the content of the active metal is from 0.01 to 30 wt.%, preferably 0.01 to 10 wt.%, more preferably 0.01 to 5 wt.% and in particular 0.3 to 1 wt.%, calculated on the total weight of the catalyst.

Specific surface area of metal in the catalyst is generally preferably 0.01 to 10 m2/g, particularly preferably 0.05 to 5 m2/g and more preferably 0.05 to 3 m2/g of catalyst. The specific surface of the metal is determined according to the method of chemisorption described J.Lemaitre and others in the book, "Characterization of Heterogeneous Catalysts", edited by Francis Delanney, ed. Marcel Dekker, new York, s-324, 1984

In applied according to the invention the catalyst 2 to the ratio of the surfaces of at least one active metal and the catalyst carrier is less than about 0.3, site is preferably less than about 0.1, and in particular about 0.05 or less, moreover, the lower limit value is about 0,0005.

Used for preparation used according to the invention catalysts 2 materials carriers have macropores and mesopores.

When used according to the invention, the substrates may have a pore distribution according to which from about 5% to about 50%, preferably from about 10% to about 45%, more preferably from about 10% to about 30% and especially from about 15% to about 25% of the volume of pores to form macropores with pore diameters in the range from about 50 nm to about 10,000 nm, and from about 50% to about 95%, preferably from about 55% to about 90%, more preferably from about 70% to about 90% and in particular from about 75% to about 85% of the volume of pores to form mesopores with a pore diameter of from about 2 nm to about 50 nm, and, accordingly, the sum of the proportions of the volumes of pores is 100%.

Total pore volume used according to the invention the media is about 0.05 to 1.5 cm3/g, preferably 0.1 to 1.2 cm3/g and in particular about 0.3-1.0 cm3/the Average diameter of pores is used according to the invention the media is from about 5 nm to 20 nm, preferably from about 8 nm to about 15 nm and in particular from about 9 nm to about 12 nm.

The specific surface of the carrier is a preference for the equipment from approximately 50 m 2/g to about 500 m2/g, more preferably from about 200 m2/g to about 350 m2/g and in particular from about 250 m2/g to about 300 m2/year

The specific surface of the carrier is determined by the BET method by nitrogen adsorption, in particular according to DIN 66131. Determination of the average diameter of the pores and the distribution of the largest carried out by mercury porometry, in particular according to DIN 66133.

Although, in principle, it is possible to use all known for the preparation of the catalyst material carriers, which have the above pore size, preferably activated carbon is used, silicon carbide, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, or mixtures thereof, more preferably aluminum oxide and zirconium dioxide.

Further detailed information in respect of catalyst 2 can be obtained from the patent application Germany And 19624485.4, relevant content of which is fully incorporated in the context of this application by reference.

Further detailed information in relation used in the method according to the invention catalysts, their structure and preparation can be obtained from the patent application Germany 19917051.7, relevant content of which is fully incorporated in the context of this application by Alki.

Formed by the reaction of low-boiling by-products during reactive distillation, if necessary, in the form of an azeotrope with the selected substances are distilled off via the head of the column and is removed from the reaction system.

Similarly, the resulting high-boiling by-products are separated through the lower part of the column.

Released in strongly exothermic reactions energy is used for distillation.

In the case of proposed according to the invention method, along with benzene may also be turning its substituted derivatives, such as toluene or xylene, to the corresponding saturated hydrocarbons.

Under the proposed according to the invention method, in principle, you can use any one - or polynuclear aromatic compounds, which are either unsubstituted or substituted by at least one alkyl group, amino group or hydroxyl group, or a combination of two or more of these groups, individually or as mixtures of two or more of these compounds, preferably individually. The length of the alkyl group that does not fall under any specific restrictions, in General, we are talking, however, about an alkyl group with 1-30 carbon atoms, preferably 1-18 carbon atoms and especially 1 to 4 carbon atoms.

D is more, according to the invention can be gidrirovanii aromatic compounds in which at least one hydroxyl group and preferably, further, at least one unsubstituted or substituted alkyl group and/or alkoxygroup with 1-10 carbon atoms linked to an aromatic nucleus to the corresponding cycloaliphatic compounds, and can also be used mixtures of two or more of these compounds.

Aromatic compounds can be mononuclear or polynuclear aromatic compounds. Aromatic compounds may contain at least one hydroxyl group, which is linked to the aromatic nucleus, and the easiest connection with this group is phenol. Aromatic compounds preferably contain one hydroxyl group on the aromatic nucleus. Aromatic compounds may be substituted in the aromatic nucleus or in the aromatic nuclei by one or more alkyl groups and/or alkoxygroup, preferably alkyl groups and/or alkoxygroup with 1-10 carbon atoms, particularly preferably alkyl groups with 1-10 carbon atoms, in particular metal, ethyl, sawn, ISO-propyl, utilname, isobutylene, tert-utilname groups; from alkoxygroup preferred alkoxygroup with 1-8 carbon atoms is kind, as, for example, methoxy, ethoxy-, propoxy-, isopropoxy, butoxy, isobutoxy-, tert-butoxypropyl. The aromatic nucleus or an aromatic nucleus, as well as alkyl groups and alkoxygroup can be unsubstituted or substituted by halogen atoms, especially fluorine atoms, or may contain other suitable inert substituents.

Gidriruemyi according to the invention compounds preferably contain at least one, preferably one to four, especially one alkyl group with 1-10 carbon atoms, which preferably is in the same aromatic nucleus, as well as at least one hydroxyl group. The preferred compounds are (mono)ALKYLPHENOLS and alkyl group may be in the o-, m - or p-position to the hydroxyl group. Particularly preferred TRANS-ALKYLPHENOLS, also called as 4-alkyl-phenols, and alkyl group preferably contains 1-10 carbon atoms and represents in particular tert-boutelou group. Preferred is 4-tert-butylphenol. Used according to the invention polynuclear aromatic compounds are, for example, β-naphthol and α-naphthol.

Aromatic compounds in which at least one hydroxyl group and preferably, further, at least one nezamedin who I am or substituted alkyl group and/or alkoxygroup with 1-10 carbon atoms linked to an aromatic nucleus, may include several aromatic nuclei linked through alkylenes group, preferably a methylene group. Linking Allenova group, preferably a methylene group, can contain one or more alkyl substituents, which can be alkyl groups with 1-20 carbon atoms and preferably alkyl groups with 1-10 carbon atoms, and particularly preferred metal, ethyl, sawn, ISO-propyl, butylene or tert-butylene group.

In addition, each of the aromatic nuclei may contain bound by at least one hydroxyl group. Examples of such compounds are bisphenol that in position 4 are connected through alkylenes group, preferably a methylene group.

In the framework of the method according to the invention particularly preferably hydronaut substituted alkyl group with 1-10 carbon atoms, preferably an alkyl group with 1-6 carbon atoms, phenol, and alkyl group unsubstituted or substituted aromatic residue, or a mixture of two or more such compounds.

According to the following preferred variant implementation of this method, hydronaut p-tert-butylphenol, bis(p-hydroxyphenyl)dimethylmethane or their mixture.

Using the proposed according to the invention method, then, can hiderow the th aromatic compounds, in which at least one amino group linked to the aromatic nucleus to the corresponding cycloaliphatic compounds, and can also be used mixtures of two or more such compounds. This aromatic compounds can be mononuclear or polynuclear aromatic compounds. Aromatic compounds contain at least one amino group bound to an aromatic nucleus. Aromatic compounds are preferably aromatic amines or diamines. Aromatic compounds may be substituted in the aromatic nucleus or an aromatic nuclei or the amino group with one or more alkyl groups and/or alkoxygroup, preferably alkyl groups with 1-20 carbon atoms, particularly preferably methyl groups, ethyl groups, methoxy-, ethoxy-, propoxy-, isopropoxy, butoxy, isobutoxy-, tert-butoxypropyl. The aromatic nucleus or an aromatic nucleus, as well as alkyl groups and alkoxygroup can be unsubstituted or substituted by halogen atoms, especially fluorine atoms, and may contain other suitable inert substituents.

Aromatic compound in which at least one amino group linked to the aromatic nucleus may also include several aromatic nuclei linked through alkylenes group, preferred the additional methylene group. Linking Allenova group, preferably a methylene group, can contain one or more alkyl substituents, which may be an alkyl group with 1-20 carbon atoms and preferably alkyl groups with 1-10 carbon atoms, and particularly preferred are methyl, ethyl, sawn, ISO-propyl, butylene, second-butylene or tert-butylene group.

Associated with aromatic nucleus of the amino group may also be substituted by one or two of the above alkyl groups.

Particularly preferred compounds are aniline, naphtylamine, diamino-benzene, diaminotoluene and bis-p-aminophenolate or mixtures thereof.

In particular, in the framework of the present method is particularly hydronaut the following aromatic compounds: benzene, toluene, xylenes, cumene, difenilmetana, tri-, Tetra-, Penta - and hexabenzyl, triphenylmethane, alkyl substituted naphthalenes, naphthalene, alkyl substituted anthracene, anthracene, alkyl substituted tetralin, tetralin, and aniline. Under this method preferably hydronaut benzene to cyclohexane.

Although the hydrogenation of aromatic compounds can be implemented in a manner that contains hydrogen gas and liquid aromatic compound, respectively, liquid aromatic compounds, injected countercurrent to the Onna, proposed according to the invention, the hydrogenation is preferably carried out in such a way that containing the hydrogen gas is injected countercurrent to the liquid aromatic compound, respectively, liquid aromatic compounds, in a column that contains one of the above catalysts. When this liquid phase can pass through the column from top to bottom, and the gaseous phase from the bottom up. Preferably the hydrogenation carried out single-stage or multistage. Described in this application, the catalyst used is at least one stage.

As gas hydrogenation can use any gases that contain free hydrogen and do not include any harmful amounts of catalyst poisons, such as carbon monoxide. You can apply, for example, exhaust gases from the reformer. As gas hydrogenation, preferably using pure hydrogen.

The hydrogenation according to the invention can be performed in the absence or in the presence of a solvent or diluent, that is, it is not necessary to carry out the hydrogenation in solution.

As solvents or diluents can be used any suitable solvents or thinners. When this choice is not critical, while the used solvent or diluent capable of forming with gidir the subject aromatic compound homogeneous solution.

The amount of solvent or diluent is not specifically limited and can be chosen depending on the needs in any way, and, however, preferred such quantities that lead to the formation of 10-70 wt.%-the aqueous solution is provided for hydrogenation of aromatic compounds.

When applying solvent under the proposed according to the invention method as the preferred solvent, respectively, the preferred solvents are used formed during the hydrogenation product, therefore, the corresponding cycloaliphatic compound or the corresponding cycloaliphatic compounds, if necessary, along with other solvents or diluents. In this case, the part formed in the process of product can be added to another gidriruemyi aromatic connection.

Proposed according to the invention has numerous advantages over methods of the prior art. Reactive distillation combines the implementation of the chemical reactions and distillation separation of selected substances and products in a single installation. This technological advantages in relation to the reaction and reduces energy consumption. Moreover, compared with the reaction the distillation in separate installations achieve savings in the case of investments.

Moreover, through the proposed according to the invention, a method of aromatic compounds with clearly lower pressures and temperatures than described in the prior art, selectively and with high yield per unit time per unit volume hydronaut to the corresponding cycloaliphatic compounds. Even at lower pressures and temperatures, the catalysts have high activity. Cycloaliphatic compounds are in the form of high purity. Even with a slight pressure cycloaliphatic compounds get high yield per unit time per unit volume. The further hydrogenation can be performed with excellent selectivity without the addition of auxiliary chemicals.

The figure 1 presents a simplified diagram of the distillation plant for implementing the method according to the invention, in which the cycloaliphatic compound is removed from the bottom of the column.

The figure 2 presents this type a simplified diagram of the distillation plant for implementing the method according to the invention, in which the cycloaliphatic compound is brought out through the side lumen.

The figures will now be explained in more detail, for example, for the case of receipt of cyclohexane from benzene.

In the case proposed in the invention method, according to figure 1, the reaction of the implementation is given in the reaction column 4 on the heterogeneous catalyst 5, as mentioned above, by means of reactive distillation. The place of supply 1 benzene is in the upper part 3 of the reaction column 4, and the place of supply of 2 hydrogen is in the lower part of the reaction column 4. Thus, carry out the backflow of reagents within the reaction column 4. Benzene reacts with a heterogeneous catalyst 5 with simultaneous distillation with the formation of cyclohexane. Cyclohexane is a high-boiling component system substances, distilled in the lower part of the column 6 and is shown in line 8.

As benzene and cyclohexane to form a low-boiling azeotrope, the concentration profile in the case of the method according to the invention is positioned so that the bottom of the column 6 no benzene, and the region of high concentrations of benzene, respectively, benzene/cyclohexane is on the site heterogeneous catalyst 5.

Formed during the reaction by-products are low-boiling components and condense, if necessary, in the form of an azeotrope with benzene or cyclohexane in the condenser 9. The largest part containing benzene cerebral flow in the form of phlegmy 10 is directed into the reaction column 4 and a small portion 7 of the head stream containing by-products output. Moreover, in the low-boiling benzene note the si also is an easy way to separate the reaction zone with a heterogeneous catalyst 5 and output with part 7 of the head of the stream.

Together with low-boiling components from the reaction column goes unreacted coming into the head part of the reaction column 4 hydrogen 11, which, if necessary, after the conclusion of the partial stream 12 with a compressor 13 are returned to the lower part 6 of the reaction column 4.

In the implementation proposed according to the invention method using the setup presented in figure 2, cycloaliphatic compound as a valuable product, in this case, cyclohexane, out through the lateral outlet 14 at the bottom of column 3b. In the case of this variant implementation in line 8 from the bottom of column 6 receive high-boiling components. In contrast to figure 1 in figure 2 the upper part of the column designated as 3A, in the rest of the symbols in figure 2 correspond to those in figure 1.

The invention is now explained in more details by the following examples.

Example

The catalyst And

In the case of this catalyst, we are talking about a commercially available catalyst with 0.5% ruthenium on the balls of aluminum oxide with meso - and macropores, respectively, the catalyst 2 of the present invention.

Catalyst B

Catalytic nozzle of this catalyst is made of metallic fabric which has been coated with ruthenium. The method of preparation described in Savkina European patent A-0564830, related to this, the contents of which are fully included in the context of this application by reference.

The implementation of the method

Experimental apparatus consisted of a heated, equipped with a stirrer, the reaction flask stainless steel with a capacity of 2 l with impaled on her two-piece distillation column (length 1 m, diameter 50 mm). The distillation column at the bottom (0.5 m) was filled in the same experience of the above catalyst And in the other the experience of a catalyst B, while the upper part of the distillation column was loaded distillation nozzle type Montz AZ-750. Benzene using a pump they dosaged in the upper section of the distillation column. Hydrogen was dosed out in distillation cubic Therefore, implemented a counter-flow of the reactants through the catalyst.

Hydrogen and the resulting by-products out of the reaction column and are condensed in the partial condenser (PC). The condensate through the dispenser phlegmy did in the book. The remaining off-gas flow was passed through memoratives trap and then to measure the volume through the gas meter.

The installation was equipped with a pressure regulator and is designed for a system pressure of 20 bar.

All incoming and outgoing mesopotami during the duration of the experience is continuously determined and recorded, that is, could make up the balance by weight depending on the time.

An alternative to this using the same experimental setup was carried out by comparative experience in the irrigation mode.

Conditions and results of experiments are presented in table 1.

Table 1

The hydrogenation of benzene to cyclohexane
ExperienceColumnSupply of benzene [g/h]Conclusion from the bottom of the column [g/h]The distillate output [g/h]Abs. pressure [bar]T the bottom of the tower [°]T the top of the column [°]The distillate benzene [%]The distillate CG [%]The distillate PP [%]The bottom of the column benzene [%]The bottom of the column CG [%]The bottom of the column PP [%]
1 (benzene)Option 1 RD92857615711875,341,41,3<100 ppm100,0<100 ppm
2 (benzene)Option 2 RO1001000615725---18,880,50,71
3 (benzene)Option 1 is D 1001005615111856,240,21,1<100 ppm100,0<100 ppm
4 (benzene)Option 2 RO1001000615125---to 12.088,0<100 ppm
Option 1: the catalyst section 1: bulk material with catalyst A;

section 2: tissue attachment, Montz B1-750;

Option 2: section 1: tissue attachment with catalyst B;

section 2: tissue attachment, Montz B1-750. RD: reactive distillation; RO: irrigation mode; T: temperature; TG: cyclohexane; PP: by-products.

1. The method of hydrogenation of unsubstituted mononuclear aromatic compounds to the corresponding cycloaliphatic compounds with gaseous hydrogen in the presence of at least one hydrogenation catalyst in the reaction column by passing the components of the reaction through a fixed (fixed) in the reaction column of catalyst (catalysts) hydrogenation and the hydrogenation carried out so that the cycloaliphatic compounds derive from b is the same allotment, or bottom of the column, or from the side exhaust and the bottom of the column.

2. The method according to claim 1, in which the components of the reaction is passed countercurrent through a fixed (fixed) in the reaction column of catalyst (catalysts) hydrogenation.

3. The method according to claim 1 or 2, in which the hydrogenation is carried out at pressures below 20 bar and at a temperature below 200°C.

4. The method according to one of claims 1 to 3, in which the hydrogenation is carried out at pressures below the bar 13 and at a temperature below 150°C.

5. The method according to one of claims 1 to 4, in which the catalyst used heterogeneous catalyst.

6. The method according to claim 5, in which the catalyst used ruthenium catalyst.

7. The method according to claim 5 or 6, in which the catalyst used ruthenium catalyst in the form of bulk material in the reaction column and/or distillation of the nozzle in the column, preferably in the form consisting of inorganic or organic fibers, coated with ruthenium distillation attachment.

8. The method according to one of claims 1 to 7, in which the hydrogenation is carried out at a pressure in the region of 1-20 bar, preferably 5-13 bar, and/or at a temperature in the region of 50-200°C, preferably 80-150°C.

9. The method according to one of claims 1 to 8, in which the hydrogenation when the partial pressure of hydrogen is the largest in the area of 0.1-20 bar, pre is respectfully 5-13 bar.

10. The method according to one of claims 1 to 9, in which the undesirable by-products during the reaction are removed through distillation head of the column.

11. The method according to one of claims 1 to 10, which receive the cyclohexane from benzene.



 

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