Catalyst of aromatic hydrocarbons hydration and method of such catalyst obtaining and application

FIELD: chemistry.

SUBSTANCE: described is composition of catalyst of aromatic hydrocarbon hydration or composition for obtaining catalyst of aromatic hydrocarbon hydration, where composition contains more than 51% of pores, which have diameter more than 350 Ǻ (35 nm), counting from their total volume, which includes amorphous silicon oxide-aluminium oxide, in which percentage of pores with diameter more than 5000 Ǻ (500 nm) counting from total volume of pores, constitutes less than 4%. Described is method of aromatic hydrocarbons hydration in hydrocarbon raw material, containing aromatic hydrocarbons in concentration from 1% wt to 80% wt, and said method includes: contact of said hydrocarbon raw material at pressure between 10 and 100 bars and temperature from 125°C to 350°C with said composition; and obtaining product, which has reduced concentration of aromatic hydrocarbons. Described is method of obtaining catalyst of hydrating hydrocarbons mentioned above, which includes obtaining carrier composition by agglomeration of mixture, which includes water and amorphous silicon oxide-aluminium oxide, and drying obtained agglomerate; and introduction of carrier of noble metal, selected from group consisting of platinum, palladium and their combination, into said carrier composition with obtaining impregnated carrier composition.

EFFECT: increased catalytic activity.

14 cl, 2 tbl, 2 ex

 

The present invention relates to the composition of the medium with high macroporosity containing amorphous silica-alumina, the catalyst for the hydrogenation of aromatic hydrocarbons, which comprises a noble metal deposited on the composition of the medium with high macroporosity, and methods of producing and using such compositions media with high macroporosity and catalyst for the hydrogenation of aromatic hydrocarbons.

In many cases, a variety of streams of products of oil refineries contain aromatic hydrocarbons with significant concentrations and often require additional processing in order to obtain a product having the required or desirable characteristics and properties. It is generally accepted that the removal of the aromatic hydrocarbons contained in diesel fuel, can promote desirable to increase the cetane number thereof, and that the removal of the aromatic hydrocarbons contained in the fuel for jet engines, can help improve the maximum height mecoptera flame such. Viscous properties of the solvent and lubricating oils can also be improved by removing aromatic hydrocarbons from these oils.

In one early patent, US 3637484 described catalytic composition, vklyuchayaego and/or palladium, besieged in heterogeneous media, which includes aoademy silica-alumina, or joint gel. Heterogeneous media has a large pore volume, and a significant part of this volume has on the pores having a diameter greater than 500 Å (50 nm). However, joint gel silicon oxide-aluminum oxide which is dispersed in a matrix of heterogeneous media, compiled by gel alumina, does not need to be porous structure, as required for the entire composite material of catalyst.

Patent US 3943053 describes the method for the hydrogenation of aromatic hydrocarbons using a catalyst comprising platinum and palladium on an inert oxide carrier. Inert oxide carrier is an aluminum oxide with a large surface area is preferable to the acidic materials such as silica-alumina. The final catalyst, subjected to calcination contains from 0.3 to 0.5% weight. metal platinum and from 0.3 to 0.9 wt%. metal palladium.

Another catalyst used for hydrogenation of the aromatic hydrocarbons contained in the hydrocarbon distillate as raw material, disclosed in US patent 5308814, which describes a catalyst comprising a hydrogenating component of the catalyst carrier. Component catalyst carrier comprises zeolite Y, and a refractory inorganic oxide such as silica, alumina or silica-alumina. Hydrogenating component of the catalyst may be a platinum and palladium, which are present in amounts ranging from about 0.1 wt%. up to about 2.0 wt%, when the weight ratio of elemental palladium to elemental platinum in the range from 10:1 to 1:10. Hydrogenating component may be deposited on the catalyst carrier or embedded in such methods of impregnation.

Patent US 6296759 describes a catalyst which comprises platinum, palladium or a combination thereof on the non-crystalline, acidic media, silicon oxide-aluminum oxide as the media get in the way "Sol-gel", and which is applicable to the hydrogenation of aromatic compounds contained in the distillate raw materials, which also contain sulfur. Way "Sol-gel" includes adding dropwise the aqueous Sol of inorganic salts of aluminum and silicon in the oil phase to form droplets. The formation of droplets makes it unnecessary to use a separate stage of molding, such as extrusion.

WO 94/10263 describes the catalyst applicable to the production of lubricating base oils. The catalyst comprises hydrogenating component supported on a carrier, on which the includes amorphous silica-alumina, which carrier has macroporosity in the range of 5 volume percent to 50 volume percent. Hydrogenating component may be selected from metals of Groups VIB and VIII of the Periodic Table. The carrier is preferably obtained by dispersing a mixture of the amorphous silicon oxide-aluminum oxide and a suitable liquid, extruding the mixture and then drying the obtained extrudates. The carrier may include the binder, and the composition of the medium can be used activators of softening and tools that facilitate the extrusion process.

It is desirable to have a composition of a carrier suitable for application to one component of the noble metal to thereby form a catalyst composition for the hydrogenation of aromatic hydrocarbons.

It is also desirable to have a catalyst composition for the hydrogenation of aromatic hydrocarbons, having a particularly good activity towards hydrogenation of aromatic hydrocarbons.

It is also desirable to have a method of hydrogenation of the aromatic hydrocarbons contained in the hydrocarbon raw material, and, in particular, the method of saturation of the aromatic hydrocarbons contained in the hydrocarbon distillate raw materials, such as jet fuel and diesel fuel in order to improve the properties thereof.

Accordingly, a composition comprising the composition of the medium having macroporosity more than 51%, and comprising amorphous silica-alumina. The noble metal may be introduced into the composition of the medium with the formation thereby of a catalyst for hydrogenation of aromatic hydrocarbons. The composition of the medium produced by sintering a mixture comprising water and amorphous silica-alumina, and drying the obtained agglomerate with the formation of the composition of the media. Introduced in the composition of the carrier of a noble metal selected from the group consisting of platinum, palladium and combinations thereof, in order in this way to get impregnated composition of the medium, which can be subjected to calcination to form catalyst for the hydrogenation of aromatic hydrocarbons. The catalytic hydrogenation of aromatic hydrocarbons can be used for the hydrogenation of aromatic hydrocarbons in the hydrocarbon raw material containing aromatic hydrocarbons with a significant concentration, by contacting the named hydrocarbon feedstock with that, with appropriate conditions for hydrogenation of aromatic hydrocarbons to obtain a product having a reduced concentration of aromatic hydrocarbons.

The invention Rel is relates to a new catalyst for the hydrogenation of aromatic hydrocarbons, which has a high catalytic activity in the hydrogenation of aromatic hydrocarbons in comparison with the prototype catalysts for the hydrogenation of aromatic hydrocarbons, and to a method of dearomatization hydrocarbon raw materials, and, in particular, dearomatization hydrocarbon distillates, such as kerosene and diesel fuel. The invention also relates to a new composition of the medium and method for producing such compositions media, which mainly can be used as a substrate or carrier for at least one noble metal, which is embedded in one to create the final catalytic composition, that is the catalyst for the hydrogenation of aromatic hydrocarbons according to the invention. This composition of the medium has unique physical properties that seem to provide a final catalyst composition having enhanced activity against saturation of aromatic hydrocarbons.

The composition of the medium is obtained using amorphous silica-alumina having unique properties, and which can be obtained by the new method, the so-called "method of variations of pH", which is fully described in concurrently pending provisional patent application No. 6/968122, filed simultaneously with the present application, entitled "Composition of the amorphous silicon oxide-aluminum oxide and method for producing and using such compositions, the description of which is incorporated herein by reference. Thus, the composition of the carrier includes amorphous silicon oxide-aluminum oxide, which is characterized in that it has certain unique properties. It appears that the physical characteristics of the amorphous silicon oxide-aluminum oxide provide the composition of the medium, with properties that make it particularly desirable for use as a substrate or carrier for at least one noble metal hydrogenating component, and, further, which provide certain preferential catalytic parameters, making the final catalytic composition of highly active when used in certain embodiments of the application. One in particular, the preferential option for the application of the final catalytic composition is in the hydrogenation or saturation of aromatic hydrocarbons contained in hydrocarbon distillates.

Amorphous silica-alumina used in obtaining the composition of the media is vysokonaporny in the sense that it contains very little of aluminum oxide, which is Krista is symbolic. The amount of crystalline aluminum oxide in an amorphous silicon oxide-aluminum oxide appears characteristic for such painting powder x-ray diffraction (XRD), in which, essentially, no XRD peaks, which are indicative of various crystalline phases of alumina. In General, the amount of aluminum oxide, which forms a crystalline phase contained in the amorphous silicon oxide-aluminum oxide is less than 10 wt%. the total weight of the amorphous silica-alumina. More specifically, amorphous silica-alumina contains less than 8 wt%. crystalline aluminum oxide, and, most specifically, he has less than 5% weight. crystalline aluminum oxide.

Amorphous silica-alumina may have a content of silicon oxide, which varies in the range of from 10 to 90 wt%, with the weight percentages calculated on the total dry weight of the amorphous silica-alumina. However, the preferred content of silicon oxide ranges from 25 to 75 wt%, and, most preferably, the content of silicon oxide ranges from 40 to 60% of the weight.. the aluminum Oxide may be present in an amorphous silicon oxide-aluminum oxide in a quantity varying in the range from 10 to 90 wt%, more specifically, from 25 to 75 wt%, and most of concr the IDT from 40 to 60 wt%.

Particularly important property of the amorphous silicon oxide-aluminum oxide is that it has a relatively high ratio of its pore volume, which accounts for its large pores, to its pore volume, which accounts for its medium and small pores. One measure of this characteristic is the ratio of pore volume (cm3/g)attributable to pores of amorphous silica-alumina having pores with a diameter of less than 2150 Å (215 nm) (A), the pore volume attributable to pores of amorphous silica-alumina having pores with a diameter of less than 210 Å (21 nm) ("In"). This attitude of "Well-to-In ratio (a/b), in General, should be less than about 2.2, and preferably, the ratio a/b exceeds the 2.4, and most preferably the ratio a/b is greater than 2.5.

Here links to the total pore volume relate to the pore volume, as determined using a Standard Test Method to determine the Distribution of the pore Volume of the Catalysts By Porosimetry by Mercury Intrusion, ASTM D 4284-88, at a maximum pressure of 4000 bar (400 MPa), under the assumption that the surface tension of mercury is 484 Dyne/cm (484 mn/m), and the wetting angle of the amorphous silicon oxide-aluminum oxide is 140°.

Amorphous silica-alumina has very largely high value PLO is ADI's surface and the total pore volume. Its surface area can vary in the range from 190 m2/g to 400 m2/g, but more specifically, such varies in the range from 200 m2/g to 350 m2/g, and more specifically, from 225 m2/g to 325 m2/g Total pore volume of the amorphous silica-alumina ranges from 0.8 cm3/g to 1.3 cm3/g, more specifically, from 0.9 cm3/g to 1.2 cm3/g and, most specifically, from 0.95 cm3/g to 1.1 cm3/year

Another important property of the amorphous silica-alumina used in obtaining the composition of the media, is that one should give solid27Al-NMR spectrum (Aluminum), which is characterized by peak pentacoordinated aluminum, having a magnitude relative to other aluminum peaks, indicative for the presence pentacoordinated aluminum that the area thereof is more than 30 percent of the total area of the three peaks in the NMR spectrum, characteristic of the three types of aluminum. More specifically, a strong peak pentacoordinated aluminum in solid state27Al-NMR spectrum of amorphous silica-alumina must be greater than 35% of the total amount of the three types of aluminum, and, most specifically, it must be more than 40% of the total amount of the three types of aluminum.

As mentioned here, the NMR spectrum of amorn the first silicon oxide-aluminum oxide is such, generated using standard methodology spectroscopy Solid-state Nuclear Magnetic Resonance (NMR, NMR), known qualified specialists in this field of technology, which use the methods of NMR for characterizing the structural configurations of solid materials. Check the NMR spectrum of the composition of the amorphous silica-alumina may be performed using any suitable device and equipment that provide the spectrum, which is essentially similar to that which can be recorded by using the NMR spectrometer, manufactured and sold by Varian, Inc. in Palo Alto, California, such as NMR spectrometer Varian 400-MR, using a 5 mm high-power solid-state NMR spin-detector firms Doty Scientific, Inc. in Columbia, North Carolina. The sample is placed in a 5 mm rotor silicon nitride (Si3N4and rotate with a frequency of 13 to 16 kHz (with speed from 780000 to 960000 rpm) in a dry nitrogen atmosphere at room temperature. The stator housing is adjusted so that when the magic angle to the external magnetic field to minimize the broadening due to the random orientation of the individual nuclei relative to the external magnetic field. The resonant frequency for nuclei of aluminum at this naprazhen the STI field is the 104.3 MHz. As the experimental conditions using a spectral width of 0.5 MHz, a pulse duration of 1.0 microseconds and the delay for relaxation (accumulation time) of 0.3 seconds.

Solid-state NMR spectrum of the core of aluminum for amorphous silica-alumina has three significant peak: the first peak, located in the region of about 65 ppm (ppm, ppm) on the scale chemical shifts, representing the centers of tetrahedral aluminum; the second peak, located in the region of about 30 ppm on the scale chemical shifts, representing the centers pentacoordinated aluminum; and the third peak located in the range from about 3 to 6 ppm on the scale chemical shifts, representing the centers of octahedral aluminum. These chemical shifts are measured relative to the resonance signal of an aqueous aluminum chloride at 0.0 ppm On the value of the chemical shift peaks above can influence the acidity and quadrupole interaction of the second order acting on the respective cores of aluminum.

The composition of the carrier according to the invention can be obtained by mixing amorphous silica-alumina and a suitable liquid, such as water, forming the mixture into particles with a certain shape, and then drying molded particles. While the preferred composition of the media receive the Ute without the addition of binders or inorganic oxide material, however, the inorganic oxide material may be mixed into the amorphous silicon oxide-aluminum oxide in the preparation of the composition of the media. Examples of inorganic oxide materials include silica, alumina, clay, magnesium oxide, titanium oxide and zirconium oxide. Of such preferred silicon oxide and aluminum oxide.

If obtaining the composition of the medium with an amorphous silica-alumina mixed inorganic oxide material, it may be present in amounts up to 50% by weight relative to the composition of the medium, and, mainly, from 5 to 30% by weight.

It is preferable to mix the raw materials, such as amorphous silica-alumina, or water, or an organic oxide, or a combination thereof, thereby to form a paste that has properties that make it suitable for extrusion or molding of extruded particles by any known extrusion method. In addition, amorphous silica-alumina and, if present, other source materials can be agglomerated to form particles of a certain shape, such as spheroids, beads or pellets, cylinders, irregular extruded particles or simply weakly bound aggregates or clusters, in any of the ways known to skilled is professionals in this area of technology, including but not limited to such, molding, tableting, extrusion, packaging, extrusion and surface finishing process.

Drying molded particles produce to remove certain quantities of water or volatile components contained in such, and may be conducted at any suitable temperature to remove excess water or volatile components. Preferably, the temperature during drying will vary in the range from about 75°C. to 250°C. the duration of the drying these particles represents any suitable period of time necessary to achieve the desired degree of reduction of the volatile components in the molded part before the introduction of the hydrogenating component.

The essential feature of the composition of the medium is the presence of such high macro porosity. It is widely accepted that the properties of the amorphous silica-alumina used to obtain the composition of the carrier are transferred to the media composition having such high macroporosity. It also seems that high macroporosity composition of the media and other properties, reported that of amorphous silicon oxide, aluminum oxide, which is used for the preparation of compositions of the media, provide end-katal the political composition, having a high activity in the hydrogenation of aromatic hydrocarbons.

The term "macroporosity" is used here to denote measures the porosity of the composition of the media, which seems to be the percentages of the total pore volume of the composition of the medium per macropores such. Macropores are pores in the composition of the carrier having a pore diameter of more than 350 angstroms (Å) (35 nm). Macroporosity composition of the carrier according to the invention is extremely high in the sense that the percentage of the total pore volume of the composition of the media, which accounts for macropores (pores having a pore diameter of greater than 350 Å (35 nm)), or macroporosity such, is more than 51 percent (%). Preferably macroporosity composition of the media is more than 52%, and more preferably macroporosity composition of the media is more than 54%. The upper limit value of macro porosity of the composition of the medium is less than 90%, or less than 80%, or even less than 70%.

For macropores in the composition of the medium, when such use in certain embodiments of the application, an important factor may be the presence to some extent narrow distribution of pore sizes, and it is believed that the unique properties of amorphous silica-alumina used to obtain the composition but the Itala, may be due to such a narrow distribution of the pore size. Indeed, this is achieved due to certain unique properties of amorphous silicon oxide-aluminum oxide, which is obtained by the aforementioned method, fluctuations in pH, which helps to ensure the preparation of the composition of the carrier according to the invention, having a high macroporosity as previously described, and a narrow distribution of the pore sizes for the macropores. It is desirable that the percentage of the total pore volume of the composition of the medium, which had the macropores such, having the diameter of pores in the range of 350 Å to 2000 Å (35-200 nm), was more than 40%, preferably more than 44%, and most preferably more than 46%.

With regard to the total pore volume of the composition of the media, which accounts for the extra-large macropores, which have a pore diameter of more than 5000 Å (500 nm), it is desirable that the percentage of total pore volume attributable to such mega macropores, was less than 4%, preferably less than 2%, and most preferably less than 1%.

Another desirable property of the composition of the media is to have any significant mesoporosity. The term "misoprostol" is used here to denote measures the porosity of the composition of the medium, which presents the percentages of the total pore volume of the composition but is of Italia, have mesopores such. In addition, it is important that a small part of the total pore volume of the composition of the medium were smaller pores in such, but to the composition of the media had quite a large portion or percentage of their total pore volume, which accounts for the mesopores, or, in other words, that the composition of the medium had a significant mesoporosity. The mesopores, as used herein, the terms represent such pores composition of the media, which have a diameter of pores in the range of from 50 Å to 350 Å (5-35 nm). It is desirable that misoprostol composition of the media was more than 30%, more preferably 35% and most preferably more than 40%.

The percentage of the total pore volume of the composition carrier, attributable to the small pores such, which have a pore diameter of less than 70 Å (7 nm), must be less than 10% of the total pore volume of the composition carrier, preferably less than 7%, and most preferably less than 5%.

Another characteristic of the composition of the media is that such has significantly high values of surface area and total pore volume. The surface area can vary in the range from 150 m2/g to 400 m2/g, but more specifically, it can be in the range from 175 m2/g to 350 m2/g, and more specifically, from 200 m2/g to 325 m /g Total pore volume of the composition of the carrier varies in the range from 0.8 cm3/g to 1.3 cm3/g, more specifically, from 0.9 cm3/g to 1.2 cm3/g, and more specifically, from 0.95 cm3/g to 1.1 cm3/year

To obtain the final catalytic composition according to the invention in the composition of the carrier injected component is a noble metal. Component of the noble metal may be introduced into the composition of the carrier using any suitable means or methods known qualified specialists in this field of technology, for the introduction of the noble metal in the catalyst carrier. For the introduction of the noble metal in the composition of the medium is preferable application of the method of impregnation, and among these methods is preferably a component of the noble metal in the composition of the medium using the well known method of initial wetting.

The solution for impregnating solution of the noble metal includes decomposing when heated salt of platinum or palladium or both of platinum and palladium dissolved in water. Examples of possible salts of platinum, which can be used include platinum compounds: chloroplatinic acid; chloroplatinate ammonium; bromopurine acid; trichloride platinum; hydrate of platinum tetrachloride; dichloride dichloro helpline; dinitrodiphenylamine; tetranitromethane sodium and nitrate tetraammineplatinum(II). Examples of possible salts of palladium, which can be used include palladium compounds: chloropalladite acid; palladium chloride; nitrate, palladium sulfate, palladium; hydroxide diaminopimelate; chloride tetraamminepalladium and nitrate tetraamminepalladium(II). The preferred platinum compound and a compound of palladium for use in the solution for impregnating represent, respectively, the nitrate tetraammineplatinum(II) and nitrate tetraamminepalladium(II).

The amount of noble metal is introduced into the composition of the medium should be such as to obtain a final catalyst composition according to the invention, having a precious metal content of which varies in the range from 0.01 wt%. up to 5% weight. for each of the noble metals, with a value of percent by weight calculated on the total weight of the final catalyst composition and calculated elemental metal. The preferred precious metal content of each component of the noble metal varies in the range from 0.1 wt%. up to 4 wt%, and most preferably from 0.2 to 3 wt%.

While the final catalytic composition may include or platinum as a component of the noble metal or palladium as to the ponent of the noble metal, you should take into account that the use of a combination of two noble metals contained in the final catalytic composition can provide improved activity in the hydrogenation of aromatic hydrocarbons. Thus, it is preferable that the final catalytic composition according to the invention include both components, as platinum and palladium. In a preferred final catalytic composition the weight ratio of elemental palladium to elemental platinum varies in the range from 1:10 to 10:1, preferably from 1:2 to 5:1, and most preferably from 1:1 to 3:1.

The composition of the medium, which is impregnated component of the noble metal, dried at any suitable temperature to remove any excess water or volatile components. In General, the temperature during drying will vary in the range from about 75°C. to 250°C. the Duration of drying the intermediate catalytic composition is a any period of time necessary to achieve the desired degree of reduction of the volatile components, and can vary from 0.1 hour up to 72 hours. After drying the impregnated composition of the medium is then subjected to calcination in the presence of oxygen-containing fluid, such as air, when the temperature is re and during the period of time, what are sufficient to achieve the desired degree of calcination to obtain the final catalyst composition (catalyst hydrogenation of aromatic hydrocarbons). In General, the temperature of calcination varies in the range from 250°C (482°F) up to 550°C (1022°F). The preferred temperature calcination varies in the range from 280°C (536°F) up to 520°C (968°F).

The final catalytic composition according to the invention basically has a surface area in the range from 175 m2/g to 600 m2/g, as determined by the method of BET (brunauer-Emmett-teller) nitrogen (N2), preferably from 200 m2/g to 550 m2/g, and most preferably from 225 m2/g to 500 m2/g pore Volume of the final catalytic composition, by definition, using standard methodology mercury porosimetry, mainly varies in the range of 0.7 ml/g to 1.3 ml/g, and median pore size in the final catalytic composition varies in the range from 50 angstroms (Å) (5 nm) up to 250 angstroms (25 nm).

The final catalytic composition according to the invention is particularly applicable to processes for the hydrogenation of aromatic hydrocarbons, and, in particular, are useful for dearomatization hydrocarbon raw materials containing aromatic hydrocarbons. One question hydrocarbon is a raw material according to the invention includes the flow of distillate from oil refineries, includes hydrocarbons that have a boiling point at atmospheric pressure in the range from about 140°C (284°F) to about 410°C (770°F). These temperatures represent approximately the temperature of the beginning and end boiling distillate raw material.

Examples of flows of products of petroleum refining, which are assumed to be included within the meaning of the term "distillate stream from oil refineries" or "distillate raw material include distillate fuel straight race, boiling in the mentioned temperature range boiling point, such as kerosene, jet fuel, light diesel oil, heating oil and heavy diesel oil, and shoulder straps from cracking, such as cycle oil from catalytic cracking (FCC), the oil coking and distillation products from hydrocracking.

Another question hydrocarbon raw material according to the invention includes the fraction of heavy fuel oil from refineries, with a temperature range of boiling points, which at least partially overlaps with the temperature range of the boiling point of the lubricating base oils. Source fraction of heavy fuel oil from the distillation of crude oil can be light or heavy vacuum gas oil obtained by vacuum distillation of the residual fraction from the at overnoy distillation, obtained from the distillation of crude oil under atmospheric pressure. The temperature of the boiling point of such vacuum gasoil mainly ranges from 300°C (572°F) up to 620°C (1148°F).

Before use in such method according to the invention, fraction of heavy fuel oil from the distillation of crude oil can be processed in stages known processes for hydrocracking and dewaxing, such as dewaxing solvent and catalytic dewaxing to obtain a product that has many properties that are desirable for the lubricating base oil. The method according to the invention may include processing the fraction of heavy fuel oil from oil distillation, which has already been processed in these process stages, as hydrocracking and dewaxing, or handling of heavy fuel oil from oil distillation, which has not yet been subjected to preliminary processing. When processing the fraction of heavy fuel oil from oil distillation, it is desirable to apply the final catalytic composition according to the invention as catalyst hydrofinishing ("bleaching") of raw material for the lubricating base oil having a spacing evaporating temperatures from 350°C (662°F) up to 580°C (1076°F), and which represents the fraction of heavy fuel oil from oil distillation subjected guide is acracking and dewaxing.

One variant of the method according to the invention includes the elimination in hydrocarbon raw material aromatic compounds by hydrogenation, to obtain or to obtain a product having a concentration of aromatic hydrocarbons, reduced compared to the concentration of aromatic hydrocarbons in the hydrocarbon raw material. In this process dearomatization hydrocarbon raw material may include aromatic hydrocarbons in concentrations varying in the range from 1 wt%. up to 80 wt%, with weight percent based on the total weight of the hydrocarbon raw material, including aromatic hydrocarbons and sulfur components thereof. More than the applicable concentration of aromatic hydrocarbons in the hydrocarbon raw material varies in the range from 2 wt%. up to 30% weight., and the most acceptable concentration of aromatic hydrocarbons in the hydrocarbon raw material varies in the range from 3 wt%. up to 20% of the weight.

The final catalytic composition according to the invention can be used as part of any suitable reactor system, which provides for the contacting of the catalyst with a hydrocarbon such raw material under proper conditions dearomatization, or hydrogenation of aromatic hydrocarbons, which may on the part the presence of hydrogen and the use of elevated pressure and temperature. One preferred reactor system is one that includes the layer of the final catalytic composition contained within a reactor vessel equipped with an inlet device for a power reactor, such as the supply nozzle, for introducing hydrocarbon feed material in the reactor tank, and an exhaust device for output streams, flowing out of the reactor, such as a discharge nozzle for the output stream for removal resulting from reactor a stream or a product having a reduced concentration of aromatic hydrocarbons from the reactor vessel.

The degree of dearomatization achieved by the method according to the invention, generally exceeds 20 mole percent of the aromatic hydrocarbons contained in the hydrocarbon raw material. But it is desirable that the method according to the invention provided the molar percentage of dearomatization hydrocarbon raw material is greater than 40 mole percent. Preferably, the method according to the invention provided dearomatization greater than 50 molar percent, and most preferably more than 80 mole percent. The term "molar percent of dearomatization" is used here to denote the fraction of moles of the aromatic hydrocarbons contained in the hydrocarbon raw material, which is haunted saturated method according to the invention, divided by the total number of moles of the aromatic hydrocarbons contained in the hydrocarbon raw material. The molar percentage of dearomatization can be calculated by dividing the difference between the total number of moles of aromatic hydrocarbons in the hydrocarbon raw material and product by the total number of moles of aromatic hydrocarbons in the hydrocarbon raw material. Thus, the product of the method according to the invention will have a reduced concentration of aromatic hydrocarbons so that it contains a number of aromatic hydrocarbons, which may not exceed 80 mole percent of the aromatic hydrocarbons contained in the hydrocarbon raw material, but preferably not more than 60 mole percent. It is preferred that the product contained a number of aromatic hydrocarbons, which may not exceed 50 mole percent of the aromatic hydrocarbons contained in the hydrocarbon raw material, and most preferably not more than 20 molar percent.

When the method according to the invention is dearomatization flow of distillate from oil distillation as the hydrocarbon raw material, the reaction pressure generally varies in the range from 10 bar (1 MPa (145 psi) 100 bar (10 MPa) (1470 psi), preferably from 20 bar (2 MPa (290 psi) to 0 bar (7 MPa) (1028 psi) and more preferably from 30 bar (3 MPa (435 psi) 60 bar (6 MPa (870 psi).

For dearomatization hydrocarbon raw material, the reaction temperature at which the hydrocarbon raw material is in contact with the final catalytic composition varies in the range from 125°C (247°F) to 350°C (662°F), preferably between 150°C (302°F) up to 325°C (617°F) and most preferably from 175°C (347°F) to 300°C (572°F).

The flow rate at which the hydrocarbon raw material is served in the reaction zone of the process according to the invention, in General, is such as to provide the time value of bulk fluid velocity (LHSV) in the range from 0.01 h-1up to 10 h-1. The term "hourly space velocity of fluid", as used here, means the numerical value of the speed at which the hydrocarbon raw material is fed into the reaction zone of the process according to the invention, in units of volume per hour divided by the volume of catalyst contained in the reaction zone that receives a hydrocarbon material. The preferred LHSV value varies in the range from 0.05 h-1up to 6 h-1, more preferably from 0.1 h-1up to 4 h-1and most preferably from 0.2 h-1up to 3 h-1.

The amount of hydrogen supplied to the reaction zone of the process according to the invention may in a great degree the Yeni depend on the amount of aromatic hydrocarbons, contained in the hydrocarbon raw material is subjected to dearomatization. In General, the amount of hydrogen relative to the amount of the hydrocarbon feedstock entering the reaction zone ranges up to 1781 m3/m3(10000 SCF/bbl (standard cubic feet/barrel). Preferably, the feed rate of hydrogen was in the range from 89 m3/m3(500 SCF/bbl) to 1781 m3/m3(10000 SCF/bbl), more preferably from 178 m3/m3(1000 SCF/bbl) to 1602 m3/m3(9000 SCF/bbl), and most preferably from 356 m3/m3(2000 SCF/bbl) to 1425 m3/m3(8000 SCF/bbl).

The following examples are presented to further illustrate certain aspects of the invention, but should not be construed as limiting the scope of the invention in any way.

Example I

Description in this example, I illustrate the preparation of the relevant invention compositions media with high macroporosity containing amorphous silica-alumina obtained by the method of variations of pH, and the final catalyst for the hydrogenation of aromatic hydrocarbons using such compositions media, and receiving traditional media containing cooked the conventional way, the silicon oxide-aluminum oxide is tion, and the final catalyst using such common carrier.

The formation of the extrudate. The mixture of the powder of silicon oxide-aluminum oxide and distilled water (mix LOI = 64% (LOI = limiting oxygen index)) were placed in a mixer for mixing paste Simpson Muller and mixed within 105 minutes. Added auxiliary means for extruding “Superfloc A-level content 2%, calculated on the dry powder, and the mixture was mixed for an additional 5 minutes. This material was then extrudible through spunbond insertion of education trendology granule size 1.6 mm after drying at a temperature of 275°F (135°C) for 3-4 hours and subjected to calcination at a temperature of 1000°F (538°C) for 2 hours. Properties of extrudates obtained from both traditional and formed by the method of variations of pH powders of silicon oxide-aluminum oxide, shown below in table 1.

Table 1
DescriptionThe extrudate AndThe extrudate
The powder of silicon oxide-aluminum oxideVariable p is Traditionally, the
The total amount of intrusion of mercurycm3/g1,04110,9606
Macroporosity (> 350 angstroms (>35 nm))%62,438,0
Pore volume 50-350 angstroms (5-35 nm) mercury porosimetry%35,4150,0
Pore volume 350-2000 angstroms (35-200 nm) mercury porosimetry%48,033,4
Pore volume > 5000 angstroms (500 nm) of the mercury porosimetry2,030,96
Pore volume of < 70 angstroms (7 nm) of the mercury porosimetry6,2945,94
Median pore diameter (volume)Angstrom600 (60 nm)74 (7,4 nm)
Median pore diameter (area) Angstrom98 (9,8 nm)57 (5,7 nm)
Surface aream2/g253395
The volume of pore waterm2/g0,9881,05

Obtaining catalyst. Nitrate solution tetraammineplatinum and nitrate tetraamminepalladium in dilute aqueous ammonia solution (pH of the solution to ~9.5) and concentrations necessary to achieve target levels of platinum (Pt) and palladium (Pd) catalyst, was impregnable media silicon oxide-aluminum oxide using the method of saturation of the pore volume. Wet impregnate dried at a temperature of 257°F (125°C) for 3 hours and then was caliciviral in air at a temperature of 545°F (285°C) for 2 hours. Then the catalysts were tested for activity saturation of aromatic hydrocarbons. The results are shown in table 2.

Example II

This example II illustrates the use of the catalyst compositions described in example I, dearomatization hydrocarbon raw material, and represents the performance of the catalysts.

Test veselinov the oil : Load = heavy naphthenic petroleum jelly. Absorption in the ultraviolet (UV) spectrum at a wavelength of 275 nm (0.5 cm cuvette) = 77,71. Test conditions: pressure = 2175 psig (15 MPa, excess), the hydrogen (H2)/oil = 4600 SCF/bbl (standard cubic feet/barrel) (819,26 m3/m3)), LHSV (hourly volume velocity of the fluid) = 0,96, temperature (T) = 420°F (215,56°C).

Test diesel oil: Load = distillate is subjected to the hydraulic control treatment (IPF nitrogen (N) and sulfur (S) < 1 million shares (ppm); aromatic hydrocarbons according to SFC (supercritical fluid chromatography) = 47.6% of the weight. Test conditions: pressure = 600 psig (4,14 MPa, excess), the hydrogen (H2)/oil = 2500 SCF/bbl (standard cubic feet/barrel) (445,25 m3/m3)), LHSV (hourly volume velocity of the fluid) = 3.0V, temperature (T) = 400°F (204,44°C).

Activation of the catalyst. The catalysts were loaded into a reactor with a fixed bed with drip irrigation in the liquid phase, with silicon carbide (SiC) as a filler layer (the volume ratio of catalyst/filler" 1:2), and processed in an atmosphere of hydrogen at a test velocity of gas and a temperature of 300°F (148,9°C) for 3 hours. The temperature was raised to 600°F (315,56°C) 50°F (10°C) per hour and was kept for 1 hour. Then the temperature was lowered to 200°F (93,33°C) before suggesting the m power and establishment of test conditions.

Table 2
Test results
The extrudateWeight percent platinumWeight percent palladiumTesting of mineral oilthe absorption at the wavelength of 275 nm, cuvette 0.5 cmTest diesel fueltemperature (F) 80%conversion of aromatic hydrocarbons
Catalyst A1A0,30,50,092350 (176,67°C)
Catalyst A2B0,150,250,085There are no data
The catalyst InC0,31,00,40390 (198,89°C)

The results presented in table 2 show that the catalytic hydrogenation of aromatic hydrocarbons obtained from the composition is medium with high macroporosity (i.e. Catalyst A1 and Catalyst A2), was active hydrogenation, surpassing that of the catalyst used in which the common carrier.

1. The composition of the catalyst for hydrogenation of aromatic hydrocarbons or composition to obtain catalyst for the hydrogenation of aromatic hydrocarbons, where the composition contains more than 51% of the pores having a diameter greater than 350 Å (35), considering of their total amount, which includes amorphous silica-alumina, in which the percentage of pores with a diameter greater than 5000 Å (500 nm) of the total pore volume is less than 4%.

2. The composition according to claim 1, where the composition contains more than 30% of pores with a diameter between 50 Å (5 nm) and 350 Å (35 mi).

3. The composition according to any one of claims 1 or 2, in which the percentage of the total pore volume of the composition contained in its macropores having a pore diameter in the range of 350 Å to 2000 Å (35-200 nm)exceeds 40%.

4. The composition according to any one of claims 1 or 2, in which the percentage of the total pore volume of the composition of the medium contained in its smaller pores having a diameter of less than 70 Å (7 nm)is less than 10%.

5. The composition according to any one of claims 1 or 2, in which the amorphous silica-alumina has A/In excess of 2.2, where a is the pore volume (cm3/g)attributable to pores of amorphous silica-alumina having pores with a diameter of less than 2150 Å (215 nm) and the volume is, attributable to pores of amorphous silica-alumina having pores with a diameter of less than 210 Å (21 nm), and named the amorphous silica-alumina exhibits a strong characteristic peak in the NMR spectrum of the Penta-coordinated aluminum, representing more than 30% of the aluminum in the above amorphous silicon oxide-aluminum oxide.

6. The composition according to any one of claims 1 or 2, in which the mentioned amorphous silica-alumina has a content of silicon oxide in the range from 10 to 90 weight percent, and the content of aluminum oxide in the range from 10 to 90 weight percent.

7. The composition according to any one of claims 1 or 2, further comprising palladium and platinum, which are present in the composition in such amounts that the weight ratio of elemental palladium to elemental platinum varied in the range from 1:10 to 10:1.

8. The composition according to any one of claims 1 or 2, in which the amorphous silica-alumina produced by the method of variations of pH.

9. The composition according to claim 7, in which the noble metal is present in the composition in amount in the range from 0.01 wt.% up to 5 wt.%, calculated on the total weight of the above composition by elemental metal.

10. The composition according to any one of claims 1 or 2, in which the above composition has a total surface area in the range from 200 m2/g to 350 the 2/year

11. The method of hydrogenation of the aromatic hydrocarbons in the hydrocarbon raw material containing aromatic hydrocarbons in a concentration of from 1 wt.% up to 80 wt.%, and named the method includes: contacting the named hydrocarbon raw material at a pressure between 10 and 100 bar and a temperature of from 125°C to 350°C with composition but any one of claims 1 or 2; and obtaining a product having a reduced concentration of aromatic hydrocarbons.

12. The method of producing catalyst for the hydrogenation of aromatic hydrocarbons according to any one of claims 1 or 2, comprising a composition of media glomerulone mixture comprising water and amorphous silica-alumina, and drying the obtained agglomerate; and the introduction in the above composition of the carrier noble metal selected from the group consisting of platinum, palladium and combinations thereof, to obtain the coating composition of the media.

13. The method according to item 12, further comprising calcining the impregnated composition of the medium with the final catalytic composition.

14. The catalytic hydrogenation of aromatic hydrocarbons obtained by the method according to any of PP and 13.



 

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1 tbl, 7 ex

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1 tbl, 7 ex

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9 ex, 1 tbl

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1 tbl, 7 ex

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2 cl, 5 tbl, 25 ex

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2 ex

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