Aromatic compound and olefin hydrogenation with using mesoporous catalyst

FIELD: chemistry.

SUBSTANCE: invention refers to method of aromatic compound and olefin hydrogenation in hydrocarbon flows. Method concerns hydrogenation of incoming hydrocarbon flow containing unsaturated components, which involves: a) formation of the catalyst including at least one metal of group VIII on noncrystalline mesoporous inorganic oxide support with at least 97 vl % of interconnected mesopores in relation to mesopores and micropores with "БЭТ" surface area at least 300 m²/g and pore space at least 0.3 cm³/g; and b) interaction of incoming hydrocarbon flow and hydrogen with the specified catalyst added in reaction hydrogenation zone in hydrogenation environment to make product with lowered content of unsaturated components. Herewith hydrogenation conditions include hourly volume liquid velocity (HVLV) within approximately more than 0.33 h^-1 to approximately 10.0 h^-1 and hydrogen circulation rate within approximately 500 SCF/barrel to approximately 20000 SCF/barrel.

EFFECT: development of effective method of aromatic compound and olefin hydrogenation in hydrocarbon flows.

23 cl, 14 ex, 2 tbl

Cross-reference to related applications

This application is a partial continuation in the process of simultaneous consideration of the patent application U.S. serial No. 10/886993 July 8, 2004, which is reproduced here as a reference.

Background of invention

1. The technical field to which the invention relates

The present invention relates to a method and catalyst for hydrogenation of aromatic compounds and olefins in hydrocarbon streams, preferably (but not limited to) in hydrocarbon distillates.

2. Description of prototype

Removal of aromatic compounds from a variety of hydrocarbon distillates (e.g., fuel for engine, diesel fuel, oil, raw materials, etc. can be difficult because of the wide range of possible mixtures of monocyclic and polycyclic aromatic compounds. Although dearomatization may require significant capitalstream for most of the treatment plants, it can also provide additional benefits. The content of distillate aromatic compounds is complex relationships with a cetane number - the main indicator of the quality of diesel fuel. Cetane number is highly dependent on the ultimacy and saturation of the hydrocarbon molecules and t is Auda whether they are molecules with a straight chain or have alkyl side chains, attached to the rings. Distillate stream containing mainly aromatic molecules with multiple alkyl side chains or without them, usually has a low cetane number, whereas a highly saturated flow usually has a high cetane number. The quality of fuel for engines also depends on a low content of aromatic compounds due to the ratio of aromatic compound/the maximum height mecoptera flame. Most fuels for engines are limited to the requirements of technical documentation aromatic content of 25 vol.% (max).

The increased demand for more paraffin distillates is also the result of environmental requirements. Dearomatization is of growing importance due to government legislation, which requires significant decrease in the content of aromatic compounds in the distillate and polynuclear aromatic compounds. Modern requirements of the U.S. environmental protection fuel limit the content of aromatic compounds in diesel fuel up to a maximum of 35 vol.%. Technical requirements California diesel fuel accounts for a maximum of 10%vol.

Many parts of the world are subjected to a phenomenon called the "dieselization", which refers to took the structure ratio requirements for diesel fuel/gasoline fuel, together with the General increase in fuel requirements. It is expected that global demand for diesel fuel will double between 2000 and 2010, to a certain extent in response to economic growth, efforts to combat global warming and General requirements for fuel efficiency. One approach to meeting these requirements is to shift to the use of poor quality fuel for automotive diesel fuel. This leads to an increased need for desulphurization and dearomatization.

However, the need for more wax distillates leads to more stringent reaction conditions for traditional metal hydrogenation catalyst, such as cobalt, molybdenum, Nickel and tungsten. In recent years, the use of mixtures of noble metals on the carrier or the zeolite gives the receiving highly active catalyst dearomatization.

U.S. patent 5151172 (Kukes et al.) considering the way hydrogenation distillate of crude oil over a catalyst containing a combination of palladium and platinum on zeolite (i.e. mordenite) media.

U.S. patent 5147526 (Kukes et al.) considering the way hydrogenation distillate of crude oil over a catalyst containing a combination of palladium and platinum on a carrier of zeolite Y with about 1.5 to 8.0% by weight. sodium.

U.S. patent 5346612 (Kukes et al.) considering the way ispolzuya the combination of palladium and platinum on a beta-zeolite media.

U.S. patent 5451312 (Apelian et al.) considering platinum and palladium on mesoporous crystalline media MSM-41. The use of mesoporous media provides advantages of reduced mass transfer limitations compared to a system with much larger pores. However, although mesoporous media provides the best molecular access compared to zeolite system, crystalline mesoporous material, however, imposes limitations due to the lack of interconnectivity of the pores. In addition, only minor changes in the composition of the oxide used in crystalline mesoporous media, is possible without disturbing the crystalline structure of the media.

Therefore, there is a need in mesoporous catalytic system, which provides system vysokostoimostnyh mesopores having a pore size that is selected within a wide range, and having greater flexibility in the choice of the inorganic oxide component of the structure.

Brief description of the invention

There is provided a method of hydrogenation of the incoming hydrocarbon stream containing unsaturated components. The method includes creating a catalyst comprising at least one metal of group VIII on non-crystalline mesoporous inorganic oxide carrier having at least 97% EOI is movazaneh mesopores in relation to the mesopores and micropores, surface area by BET method (Bruner - Emmett - teller) at least 300 m²/g and a pore volume of at least 0.3 cm³/g; the interaction of the incoming hydrocarbon stream with hydrogen in the presence of the specified catalyst at reaction conditions of the hydrogenation.

The present invention provides mesoporous catalytic system, which provides system vysokostoimostnyh mesopores having a pore size that is selected within a wide range and which has greater flexibility in the choice of the inorganic oxide component of the structure. In addition, the system of the invention provides a dispersion of zeolite in the mesoporous matrix, which greatly improves access to the crystalline zeolite.

A detailed description of the preferred option (options)

This invention provides a method of saturation (hydrogenation) of distillate hydrocarbon oil containing aromatics and/or olefins, with a catalyst comprising one or more noble metals on the catalyst carrier, which reduces the content of unsaturated components in the raw oil product.

Although other oil threads can benefit from the present invention, the preferred distillate hydrocarbon of petroleum is the ukta, processed in the present invention, can be any flow of oil, boiling in the range of from about 150°F (66°C) up to about 700°F (371°C), preferably from about 300°F (149°C) up to about 700°F (371°C) and more preferably from about 350°F (177°C) to about 700°F (371°C).

A feature of the present invention is the ability to process a hydrocarbon oil having an aromatic content of more than 20 wt.%, more than 50 wt.%, more than 70 wt.%, even up to 80 wt.%.

Distillate hydrocarbon oil may contain solid distillates with high and low sulfur content derived from crude oil with high and low sulphur, coking distillate, light and heavy oil catalytic cracking distillates light cracking and products boiling range distillate hydrocracking, hydrobromide FCC or TCC nutrition and other ways of hydrobromide. Usually light and heavy oil catalytic cycle are the most reference to ha components of the raw oil product, which is in the range of 80 wt.% (FIA). A large part of the aromatic cyclic compounds of petroleum products is a monoaromatic compounds and diaromatics connection with present small part triaromatic soy is ineni.

Raw materials, such as solid distillates with high and low sulfur content, has a low content of aromatic compounds present in the range of up to 20 wt.% aromatics (FIA). Typically, the content of aromatic compounds combined raw oil for a method of hydrogenation is in the range from about 5 wt.% to about 80 wt.%, more typically from about 10 wt.% to about 70 wt.% and, most typically, from about 20 wt.% to about 60 wt.%. In the device hydrogenation distillate is usually more appropriate to process the raw oil products to the highest aromaticity such catalytic methods have often given equilibrium concentration of aromatic compounds product at a relatively low flow rate.

The concentration of sulfur distillate hydrocarbon oil is typically a function of crude oil a mixture of high and low sulfur content, performance hydrobromide refining mounting on a barrel of crude oil and alternative dispositions of the components of the raw distillate oil. Components of the raw distillate oil with high sulfur content are usually coking distillate, the distillate light cracking and recycled products catalyti the definition of cracking. These components raw distillate oil product may have a total nitrogen concentration in the range up to 2000 hours/million, but is usually in the range of from about 5 o'clock/m to 900 hours/million

Especially preferred feedstock oil for the present invention are hydrocarbon fractions in the fuel for engines and diesel fuel with a boiling range of 150-400°C. Typical aromatic compounds contained in the raw oil products include monoaromatic compounds, diaromatics connection and triaromatic connections, especially connections, normally boiling below about 343°C. examples of the aromatic compounds contained in the raw oil products include monoaromatic compounds, such as alkyl benzenes, indāni/tetraline and deafeningly, diaromatics compounds such as naphthalenes, biphenyls and fluorine, and triaromatic compounds such as phenanthrenes and deffenatley. Although raw oil containing a substantial proportion of polyaromatic compounds are preferred (i.e. up to 100 wt.% all aromatic compounds in such commodities petroleum products may consist of polyaromatic compounds), usually recyclable raw oil product of the present invention contains a significant portion of monoaromatic compounds and relates what the super small proportion of polyaromatic compounds. The content of monoaromatic compounds all aromatic compounds in the raw material oil is usually more than 50 wt.%. For use here a typical hydrocarbon distillate fractions or mixtures thereof containing at least 10 vol.% aromatic hydrocarbon compounds. Most vysokoproizvoditelnykh raw product processed in the present invention, is a diesel fuel containing at least 10, and often at least 20, and usually more than 30% vol. compounds containing aromatic compounds, with typical intervals of about 10 to about 80, and often about 20-50 vol.%. The maximum benefit of the method of the present invention is achieved when a high concentration of aromatic compounds in the raw oil saturated without significant cracking homozygocity aromatic compounds.

Another preferred raw oil product comprises hydrocarbons viscosity of the lubricant. The enrichment method can be carried out with mineral oil lubricants or synthetic hydrocarbon lubricants, examples of which include poly-alpha-olefin ("RAO", "PSC") materials as the traditional type of PJSC, obtained using the catalysts of Ziegler-Natta and HVI-PAO materials obtained from use of the cation of the catalyst recovered from a metal oxide of group VIB (Cr, Mo, W).

Mineral oil lubricants can usually be characterized as having a minimum boiling point of at least 650°F (343°C); and usually they are neutral, i.e. the distillate material with a 95% boiling not higher than 1050°F (566°C), although other oil products, such as high viscosity cylinder oil, can also be treated the same catalytic way. Mineral oil lubricants of this type historically receive the traditional way of apteekista, including atmospheric and vacuum distillation of a crude mixture of suitable composition with subsequent removal of undesirable aromatic components by solvent extraction using a solvent such as phenol, furfural or N,N-dimethylformamide ("DMF", "DMF"). Deparafineerimine to the desired temperature fluidity of the product can be made either by way of deparaffinize solvent, either way catalytic deparaffinize (or their combination), and, particularly preferably, hydrogenation processing according to the present invention must follow any catalytic deparaffinize processing in order to saturate the olefins boiling in the lube oil range, which can be obtained through a method of catalytic deparaffinize.

Mineral oil is E. lubricants can also be obtained by catalytic hydrocracking, in which neprevyshenie high-boiling hydrocarbon stream serves as a waxy oil base. After hydrocracking the oil product is then subjected to deparaffinizing and geroudet with the regulation of turnover and a decrease in the content of olefins and possible aromatic compounds. This method, commonly called "oil hydrocracking", often used when the raw product is inadequate for traditional oil processing or when you want HVI oil product.

This method is also applicable for hydrogenation treatment of synthetic lubricating oils, particularly poly-alpha-olefins (PAO), including materials such as HVI-PAO. These types of lubricants may be obtained by polymerization or oligomerization using catalysts of the Ziegler-Natta, such as aluminiumchlorid, mortified or nortryptaline complexes, for example, water, lower alkanols or esters traditional way. The oligomers of the type of HVI-PAO can be obtained by methods described in U.S. patent 4827064 or 4827073 using the catalyst recovered from a metal oxide of group VIB, usually chromium on silica. Materials such as HVI-PAO include high-molecular variants obtained using low temperature oligomerization, karasmontana in U.S. patent 5012020. Materials such as HVI-PAO characterized by the degree of branching below is 0.19, which is the result of a unique catalyst recovered from the metal oxide in the course of the method of oligomerization.

Lubricants are subjected to hydrogenation treatment in the presence of a catalyst which contains a metal component for hydrogenation with mesoporous material of the invention and, optionally, a binder.

The hydrogenation reaction is carried out at conventional temperatures from about 100°F to about 700°F and preferably in the range of 150-500°F. Hydrogen is usually in the conditions above atmospheric, and the partial pressure of hydrogen may vary up to about 2500 psi, but usually from about 100 to 1500 psig. The circulation rate of hydrogen is usually exceed the speed required stoichiometrically for complete saturation in the range from 200% to 5000% stoichiometric excess. Once the circulation is preferred in order to maximize the purity of the hydrogen. Flow rate are usually in the range of 0.1 to 10 CASE (LHSV) (hourly volumetric rate of fluid)is usually from 1 to 3 CHOSE. The products of the hydrogenation reaction has a low degree of ninasimone in accordance with the hydrogenation treatment. In most cases, hydrocarbon mA is lanoe food, having a bromine number more than 5, may be processed in accordance with the method of the invention to obtain a product having a bromine number less than 3 and often less than 1.

When a specific device hydrobromide works with the implementation of the two-stage method, the first stage is often designed for desulphurization and denitration, and the second stage is designed to dearomatization. At these stages of commodity petroleum products coming on stage aromatization, have essentially lower content of nitrogen and sulfur and may have a lower aromatic content than the raw products transported in the device hydrobromide.

The method of hydrogenation of the present invention typically begins with the pre-heating of the raw distillate oil. Raw oil is preheated in heat exchangers supply/output stream before entering the furnace for final heating to a predetermined temperature at the inlet of the reaction zone. Raw oil can interact with the hydrogen stream before, during and/or after pre-heating. The hydrogen-containing stream can also be introduced into the reaction zone of the single-stage hydrogenation method of hydrogenation or on the first or second stage of the two-stage method is hydrogenation.

The hydrogen stream may be pure hydrogen or can be hydrogen mixed with diluents such as hydrocarbons, carbon monoxide, carbon dioxide, nitrogen, water, sulfur compounds and the like, the Purity of the hydrogen stream should be at least about 50 vol.% hydrogen, preferably at least about 65% hydrogen and, more preferably at least about 75 vol.% hydrogen for best results. Hydrogen can be made from the installation of hydrogen from catalytic reforming or by other methods of producing hydrogen.

The reaction zone may consist of one or more reactors fixed bed containing the same or different catalysts. Two-stage methods can be provided with at least one reactor with a fixed bed desulfurization and denitrogenation and at least one reactor with a fixed bed for dearomatization. The reactor with a porous layer often contains many catalytic layers. Optional stream coming from one fixed layer may be cooled before it is routed to the next stationary layer. Many catalytic layers in a single reactor with a porous layer may also contain the same or different catalysts. When in multilayer reactor with a fixed bed the catalysts are different, the initial layer or layers are usually for desulphurization and denitrogenation, and subsequent layers to dearomatization. When used mnogofaktornaya system, marraccini gas is hot Stripping for removal of H₂S and NH₃. These gases are the product of the first stage can trigger a reaction inhibition and, more importantly, can poison the noble metal (metals) on the catalyst dearomatization.

Since the hydrogenation reaction is usually exothermic, can be used miladina cooling by introducing hydrogen. Can be used in other ways, including miscegeny heat transfer. Two-stage methods can provide reduced exothermic temperature rise in the reactor vessel and provide better temperature control of the entire reactor is important for safety and optimum efficiency and durability of the catalyst.

The stream exiting the reaction zone is usually cooled, and the output stream is sent to a separator device for removing hydrogen. One of its example is an amine scrubber. H₂S sent to the sulfur plant, and NH₃often collected as a by-product of neftochimik. Part of the recycled hydrogen can retsiklirovaniya back in the way, then as part of the hydrogen may be supplied to the other installation of hydrobromide, less demanding in terms of quality (for example, pre-heaters naphtha) or be blown into the external system, such as the installation of clean fuel. The speed of the purge hydrogen is often regulated to maintain a minimum purity of hydrogen and removal of hydrogen sulfide. Recycled hydrogen is usually compressed in the compressor, add fresh hydrogen and re-introducing the way for further hydrogenation. One preferred strategy is the use of low hydrogen purity is on its way back to the installation cycle of hydrogen, where the absorber removes many of the upper stream of hydrogen installation of hydrogen.

The liquid emerging from the separator device can then be processed in desorber, where light hydrocarbons can be removed and sent to a more appropriate reservoirs of hydrocarbons. The liquid coming out of desorber, then usually sent to a mixing device to obtain the final distillate products.

The operating conditions used at the stage of hydrobromide of the present invention include high temperature reaction zone of from about 300°F (150°C) to about 750°F (400°C), preferably from about 500°F (260°C) up to about 650°F (343°C) and, most preferably, from about 525°F (275°C) to about 625°F (330°C) for best results. Temperature d is klonoa zone below the specified ranges can provide a less effective hydrogenation. Excessively high temperatures can lead to the achievement method of thermodynamic limit of reducing the content of aromatic compounds, non-selective hydrocracking equipment, deactivation of the catalyst and increased energy costs.

The method of the present invention is usually carried out at a partial pressure of hydrogen in the reaction zone in the range of from about 200 psi to about 2000 psi, more preferably from about 500 psi to about 1500 psi, and most preferably, from about 600 psi to about 1200 psi for best results. The circulation rate of hydrogen are typically in the range from about 500 standsout/bbl to about 20,000 standsout/bbl, preferably from about 2000 standsout/bbl to about 15000 standsout/barrel and, most preferably, from about 3000 standsout/ bbl to about 13000 standsout/barrel for best results. Pressure of the reaction and the speed of circulation below the specified ranges can lead to a higher rate of deactivation of the catalyst, but also less efficient desulphurization, denitration and dearomatization. Excessively high pressure reactions increase the cost of energy and equipment, and provide insignificant advantages.

Excessive flow rate can lead to a reduced total hydrogenation.

The carrier of the catalyst, designated as TUD-1 is a three-dimensional non-crystalline mesoporous inorganic oxide material containing at least 97% interconnected mesopores (i.e., not more than 3 vol.% micropores) in relation to the micropores and mesopores organic oxide material, and typically at least 98 vol.% the mesopores. The preferred method of obtaining porous catalyst carrier described in U.S. patent No. 6358486 and the patent application U.S. serial No. 10/764797 dated 26 January 2004 ("the Method of obtaining a mesoporous or combined mesoporous and microporous inorganic oxides"), both of which are cited here as reference. The average size of the mesopores of the preferred catalyst, as defined by N₂-parametria, is in the range from about 2 nm to about 25 nm. Usually mesoporous inorganic oxide receive when heated (1) predecessor reorga the systematic oxide in water and (2) an organic blowing agent at a certain temperature for a certain period of time.

The source material is generally amorphous material and may consist of one or more inorganic oxides such as silicon oxide or aluminum oxide with or without additional metal oxides. The silicon atoms may be partially substituted by metal atoms such as aluminum, titanium, vanadium, strontium, gallium, manganese, zinc, chromium, molybdenum, Nickel, cobalt, iron, etc. Preferably, the inorganic oxide selected from the group consisting of silica, alumina, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide and combinations thereof. Additional metals may be optionally introduced into the material prior to initiation of the method of obtaining a structure that contains mesopores. After the material cations in the system can be optionally replaced by other ions such as ions of an alkali metal (e.g. sodium, potassium, lithium etc). Alkaline cations can chitravati any residual acidity that is present in the TUD-1, especially in the form of Al-TUD-1 or Al-Si-TUD-1. Residual acidity may cause unwanted reactions of cracking and therefore reduce the total yield of liquid product.

Mesoporous catalyst carrier is a non-crystalline product (i.e., the crystallinity is not observed currently available x-ray method). Size d mesop the R is, preferably, from about 3 nm to about 30 nm. The surface area of the catalyst carrier, as determined by BET method (N₂), is at least about 300 m²/g and is preferably in the range of from about 400 m²/g to about 1200 m²/g pore Volume of the catalyst is at least about 0.3 cm³/g and is preferably in the range of from about 0.4 cm³/g to about 2.2 cm³/year

There are many ways to obtain a catalyst carrier TUD-1, but these ways can be classified into two types, depending on the source materials of inorganic oxides: (1) precursor containing organic compounds, and (2) inorganic precursors. In the first case, the precursor of the inorganic oxide may be preferably an alcoholate having the desirable elements selected from silicon, aluminum, titanium, vanadium, zirconium, gallium, manganese, zinc, chromium, molybdenum, Nickel, cobalt and iron, for example, an organic silicate, such as tetraethylorthosilicate (TEOS, TEOS), or an organic source of aluminum oxide, such as aluminiumprofile. TEOS, aluminiumprofile are commercially available from known suppliers.

the pH of the solution preferably is maintained above a 7.0. Optionally, the aqueous solution may contain IO is s other metals, such as described above. After stirring an organic agent, forming mesopores, which is connected with particles of silica (or other inorganic oxide) hydrogen bond, is introduced and mixed with the aqueous solution. Organic blowing agent is preferably a glycol (a compound that has two or more hydroxyl groups such as glycerin, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, etc. or representative (s) of the group consisting of triethanolamine, sulfolane, Tetraethylenepentamine and diethylaminobenzoate. Organic blowing agent should not be hydrophobic to form a separate phase in the aqueous solution, and preferably is introduced dropwise with stirring an aqueous solution of an inorganic oxide. After a certain period of time (for example, from about 1 to 2 hours) the mixture forms a thick gel. The mixture is preferably stirred for a specified period of time to facilitate mixing of the components. The mixture preferably includes alkanol, which can be added to the mixture and/or formed in place by the decomposition of the precursor of the inorganic oxide. For example, TEOS when heated gives ethanol. Propanol can be obtained by the decomposition of aluminum-isopropylate.

The second type of path SinTe is and getting the same gel is the use of inorganic precursors as starting materials. Preferred inorganic precursors contain oxides and/or hydroxides having desirable elements selected from silicon, aluminum, titanium, vanadium, zirconium, gallium, manganese, zinc, chromium, molybdenum, Nickel, cobalt and iron. The first precursor is mixed with one or more pore-formers and heated to 120-250°C for a certain period of time, for example 2 to 10 hours, sufficient for the conversion of the inorganic precursor in complexes containing organic compounds. The complexes are then mixed with water for hydrolysis and obtain a homogeneous thick gel.

The gel obtained with the two methods described above, then incubated at a temperature from about 5°to about 45°C, preferably at room temperature, with the implementation of hydrolysis and polycondensation source of inorganic oxide. Maturation, preferably, can take place for up to 48 hours, usually from about 2 h to 30 h, more preferably from about 10 h to 20 h After the stage of maturation of the gel is heated in air at about 90-100°C for a period of time sufficient for drying gel water removal (for example, from about 6 to about 24 hours). Preferably, the organic blowing agent which promotes the formation of mesopores, must remain in the gel during the stage of drying. Sootvetstvenno is, preferred organic blowing agent has a boiling point of at least about 150°C.

The dried material, which still contains organic blowing agent is heated to a temperature at which there is a significant formation of mesopores. Stage steam formation is carried out at a temperature above the boiling point of water and up to about the boiling point of the organic blowing agent. Typically, the formation of mesopores is carried out at a temperature of from about 100°C to about 250°C, preferably from about 150°C to about 200°C. stage of steam formation can, optionally, be hydrothermal in a sealed vessel under autogenous pressure. The size of the mesopores and the volume of mesopores in the final product is influenced by the duration and temperature of the hydrothermal stage. Typically, the increase in temperature and duration of treatment increases the percentage of the volume of mesopores in the final product.

After the stage of steam formation of the catalytic material is calcined at a temperature of from about 300°C to about 1000°C, preferably from about 400°C to about 700°C, more preferably from about 500°C to about 600°C and maintained at a temperature of calcination for a period of time sufficient to effect the calcination of the material. The duration with the adiya's calcination is typically in the range of from about 2 hours to about 40 hours, preferably 5-15 hours, depending, in particular, on the temperature of annealing.

To prevent the formation of hot zones, the temperature should be increased gradually. Preferably, the temperature of the catalytic material should be increased to a temperature of calcination at a speed ranging from about 0.1°C/min to approximately 25°C/min, more preferably from about 0.5°C/min to about 15°C/min, and most preferably, from about 1°C/min to about 5°C/min

In the process of annealing the structure of the catalytic material is formed finally, when organic molecules are removed from the material and decompose.

The method of calcination to remove the organic pore-forming may be replaced by extraction using organic solvents, for example ethanol. In this case, the blowing agent can be regenerated for reuse.

In addition, the powder of the catalyst of the present invention can be mixed with a binder, such as silica and/or alumina, and then molded into the desired shape (such as pellets, rings, etc.) extrusion, or other suitable methods.

The catalyst includes at least one metal component selected from group VIII of the periodic system of elements, which includes iron, cobalt, Nickel and noble meta the crystals, for example, platinum, palladium, ruthenium, rhodium, osmium and iridium. Particularly preferred metals include platinum, palladium, rhodium, iridium and Nickel. The amount of metal of group VIII is at least about 0.1 wt.% in relation to the total weight of the catalyst.

The metal of group VIII can be introduced into the mesoporous inorganic oxide by any suitable means, such as ion exchange or impregnation of inorganic oxide with a solution of soluble degradable compound of metal of group VIII, and then washing, drying and processing of the impregnated inorganic oxide such manner as the calcination decomposition compounds of the metal of group VIII, which results in the activated catalyst having the free metal of group VIII in the pores of the inorganic oxide. Suitable compounds of metals of group VIII include salts such as nitrates, chlorides, ammonium complexes, etc.

Washing of the catalyst on the basis of inorganic oxide impregnated with a metal of group VIII, optionally, is water with removing some of the anions. Drying of the catalyst to remove water and/or other volatile compounds can be performed by heating the catalyst up to drying temperature from about 50°C to about 190°C. the Annealing with the activation of the catalyst can be carried out at a temperature of from about 150°C is about 600°C for a sufficient period of time. Typically, the calcination can be carried out within 2-40 h based at least in part on the temperature of annealing.

Optionally, one or more zeolites can be introduced into the catalyst and dispersed in the mesoporous matrix. The zeolite is preferably introduced in an aqueous solution of the precursor of the inorganic oxide before the formation of the mesoporous structure. Suitable zeolites include, for example, FAU, EMT, BEA, VFI, AET and/or CLO. The zeolite is preferably present in amounts of 0.05-50 wt.% in relation to the total weight of the catalyst.

Another preferred type of hydrogenation involves the removal of impurities from food containing hydrocarbons. More specifically, it relates to a method for selective hydrogenation of compounds containing a triple bond, and/or compounds having two or more double bonds, as opposed to connection with a single double bond, and selective hydrogenation of compounds having two adjacent double bonds, in contrast to compounds where the two double bonds are separated by one or more single bonds.

Such reactions include, but are not limited to) selective hydrogenation of acetylene and/or diene impurities in the feed, containing at least one monoolefins. Other examples are selective hydrogenation of acetylene in ethyl the new thread selective hydrogenation of methylacetylene and PROPADIENE in propylene flow, selective hydrogenation of butadiene in butenova flow and selective hydrogenation of vinyl - and ETHYLACETYLENE and 1,2-butadiene in the feed, containing 1,3-butadiene.

In the petrochemical industry recyclable streams contain one or more monoolefins, and as impurities contain acetylene and/or diene compounds. Acetylene impurities include acetylene, methylacetylene and diacetylene. Diene impurities include 1,2-butadiene, 1,3-butadiene and PROPADIENE.

This thread is typically subjected to selective hydrogenation to minimize maintenance/removal of acetylene and/or diene impurities without hydrogenation desired monoolefins. This method can be carried out selective catalytic hydrogenation using a catalyst.

The specified catalyst contains a metal, preferably a noble metal deposited on the mesoporous material of the invention, and, optionally, a binder. The specified catalyst may also contain additional metals used as promoters.

Selective hydrogenation of acetylene and/or diene impurities is the one-stage hydrogenation in the presence of the catalyst described above. The power is injected in liquid form and can the t partially or completely evaporate in the process of hydrogenation. The food must be selectively hydrogencarbonates, and the flow of hydrogen gas is introduced into the reactor at a temperature of from about 0°C to 50°C. the Reactor operates at a pressure in the range of from 200 psi to 500 psi. Depending on the level of acetylene and/or diene impurities in the feed, the temperature at the inlet and allow the temperature on the release may be necessary to recycle portion of the product in the reaction zone.

The amount of hydrogen that is introduced into the reactor, based on the number of impurities in the diet. The hydrogen may be injected into the reactor with a suitable diluent, such as methane.

Should be used a suitable volumetric hourly rate of the liquid, which should be obvious to a person skilled in this technical field.

The following examples illustrate features of the invention.

Example 1

This example shows the method for the synthesis of Si-TUD-1 using an alcoholate of silicon as the source of silicon oxide. 736 parts by weight of tetraethylorthosilicate (98%, ACROS) is mixed with 540 parts by weight of triethanolamine (tea) (97%, ACROS) with stirring. After half an hour in this mixture slowly with stirring 590 parts by weight of water. After another half-hour in specified mixture of 145 parts by weight of tetraethylorthosilicate (THEON) (35 wt.%) to obtain a homogeneous gel. The gel is incubated at room temperature T. the value of 24 hours Then the gel is dried at about 98°C for 18 h and calcined at 600°C in air for 10 h with a heating rate of 1°C/min

The x-ray target material shows an intense 2 θ pic < 2°, indicating the mesoporous structure. Measurement by the BET method using nitrogen adsorption shows the surface area of 683 m²/g, an average pore diameter of about 4.0 nm and a total pore volume of about 0.7 cm³/year

Example 2

This example shows the method for the synthesis of Si-TUD-1 with the use of silica gel as a source of silicon oxide. First, 24 parts by weight of silica gel, 76 parts by weight of the tea and 62 parts by weight of ethylene glycol (EG, EG) is loaded into a reactor equipped with a condenser. After the reactor is thoroughly mixed with a mechanical stirrer, the mixture is heated to 200-210°C under stirring. In this mode removes most of the water formed in the reaction, together with a small part of the EEG from the top of the condenser. Meanwhile, a large part of the EG and the tea remains in the reaction mixture. After about 8 h heating cease and slightly brown keeptool complex fluid is collected after cooling to room temperature.

Secondly, 100 parts by weight of water is added under conditions of stirring to 125 parts by weight of a complex liquid obtained as described above. After one hour re is eshiwani the mixture forms a thick gel, the gel is incubated at room temperature for 2 days.

Thirdly, the thick gel is dried at 98°C for 23 h, then loaded into an autoclave and heated to 180°C for 6 hours Finally calcined at 600°C in air for 10 h with a heating rate of 1°C/min

The x-ray target material shows an intense 2 θ pic < 2°, indicating the mesoporous structure. Measurement by the BET method using nitrogen adsorption shows the surface area of 556 m²/g, an average pore diameter of approximately 8.1 nm and a total pore volume of about 0,92 cm³/year

Example 3

This example shows the synthesis of Al-Si-TUD-1. First, 250 parts by weight of silica gel, 697 parts by weight of the tea and 287 parts by weight of ethylene glycol (EG) is loaded into a reactor equipped with a condenser. After the reactor is thoroughly mixed with a mechanical stirrer, the mixture is heated to 200-210°C under stirring. In this mode removes most of the water formed in the reaction, together with a small part of the EEG from the top of the condenser. Meanwhile, a large part of the EG and the tea remains in the reaction mixture. After about 3 hours the reactor is cooled to 100°C, and the reactor is introduced, another mixture containing 237 parts by weight of aluminum hydroxide, 207 g of ethylene glycol and 500 g of tea. The mixture is again heated to 200-210°C and after 4 h, the heating is stopped. Lightly brown cliptobounds liquid is collected after cooling to room temperature.

Secondly, 760 parts by weight of water and 350 parts by weight of tetraethylammonium add in terms of mixing to complex liquid obtained as described above. After one hour of stirring the mixture forms a thick gel, the gel is incubated at room temperature for 1 day.

Thirdly, the thick gel is dried at 98°C for 23 h, then loaded into an autoclave and heated to 180°C for 16 hours Finally calcined at 600°C in air for 10 h with a heating rate of 1°C/min

The x-ray target material shows an intense 2 θ pic < 2°, indicating the mesoporous structure. Measurement by the BET method using nitrogen adsorption shows the surface area of 606 m²/g, an average pore diameter of approximately 6,0 nm and a total pore volume of about 0,78 cm³/year

Example 4

This example shows obtaining a catalyst of 0.90 wt.% iridium/Si-TUD-1 with initial moisture content. 0,134 parts by weight of iridium(III)chloride is dissolved in 5.2 parts by weight of deionized water. This solution is added to 8 parts by weight of Si-TUD-1 obtained in example 1, with mixing. The powder is dried at 25°C.

To determine the dispersion using a CO-chemisorption powder then restore in a stream of hydrogen at 100°C for 1 h followed by heating to 350°C at 5°C/min and maintained at this temperature for 2 hours WITH heh who Varbla shows 75% dispersion of metal, assuming stoichiometry Ir:CO 1.

Example 5

This example shows getting a catalyst to 0.9 wt.% palladium/0.3 wt.% platinum /Si-TUD-1 with initial moisture content. First ekstragiruyut Al-Si-TUD-1 obtained in example 3. Then 70 parts by weight of 1/16 inch extrudates impregnated with an aqueous solution, containing 0.42 parts by weight of tetraammineplatinum, and 12.5 parts by weight of an aqueous solution of tetraammineplatinum (5% Pd) and 45 parts by weight of water. Impregnated Al-Si-TUD-1 incubated at room temperature for 6 h before drying at 90°C for 2 hours the Dried material is finally calcined in air at 350°C for 4 h with a heating rate of 1°C/min the Dispersion of the noble metal is determined using CO-chemisorption, the powder then restore in a stream of hydrogen at 100°C for 1 h followed by heating to 350°C at 5°C/min and maintained at this temperature for 2 hours Determine 51% of the variance metal, suggesting a stoichiometry of Pt:CO 1.

Example 6

This example shows the receipt of the catalyst and 0.46 wt.% platinum/Si-TUD-1 with initial moisture content. 0,046 parts by weight of tetraammineplatinum(II)nitrate is dissolved in 4.1 parts by weight of deionized water. This solution is added to 5 parts by weight of Si-TUD-1 obtained in example 1, with mixing. The powder is dried at 25°C.

To determine the dispersion using a CO-chemisorption powder is then to restore the flow of hydrogen at 100°C for 1 h followed by heating to 350°C at 5°C/min and maintained at this temperature for 2 hours Identify 72% of the variance for the sample, suggesting a stoichiometry of Pt:CO 1.

Example 7

21 parts by weight of Si-TUD-1 obtained in example 1 are suspended in deionized water, pH adjusted to 2.5 by the addition of nitric acid. The exchange should be performed within 5 hours the Solution is then dehydrated. Si-TUD-1 and then washed 5 times with deionized water. This Si-TUD-1 are then placed in 600 parts by weight of deionized water, the pH of this solution is adjusted to 9.5 using ammonium nitrate. This exchange is performed within 1 h In the course of this exchange, the ammonium nitrate was added when necessary to maintain the pH at 9.5. After an exchange of Si-TUD-1 is washed 5 times with deionized water. Then Si-TUD-1 is dried at 25°C. using the specified treated with acid/alkali Si-TUD-1 of tetraamminepalladium(II)nitrate initial humidity get to 0.50 wt.% palladium/Si-TUD-1. 0,071 parts by weight of palladium salt is dissolved in 4.1 parts by weight of deionized water. This solution is added to 5 parts by weight of Si-TUD-1 with mixing. The powder is dried at 25°C. the Powder catalyst was then calcined in air at 350°C for 2 h using a heating rate of 1°C/min

To determine the dispersion using a CO-chemisorption calcined powder is then restored in a stream of hydrogen at 100°C for 1 h followed by heating to 350°C at 5°C/min and from the side at this temperature for 2 hours Identify 96% of the variance of the sample, suggesting a stoichiometry of Pd:CO 1.

Example 8

This example shows the receipt of 0.25 wt.% palladium/Si-TUD-1 with processed using acid/alkali TUD-1 (example 7) from tetraamminepalladium(II)nitrate initial moisture content. a 0.035 parts by weight of palladium salt is dissolved in 3.9 parts by weight of deionized water. This solution is added to 5 parts by weight of Si-TUD-1 with mixing. The powder is dried at 25°C. the Powder catalyst was then calcined in air at 350°C for 2 h using a heating rate of 1°C/min

To determine the dispersion using a CO-chemisorption calcined powder is then restored in a stream of hydrogen at 100°C for 1 h followed by heating to 350°C at 5°C/min and maintained at this temperature for 2 hours Determine 90% of the variance of the sample, suggesting a stoichiometry of Pd:CO 1.

Example 9

The catalyst of 0.38 wt.% palladium/0.23 wt.% platinum/Si-TUD-1 was obtained as follows. of 0.38 wt.% palladium/TUD-1 is obtained using the treated acid/alkali Si-TUD-1 (example 7) from tetraamminepalladium(II)nitrate initial moisture content. 0,053 parts by weight of palladium salts dissolve 3.75 parts by weight of deionized water. This solution is added to 5 parts by weight of Si-TUD-1 with mixing. The powder is dried at 25°C. the Powder catalyst was then calcined in air at 350°C in ECENA 2 h using a heating rate of 1°C/min

Impregnation of this catalyst to 0.23 wt.% platinum is obtained from tetraammineplatinum(II)nitrate initial moisture content. 0,018 parts by weight of platinum salt is dissolved 3.25 parts by weight of deionized water. This solution is added to as 4.02 parts by weight of 0.38 wt.% Pd/Si-TUD-1 with mixing. The powder is dried at 25°C.

To determine the dispersion using a CO-chemisorption calcined powder is then restored in a stream of hydrogen at 100°C for 1 h followed by heating to 350°C at 5°C/min and maintained at this temperature for 2 hours Identify 81% of the variance of the sample, suggesting a stoichiometry of Pd:CO and Pt:1.

Example 10

The catalyst to 0.19 wt.% palladium/0.11 wt.% platinum/Si-TUD-1 was obtained as follows. to 0.19 wt.% palladium/Si-TUD-1 is obtained using the treated acid/alkali Si-TUD-1 (example 7) from tetraamminepalladium(II)nitrate initial moisture content. 0,027 parts by weight of palladium salts dissolved in 3.5 parts by weight of deionized water. This solution is added to 5 parts by weight of Si-TUD-1 with mixing. The powder is dried at 25°C. the Powder catalyst was then calcined in air at 350°C for 2 h using a heating rate of 1°C/min

Impregnation of this catalyst 0.11 wt.% platinum is obtained from tetraammineplatinum(II)nitrate initial moisture content. 0,009 parts by weight of platinum salts dissolved in 3,27 parts by weight of deionized water. This solution to ablaut to parts by weight of 4.05 to 0.19 wt.% Pd/Si-TUD-1 with mixing. The powder is dried at 25°C.

To determine the dispersion using a CO-chemisorption powder then restore in a stream of hydrogen at 100°C for 1 h followed by heating to 350°C at 5°C/min and maintained at this temperature for 2 hours Determine 54% of the variance of the sample, suggesting a stoichiometry of Pd:CO and Pt:1.

Example 11

Catalysts TUD-1 is estimated at 1-inch reactor with continuous power supply and compare with the industrial catalyst. Table 1 summarizes the operating conditions. Table 2 shows the properties of the power and output streams, the output of products. It is clear that the catalyst TUD-1 gives the final product, with only 5% of aromatic compounds, whereas industrial catalyst produces a product containing 10% aromatic compounds at high flow rate. The catalyst TUD-1 shows a higher activity of saturation of aromatic compounds.

FIA is a standard indicator - fluorescently absorption - which is normal with the particular ASTM D1319. This indicator shows the percentage amount of the substituted hydrocarbons, olefins and aromatic compounds.

Example 12

In this example, get the aluminium-containing TUD-1. Sixty-five (65) parts by weight of isopropanol and 85 parts by weight of ethanol is added to the vessel with 53 parts by weight of aluminiumprofile. After stirring at 50°C for about 4 h added dropwise 50 parts by weight of tetraethyleneglycol (TEG, TEG) with stirring. After stirring for another 4 h add 10 parts by weight of water together with 20 parts by weight of isopropanol and 18 parts by weight of ethanol with stirring. After half an hour, stirring the mixture becomes white suspension, which was then incubated pikantnoi temperature for 48 h and then dried in air at 70°C for 20 h to obtain a firm gel. This solid gel is heated and autoclave at 160°C for 2.5 h and finally calcined at 600°C for 6 h in air to obtain mesoporous alumina.

On the radiograph obtained calcined mesoporous alumina has an intense peak at 2 θ of 1.6°, characteristic of materials with mesostructure. Nitric porometry shows the distribution of the pore size, ostoskorissanne about 4.6 nm. Al-NMR spectroscopic measurements show three peaks, corresponding to the four, five and shestikomnatnom aluminum at 75, 35 and 0H./million respectively. In the end, he is a typical mesoporous material of the present invention with four-, five - and shestikonechnymi aluminum.

Example 13

This example shows the use of the compositions of the present invention as a carrier of a catalyst for hydrogenation. First of 3.13 parts by weight of Al-TUD-1 from example 12 ("sample 12") impregnated with 2 parts by weight of a solution of 3.1 wt.% Pt(NH₃)₄(NO₃)₂in water by the method of initial moisture. After drying and calcination in air at 350°C for 2 h was charged to the reactor 50 parts by weight of saturated sample 12, and then restore the hydrogen at 300°C for 2 hours

As a test reactions are hydrogenation of mesitylene in the reactor with a fixed bed under a total pressure of 6 bar and with the use of power concentration mesitylene of 2.2 mol.% in hydrogen. In order to determine the rate constant of the catalyst, the reaction temperature varies in the range of 100-130°C with a step of 10°C. the Modified time of the probe in relation to the mass of catalyst is kept constant at 0.6 g of catalyst × min × l^-1. Rate constant first order reactions with respect to the mass of catalyst is 0.15 (g of catalyst)^-1× min^-1× l at 100°C.

Example 14

This example illustrates the selective hydrogenation acetylenes and que is impressive. The catalyst Pd-Ag-Al-TUD-1 are in the form of 1/16 inch extrudates and crushed to a particle size of 24/36 mesh for laboratory characterization. Selective hydrogenation is carried out in a tubular reactor with an outer diameter of 0.75 inch. The diet consists of 0.8 wt.% methylacetylene, 0.3 wt.% PROPADIENE, 22 wt.% propylene, and the rest up to 100 wt.% is isobutane. Hydrogen dissolves in this hydrocarbon stream. The molar ratio of hydrogen/(methylacetylene + PROPADIENE) is about 0.75. This mixture is then sent to the reactor. Is OCSI supported at approximately 367. At the end of the reaction determine conversion and selectivity. Selectivity is defined as the obtained propylene/transformed (methylacrolein + PROPADIENE) × 100. At 49°C and 460 psi conversion of the mixture (Meilenstein + PROPADIENE) is 29%and the selectivity is 71%.

Although the above description contains many specific data, the latter should not be construed as limiting the scope of the invention, but only as illustrations of his preferred options. Specialists in the art will see many other possibilities within the scope and spirit of the invention as defined in the attached claims.

1. The method of hydrogenation of the incoming hydrocarbon stream containing unsaturated components, to the which contains:
(a) the establishment of a catalyst comprising at least one metal of group VIII on non-crystalline mesoporous inorganic oxide carrier having at least 97% interconnected mesopores in relation to the mesopores and micropores, having a surface area by BET method of at least 300 m²/g and a pore volume of at least 0.3 cm³/g; and
b) interaction of the incoming hydrocarbon stream with hydrogen in the presence of the specified catalyst in the reaction zone hydrogenation under the conditions of the hydrogenation reaction to obtain a product having a reduced content of aromatic components;
in which the conditions of the hydrogenation reaction include hourly space velocity of fluid (COSI) from approximately 0,33 h^-1to about 10.0 HR^-1and the circulation rate of hydrogen is from about 500 standsout/bbl to about 20,000 standsout/barrel.

2. The method according to claim 1, in which the metal of group VIII is a noble metal.

3. The method according to claim 2, in which a noble metal selected from the group consisting of palladium, platinum, rhodium, ruthenium and iridium.

4. The method according to claim 1, in which the metal of group VIII is Nickel.

5. The method according to claim 1, in which the metal of group VIII is the percentage of at least about 0.1 wt.% in relation to the total weight of the catalyst.

6. The method according to claim 1, in which the PR mesoporous inorganic oxide carrier has a surface area by BET method of from about 400 m ²/g to about 1200 m²/g and a pore volume from about 0.4 cm³/g to about 2.2 cm³/year

7. The method according to claim 1, in which the conditions of the hydrogenation reaction include a temperature from about 150°to about 400°C, the partial pressure of hydrogen is from about 200 psi to about 2000 psi, CHOSE from approximately 0,33 h^-1to about 10.0 HR^-1and the circulation rate of hydrogen is from about 500 standsout/bbl to about 20,000 standsout/barrel.

8. The method according to claim 1, in which the conditions of the hydrogenation reaction include a temperature from about 260°to about 343°C., the partial pressure of hydrogen is from about 500 psi to about 1500 psi, CHOSE from about 0.5 h^-1to about 3.0 HR^-1and the circulation rate of hydrogen is from about 2000 standsout/bbl to about 15000 standsout/barrel.

9. The method according to claim 1, in which the conditions of the hydrogenation reaction include a temperature from about 275°to about 330°C, the partial pressure of hydrogen is from about 600 psi to about 1200 psi, CHOSE from about 1.0 h^-1to about 2.0 HR^-1and the circulation rate of hydrogen from about 3000 standsout/bbl to about 13000 standsout/barrel.

10. The method according to claim 1, wherein the catalyst further comprises a zeolite.

11. The method according to claim 10, in which the zeolite is selected from the GRU is dust, consisting of FAU, EMT, WEAH, VFI, AET, CLO and their combinations.

12. The method according to claim 10, in which the amount of the zeolite is from approximately 0.05 wt.% to about to 50.0 wt.% in relation to the total weight of the catalyst.

13. The method according to claim 1, in which the incoming hydrocarbon stream contains oil-containing raw materials.

14. The method according to claim 1, in which the incoming hydrocarbon stream contains more than about 70 wt.% aromatic compounds.

15. The method according to claim 1, in which the incoming hydrocarbon stream contains more than about 50 wt.% aromatic compounds.

16. The method according to claim 1, in which the specified reaction the hydrogenation zone contains at least one fixed bed of catalyst.

17. The method according to clause 16, which indicated the reaction zone by hydrogenating includes at least first and second, spaced apart, fixed the catalyst layers, in which the flow coming from the first fixed layer, is diverted to the second fixed layer.

18. The method according to 17, further comprising a stage of cooling flow coming from the first fixed layer, before he comes in the second fixed layer.

19. The method according to claim 1, further comprising a stage of pre-heating the incoming stream in the heat exchanger incoming/output stream and then the heating power of the furnace to the reaction temperature.

20. the procedure according to claim 1, wherein said method comprises the hydrogenation oily incoming hydrocarbon stream having a bromine number more than 5, in the presence of hydrogen at an elevated pressure to obtain oily product having a bromine number less than 3.

21. The method according to claim 1, wherein said method comprises selective hydrogenation of acetylene and/or diene impurities in the incoming hydrocarbon stream that contains at least one monoolefins.

22. The method according to claim 1, wherein said method comprises selective hydrogenation of olefin and/or diene impurities in the incoming hydrocarbon stream that contains at least one aromatic compound.

23. The method according to item 21, in which these impurities contain acetylene and one or more compounds containing the adjacent double bond, and the specified incoming hydrocarbon stream includes a compound containing double bonds, separated by at least one single bond.