Platinum- and tin-containing polymetallic reforming catalyst, preparation thereof and use

FIELD: petrochemical process catalysts.

SUBSTANCE: catalyst contains, wt %: group VIII metal 0.01-2.0, group IVA metal 0.01-5.0, europium 0.01-10.0, cerium 0.10-10.0, halogen 0.10-10.0m and refractory inorganic oxide 63.00-99.86.

EFFECT: enabled preparation of catalyst with relatively high activity and selectivity, low carbon sedimentation velocity, and prolonged lifetime in naphtha reforming processes.

11 cl, 6 dwg, 4 tbl

 

The present invention relates to polymetallic catalyst for conversion of hydrocarbons, which has the dual function of acidity and hydrogenation-dehydrogenation, and the method of its production. The present invention applies in particular to polymetallic reforming catalyst containing platinum and tin, and to a method thereof.

Catalytic reforming (also known as a reformer is one of the most important technologies in the refining of oil, and its main task is the production of gasoline with a high octane, aromatic compounds, have a wide application, and hydrogen with low cost. Currently widely used in industry reforming catalysts for the most part represent a bimetallic reforming catalysts, such as Pt-Re, Pt-Sn catalysts. Studies have shown that in comparison with Pt-Re catalysts Pt-Sn catalysts have a higher resistance at low pressure and higher selectivity towards aromatic compounds, there is no need in their preliminary sulfirovanie, and they are more suitable for the reforming process with a moving bed of catalyst. The acid function in bimetallic catalysts for isomerization is provided usually porous media from Ki the pilot oxides, such as aluminum oxide, and a halogen, and the function of the hydrogenation-dehydrogenation are usually provided by the metallic components of group VIII, such as platinum or palladium. The introduction of a second metal component, such as Re or Sn, can significantly improve the durability of the catalyst and to reduce the content of the noble metal is platinum.

During the catalytic reforming process occurs several competing reactions. Such reactions include dehydrogenation of cyclohexane in aromatic compounds, dehydroisomerization of alkylcyclopentanes in aromatic compounds, dehydrocyclization acyclic hydrocarbons to aromatics, hydrocracking of paraffins into lower hydrocarbons of carbon atoms less than C5the dealkylation of alkyl benzenes and isomerization of paraffins. In these reactions the yield of gasoline will decrease due to the formation in the process of hydrocracking of gases consisting of light saturated hydrocarbons; coking reaction will be to increase the rate of deactivation of the catalyst; and frequent regeneration of the catalyst will increase operating costs. Therefore the task of the experts in this field is to create a catalyst and method of reforming with high selectivity and a low deposition rate of carbon when it is time to relax is the third or fourth metal component in the bimetallic catalyst is one of the modifying agents commonly used in this field.

In U.S. patent No. 3915845 disclosed composition polymetallic catalyst for the conversion of hydrocarbons containing from 0.01 to 2.0 wt.% metal of the Pt group, 0.01 to 5.0 wt.% Germany, 0.1 to 3.5 wt.% halogen and a lanthanide compound, and the atomic ratio lanthanoide element/metal group Pt is 0.1-1,25. The metal of the Pt group is present in the catalyst in the elemental metallic state, while other metals are present as oxides. Used lanthanoide elements are lanthanum, cerium or neodymium.

In U.S. patent No. 4039477 disclosed catalyst hydrobromide modified lanthanoide metals and its application. This catalyst comprises a refractory metal oxide, the metal of Pt, Sn and at least one metal selected from the group consisting of Y, Th, U, Pr, Ce, La, Nd, Sm, Dy and Gd. In this patent, the stability of the catalyst activity is enhanced by inclusion in the composition of the catalyst lanthanoid metals and selectivity lanthanide-containing catalyst is increased by suppressing the activity of cracking due to the presence of tin. In a separate embodiment, the outputwhen the conversion of hexane on Pt-Sn-Ce-containing catalyst at a mass ratio of Ce/Pt 0,37 was higher than the yield obtained using Pt-Sn-containing catalyst.

In U.S. patent No. 6059960 discovered polymetallic Pt-Sn-reforming catalyst containing a series of lanthanides, and included in lanthanoide components are Eu, Yb, Sm, or a mixture of Eu and Yb, and more than 50% lanthanoid metals in the catalyst are present in the form of EuO. When the catalytic composition is a Pt-Sn-Eu, the relative activity and selectivity are higher in the case when the atomic ratio Eu/Pt is between 1.3 and 2.0. The selectivity of the catalyst will be reduced when this ratio is less than 1.3. The catalyst activity is greatly reduced when the atomic ratio Eu/Pt more than 2.0.

The present invention is to create a modified lanthanide Pt-Sn-reforming catalyst with high activity, high selectivity and high stability activity.

Another objective of the present invention is to provide a method for obtaining the above-mentioned catalyst.

The inventors have found that bimetallic reforming catalyst modified with cerium and europium, can increase the selectivity and the ability of the catalyst to withstand the deposition of carbon and, consequently, to increase the yield of liquid products of the reforming reaction and to increase the service life of the catalyst. In particular, polymetallics the second catalyst in accordance with the present invention contains the following components in wt.%:

the metal of group VIII0,01-2,0
the metal of group IVAof 0.01 to 5.0
Eu0,1-10,0
CEof 0.01 to 10.0
halogen0,10-10,0
inorganic oxide refractory metal63,00-99,86

Specified metal of group VIII selected from the group consisting of Pt, Pd, Ru, Rh, Ir, Os or mixtures thereof, with the preferred Pt. The metal component in the form of a metal of group VIII is an important active component of the catalyst in accordance with the present invention. Present in the catalyst metal of the Pt group may be an elementary metal or compound, such as oxide, sulfide, halide, or oxychlorine etc. or chemical combination with one or more other components of the catalyst. The preferred content of the metal of group VIII in the catalyst is 0.05-1.0 wt.% in the calculation of the elemental metal.

Present in the catalyst metal of the IVA group preferably is a Ge or Sn, more preferably Sn. This metal component can be present as elemental metal or in the form of compounds such as the oxide, sulfide, halide, or oxychlorine etc. or in the form of physical or chemical the combination with other components of the carrier and catalyst. The metals of group IVA, preferably are present in the catalytic product in the oxide state, i.e. in the form of oxide. The preferred content of metals of group IVA in the catalyst in accordance with the present invention is 0.1-2.0 wt.% in the calculation of the elemental metal.

Contained in the catalyst in accordance with the present invention lanthanoide metals are a mixture of Ce and Eu. Ce and Eu may be present in the catalyst in the form of compounds, such as oxide, hydroxide, halide, oxychlorine or aluminate, or in chemical combination with one or more other components of the catalyst. The content in the catalyst of each of Eu and Ce is preferably 0.05 to 2.0 wt.% in the calculation of the elemental metal, and more preferably 0.1 to 1.0 wt.%. The atomic ratio Eu/Pt in the catalyst in accordance with the present invention is 0.2 to 3.0:1, preferably 0.2 to 1.0:1, more preferably 0.5 to 1.0:1 and the atomic ratio Ce/Pt is 0.2 to 5.0:1, preferably from 0.5 to 3.0:1. In the recovered catalyst is present in more than 60% of CE in oxidation state +3.

Component used to regulate the amount of acid in the catalyst in accordance with the present invention, represents a halogen, preferably chlorine. The content of halogen in the catalyst is preferably 0.2 to 4.0 m is SS.%.

The specified catalyst carrier, which is typically a porous adsorptive material and has a specific surface area of 30-500 m2/g, selected from refractory inorganic oxides. The porous medium must be homogeneous and to be refractory when operating conditions. Used in this description, the term "homogeneous" means that the medium is not layered and has no concentration gradient inherent components. If the carrier is a mixture of two or more refractory materials, such materials have a relatively constant content or uniform distribution throughout the media. Refractory inorganic oxides disclosed in the present invention include:

(1) refractory inorganic oxides such as aluminum oxide, magnesium oxide, chromium oxide, boron oxide, titanium dioxide, thorium oxide, zinc oxide, zirconium oxide or a mixture of these two oxides: silica-alumina, silica-magnesia, chromium oxide-alumina, alumina-boron oxide, silica-Zirconia;

(2) various ceramics, various alumina and various bauxite;

(3) silicon oxide, silicon carbide, synthetic and natural silicates and clay. These silicates and clay may be the acid-treated or non-treated her.

In the present invention the preferred media of the inorganic oxide is Al 2O3more preferably high-purity aluminum oxide obtained by the hydrolysis of the alkoxide (alcoholate) of aluminum. The crystalline state of the aluminum oxide can be γ-Al2O3that η-Al2O3or θ-Al2O3while it is preferable γ-Al2O3or η-Al2O3. Preferred crystalline state is γ-Al2O3. The alumina powder may be formed into various shapes such as a sphere, sheet, pellet, strip or foil.

The above spherical carrier may be formed by the method of discharge of droplets in the mixture of oil-ammonia or method of discharge of droplets in the hot oil. Media in the form of a strip or foil can be obtained by conventional molding method, extrusion.

Apparent bulk density of the refractory inorganic oxide is 0.4-1.0 g/ml, the average diameter of its pores is 20-300 Å, the volume of its pores is 0.2-1.0 ml/g and specific surface area is 100-500 m2/year

The method of preparation of the catalyst in accordance with the present invention includes a separate introduction to the medium of the inorganic oxide of the metal of group IVA, Eu and CE, then the introduction of an element of group VIII metals, preferably Pt. After the introduction of each metal component is necessary what we are drying and calcination.

Upon receipt of the catalyst must first be entered IVA metal of the group, the Eu and the CoE, and the order of their entry may be optional. First, there may be a metal of group IVA, and then the Eu and the CoE, or Vice versa. Eu and CE can be introduced simultaneously or separately. However, the calcination is preferably carried out after the introduction of each metal component, thereby providing a stable combination between the introduced component and a carrier.

IVA metal component group can be incorporated into the catalyst by methods necessary to achieve a homogeneous distribution. For injection may be used precipitation, ion exchange or impregnation. Impregnation is the impregnation of the carrier with a solution of a soluble compound of a metal of group IVA and filling or dispersion solution around the material of the porous media. Suitable soluble compounds of metals of group IVA represent their oxides, chlorides, nitrates, or alkoxides, such as bromide, tin(II)chloride tin(II)chloride tin(IV)chloride pentahydrate of tin(IV)dioxide, Germany tetraethoxide Germany, tetrachloride Germany, nitrate of lead, acetate of lead or chromate of lead. Preferred are chloride tin(IV)tetrachloride Germany or chromate of lead, as part of Halogens can be introduced from Viseu asanami chlorides together with metal components. In addition, the metal components of the IVA group can also be introduced during retrieval of the media.

Cerium and europium can be introduced into the catalyst by any suitable method known to the experts in this field, such as coprecipitation, joint gelation, coextrusion with a porous carrier, or ion exchange with gelatinising the carrier and so the Preferred way is to add the corresponding hydrated oxides or oxyhalogenation cerium and europium and joint gelation or coprecipitation during retrieval of the media and subsequent drying and calcination of the solid. Suitable lanthanoide compounds that can form soluble Sol or dispersible Sol, are trichloride lanthanum or lanthanum oxide.

Another preferred method of introduction of cerium and europium involves the use of soluble compounds of cerium and europium solution for impregnation of porous media. Suitable solvents for the formation of an impregnating solution include alcohols, ethers, acids, of which preferred are inorganic acids such as HCl, HNO3and the like, and organic acids such as oxalic acid, malonic acid, citric acid and similar acids. Soluble is e connection used for impregnation of the carrier, are salts of these metals, compounds or complexes of cerium and europium, such as nitrates, chlorides, fluorides, organic alkylates, hydroxides, oxides, of which preferred are the nitrate of cerium, europium nitrate, cerium chloride, europium chloride, cerium oxide or the oxide of europium. Eu and CE can be introduced into the carrier simultaneously or separately. The introduction of Eu and CE can be performed either before or after or during the introduction of the metal of group VIII, preferably after the introduction of the metal of group VIII.

Present in the catalyst metals of group VIII are components of a noble metal which can be introduced into the carrier in any suitable manner such as coprecipitation, ion exchange or impregnation, etc. Preferred method involves the use of soluble, degradable compounds of metals of group VIII, intended for impregnation of the carrier. Non-limiting examples of suitable water-soluble compounds or complexes of metals of group VIII include: platinol acid, ildiavolovestepradfn acid, pallavoloriotorto.net acid, chloroplatinic aluminum, latinobarometro acid, trichloride platinum tetrachloride hydrate, platinum, dichlorocarbanilide platinum, dinitrodiphenylamine, tetranitro platinum(II) sodium, the palladium chloride, palladium nitrate, palladium sulfate, hydroxide diamondblade(II)chloride terminally, chloride examinable, carbonylchloride rhodium, hydrate trichloride rhodium, rhodium nitrate, hexachlororhodate(III) sodium, hexanitrate(III) sodium, tribromide iridium, iridium dichloride, iridium tetrachloride, hexanitroethane(III) sodium, GLORIETTA potassium or GLORIETTA sodium, potassium oxalate and rhodium. Preferred chlorine-containing compounds of Pt, Ir, Rh or Pd, such as platinochloride acid, ildiavolovestepradfn acid, pallavoloriotorto.net acid or a hydrate trichloride rhodium. To facilitate the introduction of halogen and homogeneous distribution of the different metal components in the material of the carrier in an impregnation solution during the process of introduction of platinum may be added hydrochloric acid or similar acids, such as hydrofluoric acid. In addition, it is generally preferable ignited media after impregnation of the carrier metal of group VIII in order to reduce the risk of leaching of metals of group VIII on other stages of impregnation. The preferred way is the introduction of a metal of group VIII after the introduction of other metal components, which minimizes loss of the metal of group VIII on other stages of impregnation. Usually the metal of group VIII uniformly dispersed in the utilizatori or dispersed so to its concentration gradually decreased from the surface to the middle of the grains of the catalyst.

At each stage of the above-mentioned operation, the introduction of metal components after the introduction of each metal component is needed drying and calcination. Drying temperature is 25-300°and the temperature of annealing is 370-700°C, preferably 550-650°C. the Calcination is usually carried out in oxygen-containing atmosphere, and the preferred atmosphere for the annealing is air. The time of annealing is determined taking into account the necessity of making the most of the metallic components present in the catalyst into the corresponding oxides. The time of ignition varies with change of temperature oxidation and depending on the oxygen content, and it is preferably 0.5 to 10 castor in accordance with the present invention may also contain other components or mixtures thereof, which act separately or in combination as modifiers catalyst designed to increase the activity, selectivity or stability of the catalyst. These catalyst modifiers include Rh, In, Co, Ni, Fe, W, Mo, Cr, Bi, Sb, Zn, Cd or Cu. These components can be introduced into the material of the carrier in any suitable way during or after the process is as it is received, either before, after or during the introduction of the other components of the catalyst in accordance with the present invention. The contents of the specified modifier is 0.05-5.0 wt.%.

The catalyst in accordance with the present invention may also contain alkali or alkaline earth metals which may be introduced into the catalyst by any known method. However, the preferred method consists in impregnating the carrier with an aqueous solution of water-soluble degradable compounds of alkali or alkaline earth metal. These alkali metals are Cs, Rb, K, Na or Li, and the above alkaline earth metals are Ca, Sr, Ba or Mg, the content of which is 0.05-5.0 wt.%.

The method of preparation of the catalyst also includes the stage of regulating the content of halogen to obtain a suitable acid catalyst. The compounds used for the introduction of Halogens, preferably represents chlorine, HCl or organic compound, which can be decomposed with obtaining chlorine, such as dichloromethane, trichloromethane, carbon tetrachloride. Temperature regulation of the content of halogen is 370-700°and its duration is 0.5 to 5.0 hours or more. During this stage, an appropriate amount of water, and the molar respect to the tion of water to HCl is 1.0-150:1. The operation regulation of the content of the halogen may occur either during, before or after calcination of the catalyst. Halogen content in the final catalyst product is preferably 0.2 to 4.0 wt.%.

In accordance with the present invention before use of the catalyst is necessary to carry out the stage of restoration for the recovery of a metal component of group VIII in the corresponding elemental metallic state and to ensure its uniform distribution throughout the media of the refractory inorganic oxide. The stage of restoration should be carried out in a substantially anhydrous environment, i.e. the water content in the reducing gas should be, for example, less than 20 ppm (mass ppm). Preferred the reducing gas is a hydrogen, but can also be used other reducing gases such as CO. Temperature recovery is 315-650°and the preferred recovery time is 0.5 to 10.0 hours. Stage of recovery can be done before loading the catalyst into the reactor, or it can be done in situ before the reaction of the reformer.

The catalyst in accordance with the present invention is suitable for catalytic reforming of naphtha to improve the octane what about the number of gasoline and yield of aromatic compounds. This naphtha rich in naphthenes and paraffins selected from fully boiling gasoline having an initial boiling point in accordance with ASTM D-86 40-80°and an end boiling point of 160 to 220°C, light gasoline with a boiling range 60-150°or heavy naphtha with a boiling range of 100-200°C. a Suitable raw materials for the reformer is a gasoline direct distillation, partially subjected to the process of reforming naphtha or dehydrogenated naphtha, thermally or catalytically crakereanda fraction of gasoline and synthetic gasoline.

When the catalyst in accordance with the present invention is used in catalytic reforming, the absolute pressure is 100 kPa to 7 MPa, preferably 350-2500 kPa; temperature is 315-600°C, preferably 425-565°C; molar ratio hydrogen/hydrocarbons is 1-20, preferably 2-10; hourly average volumetric rate of flow of the liquid raw material (LHSV) of 0.1-10 h-1preferably 1-5 hours-1.

The reforming process should be carried out in a substantially anhydrous environment. The water content of the feedstock entering the conversion zone, should be less than 50 ppm, preferably less than 20 hours per million of Water in the source for the reforming raw material may be removed using conventional adsorbents such as molecular sieves, or with what the actual content can be adjusted by appropriate methods of distillation in a fractionation column. In the feedstock water can also be removed combined method includes drying the adsorbent and the operation of the distillation. The water content of the hydrogen stream entering the conversion zone hydrocarbons, preferably 10-20 ppm or less.

The catalyst in accordance with the present invention is also suitable for other conversion reactions of hydrocarbons such as dehydrogenation, hydrogenation, hydrocracking, hydrogenolysis, isomerization, desulfuromonas, cyclization, alkylsilane, cracking and hydroisomerization of hydrocarbons.

The catalyst in accordance with the present invention preferably is used in an environment that does not contain sulfur. The desulfurization of naphtha can be accomplished in any conventional manner such as adsorption desulfurization, catalytic desulfurization, etc. In the process of adsorptive desulphurization is possible to use molecular sieves, crystalline aluminosilicates, SiO2-Al2O3c high specific surface area, activated carbon, metal-containing compounds with high specific surface, such as compounds containing Ni or Cr and having a high specific surface area, and similar compounds. For the catalytic desulfurization can be used traditional is the means, such as Hydrotreating, hydrobromide or hydrodesulfurization, and the like.

Figure 1 is a graphical dependence of selectively catalysts in accordance with the present invention compared with that of comparative catalyst containing Eu.

Figure 2 is a graphical dependence of selectively catalysts in accordance with the present invention in comparison with those of comparative catalysts a and C, containing the Eu.

Figure 3 is a graphical dependence of the activities of the catalysts in accordance with the present invention in comparison with those of comparative catalysts a and C, containing the Eu.

Figure 4 is a graphical dependence of selectively catalysts in accordance with the present invention compared with that of the CE-containing catalyst.

Figure 5 is a graphical dependence of the activities of the catalysts in accordance with the present invention compared with that of the CE-containing catalyst.

6 is a graphical relationship between the atomic ratio CE/Pt in the catalysts in accordance with the present invention and the yield of aromatic compounds.

The selectivity and stability of the activity of the catalyst in accordance with the present invention improves the camping due to concurrent modifications bimetallic catalyst through the use of cerium and europium. Compared with the catalyst, modified only by cerium or europium separately, the catalyst in accordance with the present invention provides a higher yield of liquid products and significantly reduced the rate of deposition of carbon under the same reaction conditions and the yield of aromatic compounds.

The present invention will be described in more detail by the following examples which are not limiting.

Example 1

Obtaining spherical catalyst of the present invention

(1) preparation of Sn-containing media of Al2O3

In accordance with the method of example 1 of the patent application China A 100 g of powder of aluminum hydroxide SB (obtained from Condea Chemie GmbH, Germany) and an appropriate amount of deionized water were mixed to obtain a slurry with a mass ratio of liquid/solid, equal to 2.0. Added 7.5 ml of diluted nitric acid (volume ratio 1:1), 30 g of urea and a specified quantity of a solution of tin chloride(II) in hydrochloric acid so that the Sn content in the solution was equal to 0.30 wt.% in terms of dry alumina. The resulting contents were stirred for 1 hour and was added 30 g of kerosene, 3 g of oxyethylenenitrilo fatty alcohol and stirred for a further 1 hour and then molded into the sphere of the column with the oil-AMIA the om by dripping. The wet spheres were utverjdali in ammonia water for 1 hour, then filtered, washed 2-3 times with deionized water, dried at 60°C for 6 hours at 120°C for 10 hours and was progulivali at 600°C for 4 hours to obtain Sn-containing medium (a).

(2) the Introduction of europium

100 g of the spherical carrier (a) was added to 180 ml of a solution of europium nitrate in nitric acid with a concentration of 2.27 wt.%. The ratio of liquid/solid impregnation was equal to 1.8. After soaking for 24 hours the mixture was filtered and the resulting solid was dried at 60°C for 6 hours at 120°C for 10 hours, then progulivali in an atmosphere of air containing 2-3% water vapor at 600°C for 4 hours to obtain the media containing Sn and Eu.

(3) the Introduction of cerium

Obtained in stage (2) Sn - and Se-containing media was soaked for 24 hours 180 ml of a solution of cerium nitrate with a concentration of 0.58 wt.%. The ratio of the solution/solid impregnation was equal to 1.8. The mixture was filtered, and the resulting solid was dried at 60°C for 6 hours at 120°C for 10 hours, then progulivali in an atmosphere of air containing 2-3% water vapor at 600°C for 4 hours to obtain the media containing Sn, Eu and CE.

(4) the Introduction of platinum

The media received on the preds the current stage, impregnated mixed solution obtained using a specified number of hexachloroplatinic acid, hydrochloric acid and trichloroacetic acid. The Pt content in the mixed solution should be such that the resulting catalyst contained the required amount of Pt, and the amount of hydrochloric acid and trichloroacetic acid was 1.2% and 5.0%, respectively, based on the weight of aluminum oxide and calculated on dry material. The ratio of liquid/solid in the mixed solution for impregnation of the carrier was equal to 1.8, and the impregnation time was 24 hours. Soaked and filtered, the solid is activated at 510°C for 6 hours in an air atmosphere at a molar ratio of water to HCl 60:1, and then restored at 500°With pure hydrogen with obtaining catalyst F, the composition of which is shown in table 1. The content of Pt, Sn, Eu, and CE was measured by x-ray fluorescence spectrometry, and the chlorine content was measured by an electrode method.

Example 2

Catalyst G was obtained in accordance with the method of example 1, except that the concentration of the solution of cerium nitrate for the introduction of cerium on the stage (3) was equal to 1.42 wt.%, the solid is impregnated with europium and cerium in the stages (2) and (3), progulivali in air atmosphere at 650°C for 6 hours. With the becoming of G catalyst after reduction with hydrogen is shown in table 1.

Example 3

Catalyst H was obtained in accordance with the method of example 1, except that the concentration of the solution of cerium nitrate for the introduction of cerium on the stage (3) was equal to 1.70 wt.%, impregnated with Pt and filtered, the solid is activated at stage (4) in air atmosphere at 560°and the molar ratio of water to HCl 50:1 for 6 hours. The composition of the catalyst H after reduction with hydrogen is shown in table 1.

Example 4

Catalyst I received in accordance with the method of example 1, except that in the Sn-containing media was first introduced cerium, then it was introduced europium, and the concentration of the solution of cerium nitrate, used for impregnation stage, Behold, amounted to 4.98% (mass). The catalyst composition I after reduction with hydrogen is shown in table 1.

Example 5

In the present example describes the simultaneous introduction of europium and cerium in the media using the method of joint compound.

100 g of Sn-containing medium (a)obtained in example 1 were simultaneously infused 180 ml of a solution containing 1.70 wt.% nitrate of cerium and 0.62 wt.% of europium nitrate. Obtained by filtration, the solid was dried at 60°C for 6 hours at 120°C for 10 hours, then progulivali at 600°C in air atmosphere containing 2-3% water vapor for 4 hours and then impregnated Pt in the accordance with the methodology stage (4) in example 1 to obtain catalyst J, the composition of which is shown in table 1.

Example 6

Catalyst K was obtained in accordance with the method of example 1, except that the impregnating solutions used in the stages (2) and (3), consisted of 180 ml 3.78 wt.% solution of europium chloride and 1.29 wt.% solution of chloride of cerium, respectively. The composition of the catalyst, the recovered hydrogen is shown in table 1.

Comparative example 1

Obtaining spherical catalyst containing Pt, Sn and Eu.

The catalyst obtained according to the method of example 1, except that cerium in the media did not enter, and the impregnating solution for the introduction of europium was a 180 ml of 0.62 wt.% solution of europium nitrate. The composition of the catalyst As shown in table 1.

Comparative example 2

The catalyst obtained in accordance with the method of comparative example 1, except that the impregnating solution for the introduction of europium was a 180 ml 1.36 wt.% solution of europium nitrate. The composition of the obtained catalyst are shown in table 1.

Comparative example 3

The catalyst obtained in accordance with the method of comparative example 1, except that the impregnating solution for the introduction of europium was a 180 ml 2.31 wt.% solution of europium nitrate. The composition of the catalyst shown in table 1

Comparative example 4

Obtaining spherical catalyst containing Pt, Sn and CE.

The catalyst obtained according to the method of example 1, except that europium in the media did not enter, and the impregnating solution for the introduction of cerium was a 180 ml 1.70 wt.% solution of cerium nitrate. The composition of the obtained catalyst E are shown in table 1.

Example 7

This example shows the valence (oxidation state) lanthanoide element in the catalyst of the present invention.

Spectrum of absorption of hydrogen catalysts F, G, H, I, J and comparative catalysts a, b were measured by the following method: implemented recovery when the programmed temperature using 3 mol.% H2in Not, and with the rise of temperature from room temperature to 800°With speed 8°in a minute. Peak recovery below 600°With integrated to calculate the consumption of hydrogen. The results are shown in table 2.

From the table 2 that the catalysts F, G, H, I, J have a high consumption of hydrogen in comparison with catalysts a and b that do not contain the CE. High consumption of hydrogen indicates that more than 85% CE in the catalyst of the present invention has the oxidation state +3.

Example 8

In this example, the estimation of the selectivity of the catalysts of this is th invention.

In the micro-reactor was loaded with 2 g of catalyst. As a source of raw materials used naphtha direct distillation temperature 86-151°With whose properties are shown in table 3. Evaluation conditions were as follows: pressure 0,70 MPa, an hourly average volumetric feed rate 2 h-1, the volume ratio of hydrogen/hydrocarbon 800:1. The temperature during the reaction was regulated at the level of 490°, 500°C, 510°and 520°respectively to change the yield of aromatic compounds. The evaluation results are shown in figure 1.

As follows from figure 1, in the case of the same output aromatic compounds catalysts F-I of the present invention provide an increased outputcompared with the comparative catalyst, which indicates that the selectivity of the catalysts of the present invention is significantly increased as compared with the comparative selectivity of the catalyst containing only europium.

Example 9

Catalysts J of the present invention and comparative catalysts a and C were evaluated in the microreactor under conditions assessment and using the same crude oil that used in example 8. The results are shown in figure 2 and 3.

Figure 2 shows that in case of the same content of the Eu, when achieved the same yield of aromatic compounds, o is d when using catalyst J was 2 wt.% higher output obtained when using catalyst A. the Yield of liquid productsobtained when using catalyst J was slightly higher output obtained with the use of the catalyst, which had a high content of Eu.

However, as follows from figure 3, in the case of the same output aromatic compounds, the temperature required for the catalyst, 5-8°C above the temperature required for catalyst J, which indicates that the activity of the catalyst is significantly lower than the activity of the catalyst J.

Example 10

Catalysts J of the present invention and a comparative catalyst E was evaluated in the microreactor under conditions assessment and using the same crude oil that used in example 8. The results are shown in figure 4 and 5.

Figure 4 shows that when the catalyst of the present invention compared with the comparative catalyst E, which contains only CE, in the case of the same output aromatic compounds exitwhen using catalyst J was 2 wt.% higher output obtained when using catalyst E, which indicates that the selectivity of the catalyst of the present invention is higher than the comparative selectivity of the catalysate is RA. As follows from figure 5, in the case of the same output aromatic compounds, the temperature required for catalyst E, which is the same as for catalyst J, which indicates that the activity of catalyst E is comparable to the activity of the catalyst J.

Example 11

The rate of deposition of carbon on the catalyst was evaluated in accordance with the method RIPP107-90 [see: "Analytic Methods in Petrochemical Industry" (Analytical techniques in the petrochemical industry) (test method RIPP) Cuiding Yang et al.]. The measuring device used for evaluation was a device for determining the carbon/sulfur produced by the LEGO Company, USA. The results are shown in table 4. The relative deposition rate of carbon are shown in table 4, were calculated according to the following formula:

The relative deposition rate of carbon %=The carbon content in the catalyst×100%
The carbon content in the comparative catalyst

Comparative catalyst used to determine the deposition rate of carbon was a Pt-Sn catalyst obtained in stages (1) and (4) in example 1, in which the content of Pt was equal to 0.34 wt.%, and the content of Sn was equal to 0.30 wt.%.

Ka is evident from table 4, the rate of deposition of carbon on the catalyst of the present invention to some extent less than the rate of deposition on the catalysts a, b and C, which contain only the Eu, and catalyst E containing only that, with the increase in catalyst content of CE and Eu rate of deposition of carbon on the catalyst tends to decrease. In addition, in case of the same content in lanthanide catalyst, the relative rate of deposition of carbon on the catalyst E of the present invention is lower than that for the comparative catalyst C.

Example 12

In this example, the estimation of the influence of the content of cerium on the selectivity of the catalysts of the present invention.

Catalysts F, G, H, I, J and a comparative catalyst was evaluated in accordance with the method of example 8. The evaluation results are shown in Fig.6.

As is evident from Fig.6, when the atomic ratio CE/Pt in the catalyst is less than 1.3, the yield of aromatic compounds is not reduced significantly, and Vice versa, the yield of aromatic compounds part increases when the temperature is above 500°C. However, when the atomic ratio CE/Pt in the catalyst is more than 2.2, the yield of aromatic compounds will decrease.

Table 1
# example no catalystPt, wt.%Sn, wt.%Eu, wt.%Ce, wt.%Cl, wt.%
1F0,330,300,330,181,15
2G0,330,300,330,391,12
3N0,330,300,330,490,97
4I0,330,300,331,171,20
5J0,330,300,150,481,15
6K0,340,300,490,481,16
Comparative example 1And0,330,300,15-1,18
Comparative example 2In0,330,300,33-1,15
Comparative example 30,330,300,56-1,15
Comparative example 4E 0,330,30-0,481,25

Table 2
CatalystAJBFGHI
the consumption of hydrogen, µmol/g66,783,372,2to 78.386,089,2108,8

Table 3
Density (20°C), kg/m3727,4
Distillation, ASTM D-86, °IBP/50%/EP86/109/151
Composition, wt.% naphthenes/paraffin/aromatic compounds55,70/41,38/2,92
Potential aromatic content, wt.%41,59

Table 4
no catalystABCEFGHIJK
The relative deposition rate of carbon %0,800,800,730,800,70/td> 0,650,580,400,640,53

1. Polymetallic reforming catalyst containing the following components in wt.%:

The metal of group VIII0,01-2,0
The metal of group IVAof 0.01 to 5.0
Euof 0.01 to 10.0
CEof 0.01 to 10.0
Halogen0,10-10,0
and Inorganic refractory oxide63,00-99,86

2. The catalyst according to claim 1, containing the following components in wt.%:

The metal of group VIII0,05-1,0
The metal of group IVAof 0.10 to 2.0
Eu0,05-2,0
CE0,05-2,0
Halogen0.20 to 4.0
and Inorganic refractory oxide89,00-99,55

3. The catalyst according to claim 1 or 2, in which more than 60% of CE is present in oxidation state +3.

4. The catalyst according to claim 3, wherein said refractory inorganic oxide is alumina.

5. The catalyst according to claim 4, wherein said alumina is a high purity aluminum oxide obtained by hydrolysis of alcox is Yes aluminum.

6. The catalyst according to claim 3, wherein said metal of group VIII is platinum metal group IVA is a tin and halogen represents chlorine, the atomic ratio Eu/Pt in the catalyst is 0.2 to 3.0:1 and the atomic ratio Ce/Pt in the catalyst is 0.2 to 5.0:1.

7. The catalyst according to claim 6, in which the atomic ratio Eu/Pt in the catalyst is 0.5-1.0:1 and the atomic ratio Ce/Pt in the catalyst is 0.5 to 3.0:1.

8. The method of preparation of the catalyst according to claim 1, which includes a separate introduction to the medium of the inorganic oxide of the metal of group IV, Eu and CE, the subsequent introduction of a metal of group VIII, drying and calcination of each component after each injection.

9. The method of claim 8, wherein said metal of group VIII is platinum.

10. The method according to claim 8, in which the Eu and the CoE simultaneously injected into the carrier by co-precipitation or co-impregnation during the preparation of the catalyst.

11. The method according to claim 8, in which the halogen is injected method of regulating the water content and chlorine, in which the temperature is 370-700°and the molar ratio of water to HCl is 1.0-150:1.



 

Same patents:

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2 cl, 1 tbl, 3 ex

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2 cl, 1 tbl, 3 ex

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10 cl, 5 ex

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