The catalyst for conversion of hydrocarbons, a method of catalytic reforming of the original naphtha using catalyst

 

(57) Abstract:

The invention relates to the refining sector, namely the catalytic reforming of the original naphtha. Describes a new catalyst and its use in hydrocarbon conversion. The catalyst contains a refractory inorganic oxide, a platinum group metal, a metal of group IVA (IUPAC 14) and europium in a certain ratio. Effect: the use of this catalyst in the conversion of hydrocarbons, particularly in the reforming process, leads to a significantly improved selectivity to the desired gasoline or aromatic product. 2 S. and 4 C.p. f-crystals, 4 Il., table 2.

The object of the present invention is a new bi-functional catalytic composite characterized by a combination of three or more metals in a certain concentration in the final catalyst and its use in the conversion of hydrocarbons. Catalysts having as a function of hydrogenation-dehydrogenization and the cracking function are widely used in many applications, especially in the oil and petrochemical industry, to accelerate a wide range of reactions in the conversion of hydrocarbons. The cracking function usually refers to substances Kitwe substrate or carrier for a heavy metal component, such as metals VIII (IUPAC 8-10) of the group, which primarily contribute to the function of hydrogenation-dehydrogenization. Other metals in a related or elemental form may affect one or both functions - the cracking and hydrogenation-dehydrogenization.

In another aspect, the present invention covers advanced techniques that originate from the application of new catalysts. These catalysts with dual function is used to accelerate a wide variety of reactions in the conversion of hydrocarbons, such as dehydrogenase, hydrogenation, hydrocracking, hydrogenolysis, isomerization, desulfurization, cyclization, alkylation, polymerization, cracking and hydroisomerization. In a specific aspect, an improved method of reforming uses considered a catalyst to improve the selectivity to gasoline and aromatic products.

Catalytic reforming process includes a number of competing processes or sequences of reactions. They include dehydrogenization of cyclohexanol to aromatic compounds, dehydroisomerization of alkylcyclopentanes to aromatic compounds, dehydrocyclization acyclic hydrocarbons to aromatic acibenzolar and isomerization of paraffins. Some reactions taking place during the reforming process such as hydrocracking, which produce light paraffin gases, have a deleterious effect on the yield of products boiling in the gasoline range. Improved methods in catalytic reforming process, therefore, is aimed at strengthening these reactions, a high yield of gasoline fraction at a given octane number.

It is particularly important that the catalysts with dual function demonstrate ability as an effective initial performance of their specific functions, and satisfactory implementation for extended periods of time. The options used in the field to measure how well a particular catalyst performs its specified function in a particular environment reactions of hydrocarbons, are activity, selectivity and stability. In the environment of reforming these parameters are defined as follows:

(1) Activity is a measure of the ability of a catalyst to convert hydrocarbon reactants to products at a given level of hardness with hardness level, the combination of a reaction conditions: temperature, pressure, time of contact and the partial pressure of the Sabbath. +") of the product from the specified stream feedstock at a given hardness level or Vice versa, as the temperature required to achieve a given octane number.

(2) Selectivity refers to the percentage of the output of petrochemical aromatic compounds or gasoline products5+from the specified stream feedstock at a particular level of activity.

(3) Stability refers to the rate of change in activity or selectivity per unit time or the processed feedstock. The stability of the activity is usually measured as the rate of change of the working temperature per unit time or the source of raw materials to achieve a desired octane number of the product5+and a lower rate of temperature change corresponds to the best stability of activity because of the catalytic reforming process typically operate at a relatively constant octane number of the product. The stability of the selectivity is measured as the rate of decrease of the yield of aromatic compounds or product5+per unit of time or of raw materials.

Programs to improve the characteristics of the reforming catalysts are stimulated perfoance to reduce harmful emissions from vehicles. Methods of refining gasoline, such as catalytic reforming process must operate at a higher efficiency with greater flexibility to meet these changing requirements. The selectivity of the catalyst becomes even more important for a given gasoline components for these requirements, at the same time avoiding loss of less valuable products. The main problem encountered specialists in this field, therefore, is the development of more selective catalysts, at the same time maintaining effective activity and stability of catalyst.

There are many multimetallic catalysts for catalytic reforming of a petroleum feedstock. Most of them includes the choice of the metals of the platinum group, rhenium and metals of group IVA (IUPAC 14).

U.S. patent US-A-3915845 discloses the conversion of hydrocarbons using a catalyst containing a platinum group metal, a metal of group IVA, halogen and lanthanide atomic ratio to the platinum group metal from 0.1 to 1.25. The preferred lanthanide is lanthanum, cerium and especially neodymium. U.S. patent US-A-4039477 discloses a catalyst for catalytic hydrobromide hydrocarbons is Oia, thorium, uranium, praseodymium, cerium, lanthanum, neodymium, samarium, dysprosium and gadolinium with favorable results observed at relatively low relationship last metal to platinum. U.S. patent US-A-5254518 discloses a catalyst containing a noble metal of group VIII, the oxide of group IVB and amorphous silica-alumina, which caused the oxide of rare earth metal, preferably Nd or y

The invention

The objective of the invention is to provide a new catalyst for improved selectivity in the conversion of hydrocarbons. The next task of the invention is to provide a method of reforming process having improved selectivity with respect to the output of gasoline or aromatics.

The invention, more specifically, proceeds from the discovery that a catalyst containing platinum, tin or europium on halogenated aluminum oxide shows a favorable attitude flavoring to cracking in the reaction of the reforming of hydrocarbons.

The main embodiment of the present invention is a catalyst containing refractory inorganic oxide, a metal of group IVA(IUPAC 14) metal of the platinum group metal of some lanthanides. Atomic unexepectedly 1.5 or more, and most preferably from 2 to 5. The catalyst in the optimal case, also preferably contains a halogen, especially chlorine. In preferred embodiments of the refractory inorganic oxide is alumina, the platinum group metal is platinum, a metal of group IVA (IUPAC 14) is tin, metal number of lanthanide selected from at least europium and ytterbium. Particularly preferred catalyst contains tin, platinum and europium, mainly in the form of EuO on the media aluminum oxide.

In another aspect the invention provides a method for the conversion of hydrocarbon feedstock using this catalyst. The preferred hydrocarbon conversion is catalytic reforming of a petroleum feedstock using a catalyst of the present invention to increase the output of gasoline and/or aromatic compounds. Conversion, more preferably, contains dehydrocyclization day to increase the yield of aromatic compounds. Optimally oil feedstock contains hydrocarbons in the range FROM6-C8that provide one or more of benzene, toluene and xylene, in the catalytic reforming process.

Brief the th raw material with the use of catalysts of the prior art and catalysts of the present invention.

Fig. 2 compares the selectivity for reforming catalysts of the prior art and catalysts of the present invention when processing oil feedstock.

Fig.3 shows the output WITH5+depending on aromatic compounds for the three Unit-containing catalysts compared to a reference catalyst containing Unit.

Fig. 4 depicts the relative activity and selectivity of S-containing catalysts as a function of the content Unit.

Description of the preferred embodiments

The main embodiment of the present invention, therefore, is the catalyst containing the medium of the refractory inorganic oxide, at least one metal of group IVA (IUPAC 14) of the Periodic table (See. Cotton and Wilkinson, Advanced Inorganic Chemistry, Jonn Wiley & Sons (Fifth edition, 1988), the platinum group metal and the metal of the number of pantaneiro.

Refractory carrier used in the present invention, is typically a porous, absorbent, with a large surface area carrier having a surface area of from 25 to 500 m2/, Porous media must also be uniform in composition and relatively refractory orca must be non-sliced, not to have a gradient of particle concentration, characteristic of its composition, and completely homogeneous in composition. Thus, if the substrate is a mixture of two or more refractory substances, the relative amount of these substances must be constant and uniform throughout the volume of the media. Intended for inclusion in the scope of the present invention the substance of the media, which are traditionally used in catalysts for conversion of hydrocarbons with double function, are the following:

(1) refractory inorganic oxides such as magnesium oxide, titanium dioxide, zirconium dioxide, chromium oxide, zinc oxide, thorium oxide, boron oxide, silica-alumina, silica-magnesia, chromium oxide-alumina, alumina-boron oxide, silica-Zirconia, and so on,

(2) ceramics, porcelain, bauxite,

(3) silica or silica gel, silicon carbide, clays and silicates, which are prepared synthetically or are in a natural way, which may or may not be treated with acid, for example, attapulgite, diatomaceous earth, mullerova earth, kaolin or diatomaceous earth,

(4) the crystalline zeolite aluminosilicates, such as X-zeobit, Y-zeolite, mordenite, zeolite, zeolite elalami, located in the cation exchange centers,

(5) neoreality molecular sieves, such as alumophosphate or aluminosilicate, and

(6) combinations of one or more compounds from one or more of these groups.

Preferably, the refractory carrier contains one or more inorganic oxides, notably alumina is a preferred refractory inorganic oxide for use in the present invention. Suitable substances aluminum oxide is crystalline aluminum oxide, known as gamma-, ETA - and tetta-alumina, with gamma - or ETA-alumina giving best results. The preferred refractory inorganic oxide will be apparent volume weight of from 0.3 to 1.0 g/cm3and the surface area is characterized so that the average diameter of pores is 20-300 angstroms, the pore volume is 0.1-1 cm3/g and a surface area equal 100-500 m2/,

Referring to the fact that the aluminum oxide is the preferred refractory inorganic oxide, particularly preferred alumina is the one that is described in US-A-3852190 and US-A-401 2313 as a side product of the reaction of the Ziegler synthesis of higher alcohols, as described in the Deposit Ziegler currently ships company Vista Chemical Company under the trademark Catapal" or Condea Chemie GmbH under the trade mark "Pural". This material is extremely high-purity pseudoboehmite, which after firing at high temperature gives high-purity gamma-alumina.

The alumina powder may be molded in any desired shape or type of substance carrier, known in the art, such as spherical, in the form of rods, pellets, beads, tablets, extrudates, etc., forms, methods, known in the art for forming ingredients of the catalyst.

The preferred form of the catalyst carrier of the present invention is spherical. Spheres of aluminum oxide can be produced continuously well-known oil-drop method, which includes: obtaining a Hydrosol of alumina by any known method and, preferably, the interaction of aluminum metal with hydrochloric acid; combining the resulting Hydrosol with a suitable gelling agent; and dropping the resulting mixture into an oil bath which is maintained at elevated temperatures. Droplets of the mixture remain in the oil bath until then, until they harden and do not form spheres (balls) hydrogel. The balls are then continuously removed from the oil bath and typically subjected to specific treatments is acteristic. Received matured and thickened the particles are then washed and dried at a relatively low temperature 150-205oWith and subjected to the procedure of annealing at a temperature of 450-700oC for 1-20 hours. This processing causes the conversion of the hydrogel of aluminum oxide to the corresponding crystalline gamma-alumina. US-A-2620314 provides additional details and is mentioned here as a reference.

An alternative form of the substance carrier is a cylindrical extrudate, preferably prepared by mixing the alumina powder with water and suitable peptization, such as HCl up until does not form an extrudable paste. The amount of water added to form a paste, usually enough to get the loss on ignition (LOI) at 500oC 45-65 wt.%, where a value of 55 wt.% is preferred. The rate of addition of acid is usually sufficient to obtain 2-7 wt.% volatile alumina powder used in the mixture, where a value of 3-4 wt.% is preferred. The resulting paste ekstragiruyut through the stamp of a suitable size to form extrudate particles. These particles are then dried at a temperature of 260-427oC for 0.1 to 5 o essence, pure aluminum oxide Ziegler, with the apparent volumetric weight of 0.6 to 1 g/cm3and surface area of 150-280 m2/g (preferably, 185-235 m2/g with a pore volume of 0.3-0.8 cm3/g).

The metal of group IVA (IUPAC 14) is an essential ingredient of the catalyst of the present invention. From metals of group IVA(IUPAC 14) are preferred germanium and tin, and the tin is particularly preferred. This component may be present in the form of elemental metal in the form of chemical compounds such as the oxide, sulfide, halide, oxychloride, etc. or in the form of a physical or chemical combination with the porous carrier substance and/or other components of the catalytic composite. Preferably, a substantial portion of the metal of group IVA (IUPAC 14) were present in the final catalyst with a degree of oxidation higher than the elemental metal. The metal component of the group IVA(IUPAC 14) optimally used in a quantity sufficient to obtain a final catalytic composite containing 0.01 to 5 wt.% metal, calculated on an elemental basis, with best results obtained at levels of metal is 0.1-2 wt.%

The metal component of the group IVA (IUPAC 14) can be weenie with a porous substance carrier, ion exchange with the carrier substance or impregnation of the carrier substances at any stage of the preparation. The method of introducing a metal component, a group IVA (IUPAC 14) into the catalytic composite involves utilization of a soluble degradable compound of metal of group IVA (IUPAC 14) for impregnation and dispersion of the metal in the porous substance of the media. The metal component of the group IVA(IUPAC 14) can be impregnated either before, simultaneously with, or after other components are added to the substance of the media. Thus, the metal component of the group IVA (IUPAC 14) can be added to the substance of the medium by mixing the latter with an aqueous solution of a suitable metal salt or soluble compounds, such as dobroesti tin, dehority tin tetrachloride tin tetrachloride pentahydrate of tin; or oxide of germanium, tetraethoxide Germany, tetrachloride Germany; or nitrate, lead acetate, lead chlorate, lead, etc. connections. Using chloride compounds of a metal of group IVA(IUPAC 14), such as tin tetrachloride, tetrachloride Germany or chromate of lead is particularly preferred, because it facilitates the implementation as a metal component, and at least nestum hydrogen during a particularly preferred stage peptization of the alumina, as described above, in accordance with the present invention obtain a homogeneous dispersion of the metal component, a group IVA (IUPAC 14). In an alternative embodiment of an organic compound of a metal, such as chloride trimetoprima and tin dichloride, introduced into the catalyst during the peptization of the binder based on the inorganic oxide, most preferably during the peptization of the alumina hydrogen chloride or nitric acid.

Another essential ingredient of the catalyst is a metal component of the group of platinum. This component includes platinum, palladium, ruthenium, rhodium, iridium, osmium, or mixtures thereof, preferred is platinum. The platinum group metals may be present in the final catalytic composite in the form of compounds such as the oxide, sulfide, halide, oxyhalide, etc., in chemical combination with one or more other ingredients of the composite or in the form of elemental metal. The best results are obtained when essentially all of these components are present in the elemental state and uniformly dispersed in the carrier substance. This component may be present in the final catalytic composite in any amount which auctionsmega composite, designed for elementary basis. Excellent results are obtained when the catalyst contains from 0.05 to 1 wt.% platinum.

The metal component of the group of platinum can be introduced into the porous substance of the carrier in any suitable way, such as joint precipitation, ion exchange or impregnation. The preferred method of preparation of the catalyst involves the use of soluble degradable compounds of platinum group metals for impregnation substance carrier relatively homogeneous way. For example, a component may be added to the carrier by mixing the latter with an aqueous solution of hexachloroplatinic or iridogoniodysgenesis or paradichlorobenzene acid. Other water-soluble compounds or complexes of platinum group metals may be employed in impregnation solutions and include chloroplatinic ammonium, platinumrose-standartnuyu acid, tripoid platinum, tetrachlorethene platinum dichloride, dichlorocarbene platinum, dinitrodiphenylamine, tetranitromethane (II) sodium, palladium chloride, palladium nitrate, palladium sulfate, hydroxide, diaminopentane (II) chloride tetraamminepalladium (II) chloride examinationthe, tribromide iridium, iridium dichloride, iridium tetrachloride, hexanitroethane (III) sodium, GLORIETTA potassium or sodium, radioclit potassium, etc. Using chloride compounds of platinum, iridium, rhodium or palladium, such as platinochloride, iridochoroiditis or paradichlorobenzene acid or hydrate trichonida rhodium is preferred because it is easier to implement as the metal component of the platinum group and at least minor amounts of the preferred halogen component in a single phase. Salt, or the like acid is usually added in the impregnation solution in order to additionally facilitate the introduction of the halogen component and a uniform distribution of metallic components in the substance of the media. In addition, it is generally preferable to impregnate the carrier substance after annealing to minimize the risk of washing away the valuable platinum group metals.

Usually metallic platinum group component is uniformly dispersed in the catalyst. Homogeneous dispersion of the platinum group metals are preferably define a scanning transmission electron microscope (STEM), comparing conc the economic components of the platinum group may be present as a component of the surface layer, as described in US-A-4677094 included in the description by reference. The term "surface layer" means a layer of catalyst particles adjacent to the surface of the particles, and the concentration of the metal surface layer decreases from the surface to the center of the catalyst particles.

Metal series lanthanides is another essential component of the present catalyst. In the series of lanthanides include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. Favorable elements are those that are able to form stable ions +2, i.e., Sm, Eu and Yb (CRC Handbook of Chemistry and Physics, 75th edition 1994-1995, CRC Press, Inc.), moreover, ytterbium and europium are preferred, and europium are particularly preferred. Lanthanoide components, in General, may be present in the catalytic composite in any catalytically available form, such as the elemental metal, a compound such as oxide, hydroxide, halide, oxyhalide, aluminate, or in chemical combination with one or more other ingredients of the catalyst. Although not designed for such a limitation of the present invention, it is assumed that the best results are obtained when the LAN who are in oxidation state above than elemental metal, such as oxide, oxyhalide or halide or mixtures thereof, and further described stages of oxidation and reduction, which are preferably used in the preparation of the present catalytic composite especially designed for this purpose. In a particularly advantageous embodiment of the preparation stage and conditions are selected to obtain the form of favorable lanthanide, which forms mainly stable ions +2 (i.e., more than 50% of the lanthanides, such as SmO, EuO and/or YbO. Optimally, more than 80% on an atomic basis, of the lanthanide is present in the form +2 oxide, such as preferred europium in the form of EuO. As the ultimate recovery of the catalyst can be carried out in situ in the plant reformer, the catalyst according to the invention can detect such proportions of the oxides or receiving, or immediately before its use in the process of reforming.

Metal lanthanoide components can be incorporated into the catalyst in any amount which is catalytically effective, with good results are obtained with 0.05 to 5 wt.% lanthanides on an elementary basis in the catalyst. The best results are usually reached with Lantano-DAMI from 0.2 to 2 wt.% in races which I this catalyst is at least 1.3:1, preferably of 1.5:1 or more, especially from 2:1 to 5:1.

Lantanoides component is introduced into the catalytic composite in any suitable known manner, such as by co-deposition, joint thickening or co-extrusion with a porous substance media, ion exchange with geleobrazovanie substance carrier or impregnation of the porous carrier substances or after, before, or during drying and firing. In the scope of the present invention include all known methods of injection and simultaneous distribution of the metallic component in a catalytic composite as needed, so that the particular method of introduction is not intended as an essential characteristic of the present invention. Preferably used the method leads to a relatively homogeneous dispersion lantanoides component in the substance of the media, although the ways that lead to inhomogeneous distribution of lanthanides, are within the scope of the present invention.

One suitable way of introducing lantanoides component into the catalytic composite involves joint salustiana or joint deposition lantanoides component in the form corresponding to the This method typically involves the addition of a suitable Sol-soluble or Sol-dispersible lantanoides component, such as trichloride of lanthanide oxides of the lanthanide, and similar to the Hydrosol of alumina and then combining lanthanide-containing Hydrosol with a suitable gelling agent and dropping the resulting mixture into an oil bath and so on, as explained in detail above. Alternatively, lantanoides the connection can be added to the gelling agent. After drying and calcination of the obtained gel carrier substances in the air get thick combination of aluminum oxide and lanthanide oxide and/or oxychloride.

One of the preferred ways of implementing lantanoides component into the catalytic composite involves utilization of a soluble degradable compounds of the lanthanide in solution for impregnation of a porous material medium. Typically, the solvent used in this impregnation stage, chosen on the basis of the ability to dissolve the desired lantanoides connection and save it in the solution as long as it not equally distributed through the material of the carrier without harmful impact on the substance of the media or other ingredients of the catalyst. Suitable solvents include alcohols, ethers, acids, etc. and the aqueous acidic solution is to prefer the carrier with an aqueous acidic solution of a suitable salt of a lanthanide, complex or compound, such as nitrate, chloride, fluoride, organic alkyl, hydroxide, oxide, etc. connections. Suitable acids for use in the impregnation liquor are: inorganic acids such as hydrochloric acid, nitric acid, etc., and strongly acidic organic acids such as oxalic acid, malonic acid, citric acid, etc. Lantanoides component can be impregnated into a carrier or prior to, simultaneously with, or after the component metal of the platinum group.

Alternatively, a homogeneous distribution of the lanthanide in the media lanthanoide metal surface layer may be embedded in the catalyst particles by any method suitable for implementation of a decreasing gradient of metal from the surface to the center of the particle. Preferably, the metal is impregnated into a carrier in the form of a compound which decomposes upon contact with the carrier, freeing the metal on the surface or near the surface of the particles. Other means, which do not limit the invention include the use of compounds of the metal, which forms complexes with the carrier or which does not penetrate into the particles. An example is multidentate ligand, such as carbon and the polar group, which can strongly connect with a native oxide. Alternatively, lanthanoide metal may be introduced into the catalyst by impregnation spray.

Optionally, the catalyst may also contain other components or mixtures thereof, which act independently or in conjunction as a catalytic modifiers to improve the activity, selectivity or stability. Some well-known catalyst modifiers include rhenium, indium, cobalt, Nickel, iron, tungsten, molybdenum, chromium, bismuth, antimony, zinc, cadmium and copper. Catalytically effective amounts of these components can be added in any suitable way to the substance of the medium during or after its preparation or catalytic composite before, during or after implementation of the other components.

An optional component of the catalyst is particularly useful in embodiments the conversion of hydrocarbons of the present invention containing reaction dehydrogenization, dehydrocyclization or hydrogenation are alkaline or alkaline-earth metal components. More precisely, this optional ingredient selected from the group consisting of compounds of alkali m is Riya and magnesium. Usually, good results are obtained in those embodiments when this component is from 0.01 to 5 wt.% composite, calculated on an elemental basis. These optional alkaline or alkaline-earth metal components can be embedded in the composite by any known method, impregnation with an aqueous solution of a suitable water-soluble, degradable compounds is preferred.

As stated above, you must use at least one stage of oxidation for the preparation of the catalyst. The conditions applied for the implementation stage of oxidation, choose to convert essentially all of the metal components in the catalytic composite in their corresponding oxide form. Stage oxidation is usually carried out at a temperature of from 370oC to 600oC. Used oxygen atmosphere usually contains air. Usually oxidation step must be completed within 0.5 to 10 hours or more, and the exact period of time is such that you want to convert essentially all of the metal components in their corresponding oxide form. This time will, of course, vary with the temperature oxidation and content Kacie can be used in the manufacture of the catalyst. As described above, the phase adjustment of the halogen can perform a dual function. Firstly, the phase adjustment of the halogen can help in a homogeneous dispersion of the metal of group IVA(UPAC 14), and other metal component. In addition, the phase adjustment of the halogen may serve as a means of implementing the required level of halogen in the final catalytic composite. Phase adjustment uses halogen halogen or halogen-containing compound in air or oxygen atmosphere. As the preferred halogen for introduction into the catalytic composite involves chlorine is the preferred halogen or halogen-containing compound that is applied during the stage of adjustment of the halogen is chlorine, Hcl or a precursor of these compounds. When performing phase adjustment halogen-free catalytic composite is in contact with the halogen or halogen-containing compound in air or in oxygen atmosphere at an elevated temperature from 370oC to 600oC. Additionally, it is desirable to have water present during the stage of contact in order to facilitate the regulation. In particular, when the halogen component of the catalyst contains chlorine, preferably used is about 5 hours or more. Because of the similarity of conditions of phase adjustment of the halogen can be carried out during the stage of oxidation. Alternatively, the phase adjustment of the halogen may be performed before or after the oxidation steps, as required in the specific method used for the preparation of the catalyst in accordance with the invention. Regardless of the applied method of fine tuning of the halogen, the halogen content in the final catalyst should be such that sufficient halogen, elemental basis, from 0.1 to 10 wt.% from the final composite.

The preparation of the catalyst, you must also perform stage of recovery. The recovery phase is designed to recover essentially all of the component metal of the platinum group to the corresponding elemental metallic state and to ensure a relatively uniform and accurately divided dispersion of this component in the refractory inorganic oxide. Preferably, the recovery phase was carried out in essentially free from water environment. Preferably, the regenerating gas is essentially pure dry hydrogen (i.e., less than 20 parts per million by volume of water). However, you can primenjena catalytic composite in terms including temperature recovery from 315oC to 650oC for a time of from 0.5 to 10 hours or more, effective to recover essentially all metallic platinum group component to the elemental metallic state. The recovery phase may be performed prior to the loading of the catalytic composite in the area of conversion of hydrocarbons or may be performed in situ as part of the initial procedure of the process of conversion of hydrocarbons. However, if you use the latter method, should be taken proper precautions for pre-drying installation conversion of hydrocarbons to essentially free from water condition and should be essentially free from water hydrogen-containing regenerating gas.

Optionally, the catalytic composite may be subjected to the preliminary stage of sulfatirovnie. Optional sulfur component can be introduced into the catalyst by any known method.

The catalyst according to the present invention has a practical application as a catalyst for conversion of hydrocarbons. Hydrocarbons, which must be converted, in contact with the catalyst at conditions ospery to 200 atmospheres abs. (101,3 kPa to 20.26 MPa) and hourly volumetric velocity of the fluid from 0.1 to 100 h-1. The catalyst is particularly suitable for catalytic reforming feedstock gasoline range, and can also be applied to dehydrocyclization, isomerization of aliphatic and aromatic compounds, dehydrogenization, hydrocracking, disproportionation, dealkylation, alkylation, transaminirovania, oligomerization and other transformations of hydrocarbons.

In the preferred embodiment of the catalytic reforming process of the original hydrocarbons and rich hydrogen gas is preheated and loaded into the reforming zone containing usually from two to five consecutive reactors. Suitable heating means are positioned between reactors to compensate for the total endothermic heat of the reactor in each of the reactors. The reactants may be contacted with the catalyst in individual reactors or when moving up, down or in the radial direction with the preferred radial flow regime. The catalyst is contained in a system with a fixed layer or, preferably, in the system with a movable layer associated with continuous catalyst regeneration. Alternative the regenerative operation, when the whole plant is stopped for catalyst regeneration and reactivation, or swing reactor, in which a separate reactor is isolated from the system, regenerate and reactivit, while the other reactors remain in operation. The preferred continuous regeneration of the catalyst together with a system of movable layer is disclosed, however, in US-A-3647680, US-A-3652231, US-A-3692496 and US-A-4832291, which are included in the description by reference.

Resulting from the reforming zone, the stream passes through a cooling means to a separation zone, typically supported at a temperature of 0oS-65oWith, which is rich in hydrogen gas separated from the liquid stream, commonly called "non-stabilized product of the reforming process". The resulting stream of hydrogen can then be recycled through a suitable compression tool back into the zone of the reforming process. The liquid phase from the separation zone is typically removed and treated in a fractionation system in order to regulate the concentration of butane, whereby controlling the evaporation head of the faction of the obtained product of the reforming process.

The operating conditions used in the method of reforming the present invention, include pressure, in the but at a pressure of from 350 to 2500 kPa (abs.). The temperature of the reformer is in the range from 315oC to 600oC, preferably from 425oC to 565oC. As is well known to experts in the field of reforming, the initial selection of the temperature of this broad range is made primarily as a function of the desired octane number of the resulting product of the reforming process, considering the characteristics downloadable raw material and catalyst. Usually the temperature is then slowly increased during operation to compensate for the inevitable deactivation that occurs to obtain a product with a constant octane number. A sufficient amount of hydrogen serves to provide a quantity of from 1 to 20 moles of hydrogen per mole of hydrocarbon entering the reforming zone, with excellent results being obtained when using from 2 to 10 moles of hydrogen per mole of hydrocarbon feedstock. Also hourly space velocity of fluid (LHSV) used in reforming is selected in the range from 0.1 to 10 h-1with the preferred value in the range from 1 to 5 h-1.

Hydrocarbons, which are loaded into the system reformer is preferably oil feedstock containing naphthenes and paraffins that boil within the gasoline naphthenes and paraffins, although in many cases may be aromatic compounds. This preferred class includes gasoline direct distillation, natural gasolines, synthetic gasolines, etc., an alternative embodiment is often beneficial for download thermally or catalytically brakirovochnye gasoline, partially reformiruia (improved) the gasoline-ligroin fraction (naphtha) or dehydrogenation the gasoline-ligroin faction. A mixture of gasoline, ligroin fractions of direct distillation and kreiranih the gasoline-ligroin fractions of the gasoline range can also be used. Download feedstock from naphtha gasoline range can be gasoline with a boiling point of only gasoline range having an initial ASTM D-86 boiling points from 40-80oWith and end boiling point ranging from 160 to 220oWith, or may be a selected fraction, which will typically be a fraction higher boiling point, usually related to the so-called heavy nafta - for example, nafta, boiling in the range of 100-200oC. If the reforming process is aimed at obtaining one or more of benzene, toluene or xylene, the boiling range may primarily or mainly to be in the range of 60-150o

It is generally preferable to use the present invention, essentially anhydrous conditions. Essential to achieve this condition in the zone of the reformer is to control the level of water present in the feedstock and the hydrogen stream which is fed to the area. Best results are usually obtained when the total amount of water entering the conversion zone from any source is maintained at a level less than 50 ppm and preferably less than 20 ppm, expressed as the equivalent weight of water in the feedstock. In the General case this can be accomplished by careful control of water present in the feedstock and hydrogen flow. Raw materials can be dried by any known suitable means vysusene, such as a conventional solid adsorbent having a high selectivity for water, for example sodium or calcium crystalline aluminosilicates, silica gel, activated alumina, molecular sieves, anhydrous calcium sulfate, sodium with a large surface area, etc. adsorbent fractionation or similar installations. In some cases, it may be advantageously used in combination drying of the adsorbent and drying by distillation to exercise almost complete removal of water from the feedstock. Preferably, the feedstock is dried to a level corresponding to less than 20 ppm H2About equivalent.

Preferably, to maintain the water content in the stream of hydrogen included in the conversion zone of the hydrocarbon-level from 10 to 20 ppm by volume or less. In cases where the water content in the stream of hydrogen is above this limit, it can usually be done by contacting the stream of hydrogen with a suitable desiccant, such as mentioned above, under normal drying conditions.

It is preferable to use the present invention, essentially free from sulfur environment. Any known in this field controls can be used to process the original naphtha, which must be loaded into the reaction zone of the reformer. For example, the original thread can be subjected to adsorption processes, catalytic processes, or combinations of these. Methods adsorption can use molecular sieves, alumina - silica with a high surface area, carbon molecular sieves is resti, such as Nickel or copper, etc., it is Preferable that this feedstock was processed in the usual way prior catalytic processing, such as Hydrotreating, hydrobromide, hydrodesulfurization and so on, to remove essentially all of the sulfur, nitrogen and producing water pollution and to saturate any olefins that may be contained therein. Catalytic processes may use conventional catalytic methods of reducing sulfur, known in this area, including the holders of the refractory inorganic oxide containing a metal selected from the group consisting of group VI-B(6), group II-B (12) and group VIII(IUPAC 8-10) of the Periodic table.

One embodiment according to the invention includes a method of transforming the original naphtha under conditions of catalytic dehydrocyclization. In particular, the preferred source nafta contains6-C8nonaromatic hydrocarbons. Conditions dehydrocyclization include a pressure from 100 kPa to 4 MPa (abs. with the preferred pressure is from 200 kPa to 1.5 MPa, a temperature of from 350oC to 650oC and hour space velocity of the liquid is from 0.1 to 10 h-1. Preferably, the hydrogen can be applied is as per mole of the original hydrocarbon.

Preferably, the original nafta alternative embodiment of the method of dehydrocyclization contained a greater proportion of paraffins, as a method of dehydrocyclization is the conversion of paraffins to aromatics. Because of the high values WITH6-C8aromatic compounds are additionally preferably, the original nafta contained WITH6-C8paraffins. However, despite this preference, the original naphtha may contain naphthenes, aromatics, and olefins in addition to C6-C8paraffins.

EXAMPLE 1

Known from the prior art spherical catalyst containing platinum and tin on alumina, prepared by conventional means as control catalyst for comparison with the catalysts according to the present invention. Tin is introduced into the Sol of aluminum oxide according to the prior art and tin-containing Sol of aluminum oxide is formed by dripping in oil to form 1.6 mm spheres, which is treated with water vapor to dry at 10% LOI and calcined at 650oC. Spherical carrier is then impregnated with hexachloroplatinic acid in Hcl the date of receipt of 0.38 wt.% Pt in the final catalyst. Profit and 565oC.

The final control determines the Catalyst X, which has the following approximate composition, wt.%:

Platinum - 0,38

Tin - 0,3

EXAMPLE 2

Spherical catalyst containing platinum, ytterbium and tin on alumina is prepared to demonstrate the features of the invention. Tin is introduced into the Sol of aluminum oxide in accordance with the prior art and tin-containing Sol of aluminum oxide is formed by dripping in oil to form 1.6 mm spheres, which is treated with water vapor to dry at 10% LOI and calcined at 650oC. Spherical carrier is then impregnated with nitrate ytterbium 3.5% nitric acid to obtain 1,1% Yb in the final catalyst in the ratio of solution to media 1:1. The resulting composite is subjected to treatment with water vapor to dry (10% LOI and calcined at 650oC with 3% water vapor. The obtained calcined composite is impregnated with hexachloroplatinic acid in Hcl to get to 0.38 wt.% Pt in the final catalyst. The impregnated catalyst is dried and oxychloride at 525oWith 2 M Hcl in the air and restore the pure hydrogen at 565oC. End of Yb-containing catalyst identified as Catalyst a and has the following privliage lanthanum, samarium and dysprosium prepared in the same way that itembesonderhede catalyst. The content of the lanthanide in the final catalysts were the following, each catalyst has essentially the same content of tin and platinum as the Catalyst AND:

The catalyst was 0.9 wt.% La

The catalyst is 1.0 wt.% Sm

Catalyst D - 1.1 wt.% Dy

EXAMPLE 3

Tests in the pilot plant were structured to compare the selectivity to aromatic compounds in the process of reforming catalysts according to the invention and known. The tests are based on the reforming of naphtha over the catalysts at a pressure of 0.8 MPa (abs.), hourly volumetric velocity of the fluid 3 h-1and a molar ratio hydrogen/hydrocarbons equal to 8. Range conversion is studied using temperature changes to obtain data points at 502oWITH 512oWITH 522oWith and 532oC. the naphtha for the comparative tests is gidroaparatura obtained from petroleum naphtha obtained from a paraffinic crude oil from the middle of the continent, which has the following characteristics:

Share - 0,737

Distillation, ASTM D-86,oC IBP - 87

10% - 97

50% - 116

90% - 140

EP - 159

wt.% paraffin - 60
5+in Fig.1 for catalysts a, b, C, D, and X. the Yield of aromatic compounds is defined as output in wt.% (benzene + toluene + aromatic compounds WITH5+aromatic compounds C9). Since a high yield of aromatic compounds is usually essential aim of the catalytic reforming process, a high yield of aromatic compounds relative to the exit WITH5+the high selectivity. Catalysts a, b, C and D according to the invention show the yield of aromatic compounds 2-3% higher for the same output WITH5+.

EXAMPLE 4

Tests in the pilot plant were structured to compare the selectivity and activity of the catalysts With and X days of reforming the original naphtha. Naphtha day comparative tests take the same as in example 3. Each test is based on the conditions of the reformer containing a pressure of 0.8 MPa (abs.), hourly space velocity of the liquid 3 h-1and the ratio of hydrogen/hydrocarbon equal to 8. Range conversion is studied using temperature changes to obtain multiple data points at 502oWITH 512oWITH 522oWith and 532oC. the Conversion of paraffins + naphthenes) at each temperature was the e conversion for catalyst C. A graph of the dependence of selectivity on the conversion shown in Fig.2.

EXAMPLE 5

Three spherical catalyst containing platinum, europium and tin on alumina is prepared to demonstrate the features of the invention. Tin is introduced into the spherical carrier of aluminum oxide in accordance with the prior art, as described in example 2. Spherical carrier is then impregnated with europium nitrate 3.5% nitric acid to obtain three different levels UOM in the final catalyst in the ratio of solution to media 1:1. The resulting composite is subjected to treatment with water vapor to dry (10% LOI and calcined at 650oC with 3% water vapor. Obtained whether the composites impregnated with platinochloride Noi acid in Hcl to get to 0.38 wt. % Pt in the final catalyst. The impregnated catalyst is dried and oxychloride at 525oC 2 M Hcl in the air and restore the pure hydrogen at 565oC. End Unit-containing catalysts is defined as the catalysts E,F and G and have the following approximate composition in wt.%, presented in table 1.

EXAMPLE 6

Catalyst G test in comparison with the known from the prior art catalyst X to determine presets is using 5 mol. % H2in Ar with increasing temperature from room temperature up to 600oC at a rate of 10oWith in a minute. The consumption of hydrogen for catalyst G higher than for catalyst X 33 Ámol/g, indicating a recovery of over 90% of EU+3in the Eu+2.

EXAMPLE 7

Tests in the pilot plant were structured to compare the selectivity and activity of catalysts E, F and G with the selectivity and activity of the catalyst for reforming of the original naphtha. Naphtha for comparative tests take the same as in example 3.

Each test is based on the conditions of the reformer containing a pressure of 0.8 MPa (abs. ), hourly space velocity of the liquid 3 h-1and the ratio of hydrogen/carbon equal to 8. Range conversion is studied using temperature changes to obtain multiple data points at 502oWITH 512oWITH 522oWith and 532oC. Comparative conversion of paraffins+naphthenes), the output of the product5+and the yield of aromatic compounds expressed in wt.% in table 2.

Fig.3 depicts a graph of the yield of aromatic compounds depending on the output WITH5+based on the above values, showing a higher yield of aromatic compounds is ti and selectivity were obtained from the above values and is shown in Fig.4. Activity was calculated as percent reduction in conversion from a base catalyst X for each temperature and displayed on the graph depending on the atomic relations Eu/Pt for the respective catalysts. The selectivity obtained from Fig.3 by measuring the changes of the outputs of aromatic compounds between the catalysts in the whole range of outputs5+and divided by the output FROM5+, i.e. the mean value of the yield of aromatic compounds, expressed as % of output WITH5+. When displaying the graph of the latter in Fig. 4, the extension of the line to a higher ratio of Eu/Pt catalyst G shows more than a thin line, because there is only a slight overlap line for catalyst G lines of other catalysts in Fig.3.

Fig.4 depicts accelerating decrease in conversion with increasing content of europium in the catalyst, when the relationship with the Eu/Pt increases from 1 to 2, and the slope becomes even more for relationships, greater 2. The ratio of selectivity to respect Eu/Pt, on the other hand, is more linear. Although the choice of relations Eu/Pt will depend on the relative importance of selectivity and activity, very high relationship will be great with the in, containing a metal component is platinum-group metal component, a group IVA, halogen, metal component of the group of lanthanides, where part of lanthanide present in the form of oxide, and the carrier is a refractory inorganic oxide, characterized in that the metal of the lanthanide catalyst contains europium, and the atomic ratio of europium to platinum group metal is at least 1: 3, where more than 50% of europium is present in the form of the Sole, with the following ratio of components, wt. %:

The platinum group metals - 0,01-2,0

The metal of group IVA of 0.01 to 5.0

Halogen is 0.1-10

Europium - 0,05-5,0

Media - Rest

2. The catalyst p. 1, characterized in that, as the refractory inorganic oxide includes aluminum oxide.

3. The catalyst PP. 1 and 2, characterized in that as a platinum group metal includes platinum.

4. The catalyst PP. 1-3, characterized in that as the metal of group IVA contains tin.

5. The catalyst PP. 1-4, characterized in that the halogen includes chlorine.

6. Method for catalytic reforming of the original naphtha, comprising contacting the feedstock at reforming conditions: rate is odorata supplied to the hydrocarbon 2-10 in the presence of a catalyst, characterized in that the catalyst used, the catalyst according to any one of paragraphs.1-5.

 

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