Method of impregnation by a metal of a molecular sieve extrudate with a cementing material

FIELD: powder metallurgy; method of impregnation by a metal(of VIII group) of a molecular sieve extrudate with cementing material with the help of ion exchange with an aqueous solution of metal salt of VIII group.

SUBSTANCE: the invention presents a method of impregnation by metal of VIII group of an extrudate of a molecular sieve with cementing material, in which the cementing material represents a refractory oxidic material with a low acidity, practically free of aluminum oxide, using: a) impregnation of porous volume of an extrudate of a molecular sieve with cementing material with an aqueous solution of nitrate of the corresponding metal of VIII group with pH from 3.5 up to 7, in which the molar ratio between cations of a metal of VIII group in a solution and a number of centers of the adsorption available in the extrudate, is equal to or exceeds 1; b) drying of the produced at the stage a) extrudate of the molecular sieve with the cementing material. The technical result is good distribution of the metal and a short period of drying.

EFFECT: the invention ensures good distribution of the metal and a short period of drying.

9 cl, 1 tbl, 4 ex

 

The technical field to which the invention relates.

The invention relates to a method for impregnation of a metal of group VIII of the extrudate molecular sieve with a binder material in which the binder material is a weakly acidic refractory oxide binder material, containing no alumina. In particular, the invention relates to a method for impregnation of a metal of group VIII of the extrudate molecular sieve with a binder material using ion exchange with an aqueous solution of salt of metal of group VIII.

The level of technology

A similar method described in document WO-A-9641849. In this patent publication describes the impregnation of platinum or palladium delaminating associated with silica zeolite ZSM-5 with an aqueous solution of hydroxide tetraammineplatinum or hydroxide tetraamminepalladium. After impregnation associated with silica zeolite ZSM-5 is dried for 2 h at 120°and calcined 2 hours at 300°C. Then the catalyst is activated by recovery of platinum or palladium.

The disadvantage of the impregnation method described in document WO-A-9641849 is a long drying period. Reduced drying period leads to a less favorable distribution of platinum or palladium on the associated with silica zeolite ZSM-5. It is well known that the best allocation possible to obtain, e is whether the molecular sieve prior to impregnation translate of H-shape in ammonium form. The term “ammonium form” means that the ions H+or their part in the molecular sieve are replaced by ammonium ions. An example of the translation of molecular sieves in ammonium form before impregnation are described in U.S. patent No. 5397454. In this patent publication describes the impregnation of the powder of zeolite SSZ-32 palladium. Prior to impregnation of the zeolite is subjected to four sequential stages of ion exchange with ammonium nitrate. Thereafter, the zeolite is suspended in an aqueous solution of ammonium hydroxide. Then slowly add a solution of nitrate tetraamminepalladium, the pH is increased to 9.5 by the addition of ammonium hydroxide.

In the document WO-A-9812159 describes the impregnation method, in which mordenite molecular sieve is first transferred to the ammonium form before contact with the aqueous solution containing PD(NH3)4(NO3)2.

The disadvantage of ways WO-A-9812159 and U.S. patent No. 5397454 is the long processing time for impregnation. It would be advantageous if the extrudate molecular sieves in the protonated form can be used directly in the method of impregnating the extrudate molecular sieve with a binder material.

In U.S. patent No. 4568656 described the way in which the exchange of the potassium form of zeolite L is impregnated with an aqueous solution with a pH ranging from 8.5 to 12.5 and containing a salt of platinum and eplatinum salt.

The invention

The purpose of this breath is retene is to develop a method of impregnating a metal of group VIII of the extrudate molecular sieve with a binder material with a short drying period and obtaining a good distribution of the metal. Short drying period is desirable when the catalyst was prepared in an industrial scale.

This goal is achieved as follows. In the method of impregnating a metal of group VIII of the extrudate molecular sieve with a binder material in which the binder material is a refractory oxide material with low acidity, which practically does not contain aluminum oxide and in which the molecular sieve is in the protonated form, use:

a) contacting the extrudate molecular sieve with a binder material with an aqueous nitrate solution of the respective metal of group VIII with a pH of from 3.5 to 7, in which the molar ratio between the metal cations of group VIII in the solution and the number of adsorption centers present in the extrudate, is equal to or greater than 1,

b) drying the extrudate molecular sieve with a binder material obtained in stage a).

It was shown that the method according to the invention ensures a good distribution of the metal of group VIII in a short period of drying. A further advantage of the method according to the invention is that the molecular sieve or the extrudate molecular sieve with a binder material can be used directly in the protonated form, without the need of initial translation of molecular sieve in the ammonium form.

The choice of molecular with whom one is not essential to realize the benefits of the invention, namely, a good metal distribution and short drying period. Examples of molecular sieves include metroselect, metallophosphates and metallophthalocyanine. Possible metal components in the framework of molecular sieves include such metals as Al, Fe, In, Ga, Ti, or combinations of these metals. Preferred molecular sieves are aluminosilicates, alumophosphate and aluminosilicate, such as SAPO-11, SAPO-31 and SAPO-41. Particularly preferred molecular sieves are silicates, which, in addition, referred to as zeolites. Examples of suitable zeolites include ZSM-4 (omega), ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, beta, X-, Y -, and L-zeolites, as well as ferrierite and mordenite. When the catalyst obtained after impregnating the extrudate molecular sieve with a binder material that is supposed to be used for catalytic dewaxing, it is preferable that the zeolite crystallites had pores with a maximum diameter of from 0.35 to 0.80 nm. Preferably the zeolite crystallites include zeolites of the MFI type, having pores with a diameter of 0.55 and 0.56 nm, such as ZSM-5 and silicalite, offretite having pores with a diameter of approx 0.68 nm, and the zeolite group ferrierite having pores with a diameter of 0.54 nm, such as ZSM-35 and ferrierite. Another preferred class of zeolite crystallites includes zeolites type SOUND. Examples of the zeolite is s crystallites type TON are ZSM-22, Theta-1, Nu-10, which are described in U.S. patent No. 5336478 and EPA-57049 and EPA-65400. Another preferred class of zeolite crystallites is of type MTW. Examples of the zeolite crystallites with topology type MTW, are ZSM-12, Nu-13, silicalite TEA, TPZ-3, TPZ-12, VS-12 and Theta-3, which are described, for example, in U.S. patent No. 3832449, EPA-513118, EPA-59059 and EPA-162719. The following preferred class of zeolite crystallites is of type MTT. Examples of the zeolite crystallites with topology type MTT, are ZSM-23, SSZ-32, ISI-4, KZ-1, EU-1, EU-4 and EU-13, which are described, for example, in U.S. patent No. 4076842 and 4619820, EPA-522196, EPA-108486 and EPA-42226.

The size of the primary crystallites molecular sieves may vary in a wide range from 0.001 to 5 mm For tasks catalytic dewaxing convenient to the crystallite-size zeolite was less than 100 μm. Preferably use small crystallites in order to achieve maximum catalytic activity. Preferably used crystallites less than 10 microns and more preferably less than 1 micron.

The extrudate molecular sieve with a binder material contains a refractory oxide binder material with low acidity, which practically does not contain aluminum oxide. In the invention suitable binder material includes a refractory oxides with low acidity, such as dioxide, cream the Oia, zirconium dioxide, titanium dioxide, dioxide, germanium, boron oxide and mixtures of two or more such oxides. However, the most preferred binder material is silicon dioxide. The binder material can be a natural material or may be in the form of a gel-like precipitation, sols, colloidal solutions or gels. The binder material may also be in the form of a mixture of these forms. The preferred extrudates are those obtained by the method described in U.S. patent No. 5053374.

The mass ratio of molecular sieve and a binder material may be in the range from about 5:95 to 95:5. In some cases, the low content of the molecular sieve may be preferable, for example, if the desired high selectivity, and high content of molecular sieve may be preferred, if desired increased activity.

After the extrusion, the extrudate molecular sieve with a binder material is dried in the period from 15 min to 24 h, more preferably from 1 to 3 hours at a temperature of from 10 to 350°S, more preferably from 120 to 150°C. After that, the catalytic composition is subjected to annealing, typically at a temperature of from 400 to 900°With, by heating in air for from 1 to 48 h, preferably from 1 to 10 p.m.

Stage a) of the method according to the ACLs to the invention includes contacting the extrudate molecular sieve with a binder material with an aqueous solution of nitrate salts of the respective metal of group VIII with a pH below 8, moreover, the molar ratio between the metal cations of group VIII in the solution and the number of adsorption centers present in the extrudate, is equal to 1 or greater than 1. Preferably the molar ratio between the metal cations of group VIII in the solution and the number of adsorption centers is from 1 to 20. Under the centre of adsorption understand the site on which theoretically can adsorb one cation of a metal of group VIII. The calculation of the number of adsorption centers per 1 g of extrudate can be performed as follows. The extrudate has a constant value of moles N+1 g of extrudate. The number of moles of H+1 g of extrudate is determined using temperature programmed desorption (TPD) of ammonia, as described in the journal Zeolites, 19, pp.288-396, 1997. According to the invention the number of adsorption centers in moles represents the number of moles of H+1 g of extrudate related to the valence of the cation, which is taken for impregnation. Thus, the molar ratio between the metal cations of group VIII in the solution and the number of centers of adsorption is defined as the number of moles of cations of a metal of group VIII, are related to the number of adsorption centers in moles, as defined above. It should be understood that formed after impregnation the catalyst extrudate containing modified molecular sieve with a binder material) may (and usually will) contain more metal of group VII, than the amount which can be calculated, taking into account the number of adsorption centers. Preferably, the final catalyst has a molar ratio of cations of a metal of group VIII present in the extrudate, to the number of adsorption centers present in the extrudate, is equal to the above value.

The above ratio can be achieved by any method known from the prior art. For example, this ratio may be achieved by use of such large quantities or high concentrations of nitrate salt of the metal of group VIII in an aqueous solution, to obtain the above value.

In a preferred variant embodiment of the above ratio can be achieved by reducing the number of centers of adsorption in the molecular sieve or the extrudate molecular sieve with a binder material prior to contacting the extrudate molecular sieve with a binder material with the solution of stage a). The number of centers of adsorption in the molecular sieve can be reduced by reducing the number of acid sites in the zeolite crystallites. Reducing the number of acid sites can be achieved by methods known from the prior art, for example, subjecting the extrudate molecular sieve with a binder material to hydrothermal treatment, nab the emer by treating the particles with water vapor at a temperature between 400 and 900° C.

If the extrudate molecular sieve with a binder material contains silicates as molecular sieves, it was found that it is advantageous to expose the molecular sieve or the extrudate molecular sieve with a binder material dialuminium treatment before impregnation with the metal of group VIII by the method according to the invention. Dealumination leads to a decrease in the number of groups of the alumina present in the aluminosilicate, and therefore to decrease the molar fraction of the centers of adsorption. Dealumination can be carried out using methods known from the prior art. A particularly effective methods are those in which there is selective dealumination, or any way that is selectively flowing on the surface of the zeolite crystallites.

Examples of methods dealumination described in document WO-A-9641849. Preferably dealuminated carried out according to the method in which the molecular sieve or the extrudate molecular sieve with a binder material in contact with an aqueous solution ferrosilicates salt, and ferrosilicate salt represented by the formula

(A)2/bSiF6,

in which a represents a metal or non-metal cation that is different from the proton (H+and having a valency of b. Examples of cations b are alcelam the deposits, NH

+
4
, Mg++Li+, Na+To+BA++Cd++, C+, CA++Cs+, Fe++With++, Pb++, Mn++, Rb+Ag+, Sr++, TL+and Zn++. Preferably a represents an ammonium cation. Molecular sieve or extrudate molecular sieve with a binder material can be contacted with ferrosilicates salt, taken in an amount of at least 0,0075 mol per 100 g of the zeolite material, while the pH is from 3 to 7. The example of the above method dealumination disclosed in the U.S. patent And 5157191.

The method according to the invention can be used for impregnation of any metal of group VIII, such as Pt, Pd, Ni, Ru and Co. The corresponding nitrate salt of the metal of group VIII can be a simple salt, such as, for example, Nickel nitrate, or a complex salt, such as, for example, PT(NH3)4(NO3)2Pd(NH3)4(NO3)2, PT(NH3)6(NO3)4or Pd(NH3)6(NO3)4. For tasks catalytic dewaxing preferred are salts of Pt, Pd, Ni, and platinum is particularly preferred. For catalytic dewaxing preferred nitrate salts of a metal of the group VIII is Nickel nitrate, PT(NH3)4(NO3)2and Pd(NH3)4(NO3)2. The total number of platinum, palladium or Nickel, which are impregnated extrudate molecular sieve with a binder material is preferably less than 10 wt.% in the calculation of the element and in attributing to the total weight of the extrudate molecular sieve with a binder material, preferably it is in the range from 0.1 to 1.0 wt.%.

For impregnating the extrudate molecular sieve with a binder material according to the method of the invention can use a variety of techniques known from the prior art, such as, for example, the circulation of the impregnating solution and impregnation of the pore volume. Preferably the method of impregnation of the pore volume, which is a very time-efficient method. In this technique, the volume of solution containing a salt of metal of group VIII, which is in contact with the extrudate, almost equal to the volume of the pores of the extrudate molecular sieve with a binder material which is impregnated (see also the book Studies in Surface Sci. and Catalysis, v.58. Introduction to the science and practice of zeolites, H. Van Bekkum et al. Elsevier, 1991, p.503).

The concentration of the aqueous solution of salt of metal of group VIII, which is used to produce the desired amount of metal distributed on the extrudate molecular sieve with a binder material, MoE, what should be changed within wide limits, moreover, it affects the duration of the impregnation. Preferably the concentration of the metal of group VIII is less than 20%. When using the method of impregnation of the pore volume preferably this concentration is in the range from 0.02 to 10 wt.%, more preferably from 0.2 to 2.0%. The duration of the impregnation usually varies from 5 min to 24 h, more preferably from 5 minutes to 3 hours

Used in stage a) aqueous solution has a pH less than 8, preferably from 3.5 to 7. The aqueous solution may contain ammonium ions, provided that the pH is within the specified interval. Preferably ammonium ions are practically absent in the solution.

Used in stage a), the temperature is not set specific and can vary from below room temperature to about 100°S, more preferably from 15 to 65°C. Preferably the impregnation is carried out at room temperature as the most convenient.

The pressure may vary within a wide range and is not defined specifically. Because of the convenience of the impregnation stage a) according to the method of the invention is preferably carried out at atmospheric pressure.

Other metals can optionally be present in the extrudate molecular sieve with a binder material prior to impregnation nitrate salt of the metal of group VIII according to the method of the invention.

According to the method of the invention at the stage b) is happening the drying of the extrudate molecular sieve with a binder material, obtained in stage a). The extrudate molecular sieve with a binder material, modified at the stage a), can be dried at a temperature varying from room temperature up to 350°With, in accordance with any mode of drying known in the prior art. In a preferred variant embodiment of the extrudate molecular sieve with a binder material is dried in accordance with accelerated drying regime, the duration of which is less than 90 min and in which the temperature was raised from about room temperature up to more than 200°C, preferably to more than 250°C. the drying may include a continuous, linear or non-linear temperature rise, or may include the stage at which the temperature is maintained stable. For periodic preferred methods accelerated the drying process involves the following stages: temperature rise speed of 10 to 20°C/min to a temperature of from 150 to 200°; holding at that temperature for a time from 5 to 15 min; temperature rise speed of 10 to 40°C/min to a temperature of from 250 to 300°; holding at that temperature for a time from 10 to 20 min, cooling to room temperature. For continuous processes are preferred rapid drying mode includes continuous rise of temperature, and the temperature increase may be gradual is whether the speed of temperature rise varies. When using this fast-drying, you can cut the drying time, which is particularly beneficial when obtaining a catalyst on an industrial scale. As will be clear from the examples, the impregnation method of the invention allows the use of such accelerated drying and at the same time allows you to get a good metal distribution in the extrudate molecular sieve with a binder material.

After drying the extrudate molecular sieve with a binder material optionally calcined at a temperature of between approximately 350 and 500°C.

The catalyst containing extrudate molecular sieve with a binder material, may be activated prior to use by any method known from the prior art, for example by reduction with hydrogen cation metal of group VIII. The catalyst obtained after processing the extrudate molecular sieve with a binder material by the method according to the invention, can be used in any process of transformation of hydrocarbons, examples of such processes of transformation of hydrocarbons are hydrocracking, isomerization, alkylation, hydrogenation, dehydrogenation, polymerization, reforming, catalytic cracking and catalytic hydrocracking. The catalyst can be conveniently used in the process for catalytic dewaxing. Under the catalytic deparaffinize the second refers to the method of reducing temperature yield strength of base products lubricating oils by selective transformation of those components of the oil feedstock, which give a contribution to the high temperature yield strength products, in connection with low temperature fluidity. Products that contribute to a high temperature yield strength products, have a high melting point. These compounds belong to the wax. Waxy compounds include, for example, normal paraffins with a high melting point, ISO and monocyclic compounds. Preferably the temperature fluidity is reduced at least 10°and more preferably, at least 20°C. Examples of such methods catalytic dewaxing described in the above-mentioned document WO-A-9641849.

The catalyst may be used in the catalytic dewaxing of any hydrocarbon. Accordingly, the catalyst may be used in the catalytic dewaxing of lubricating oils, base oil products and other raw materials having a relatively high content of paraffin compounds. Examples of commodities that have a high content of paraffin compounds are synthetic paraffin and the refined (the paraffin refined of the Fischer-Tropsch process), the residual fraction hydrocracking (gidroprofil) and paraffin GAC obtained hydrotreated dewaxing or treated by selective solvent paraffin is the simple distillates.

Information confirming the possibility of carrying out the invention

Further, the method according to the invention will be illustrated in the following limitiruyuschie examples.

Comparative example a

The extrudate ZSM-5/silica (30/70% by weight)heated at 800°C, treated with a 0.01-molar aqueous solution of ammonium fluorosilicate preparation (GFA), washed, dried and calcined. This extrudate contains 0,048 mmol H+/g of extrudate. Then impregnate 22,65 g of extrudate platinum (approximately 0.7 wt.%) by impregnation of the pore volume within 5 min 5-molar aqueous solution (16,23 ml)containing 2,79 g hydroxide tetraammineplatinum, PT(NH3)4(OH)2(5.9 wt.% platinum). the solution pH is above 8. The impregnated extrudate is not washed and dried in mode, slow drying: dried for 2 h at 120°C, then the temperature was raised at a rate of 25°C/min to 190°and maintain a constant for 1 h; then the temperature again increases with the speed of 50°C/min to 300°C and maintained at this temperature for 1 h then the extrudate is cooled to room temperature. Content 0,048 mmol N+/g extrudate corresponds 0,024 mmol centers for adsorption of cations Pt2+. In 22,65 g of extrudate contains 0.54 mmol centers of adsorption. From these data we can calculate that the soda solution is separated 0.84 mmol cations Pt 2+. Thus, the molar ratio of cations platinum and centers of adsorption is 1.55V. The resulting distribution of platinum visually analyze and assess as satisfactory.

Comparative example

The extrudate ZSM-5/silica (30/70% by weight)heated at 800°C, treated with a 0.01-molar aqueous solution of ammonium fluorosilicate preparation, washed, dried and calcined. This extrudate contains 0,048 mmol N+/g of extrudate. Then impregnate 29,15 g of extrudate platinum (approximately 0.7 wt.%) by impregnation of the pore volume within 5 min aqueous solution (20,96 ml)containing 3,59 g hydroxide tetraammineplatinum, PT(NH3)4(OH)2(5.9 wt.% platinum). the pH of the solution exceeds 8. The impregnated extrudate is not washed, and dried in a regime of accelerated drying: temperature increase with the speed of 15°C/min to 180°and maintain this temperature for 10 min; again increase the temperature at a speed of 30°C/min to 290°C; hold at this temperature for 15 minutes the Molar ratio of cations platinum and centers of adsorption is 1.55V. Data on the distribution of platinum is not obtained, since the hydroxide tetraammineplatinum not decomposed.

Example 1

The extrudate ZSM-5/silica (30/70% by weight)heated at 800°With handle from 0.01 molar in denim solution of ammonium fluorosilicate preparation (GFA), washed, dried and calcined. This extrudate contains 0,048 mmol N+/g of extrudate. Then impregnate 29,15 g of extrudate platinum (approximately 0.7 wt.%) by impregnation of the pore volume within 5 min aqueous solution (20,96 ml)containing 6,82 g nitrate tetraammineplatinum, Pt(NH3)4(NO3)2(2.99 wt.% platinum). the pH of the solution is approximately equal to 6. The extrudate is not washed, and dried in a regime of accelerated drying: temperature increase with the speed of 15°C/min to 180°and maintain this temperature for 10 min; again increase the temperature at a speed of 30°C/min to 290°C; hold at this temperature for 15 minutes thereafter, the extrudate is cooled to room temperature. The molar ratio of cations platinum and centers of adsorption is 1,49. You get a good distribution of platinum.

Example 2

The extrudate ZSM-5/silica (30/70% by weight)heated at 800°C, treated with a 0.01-molar aqueous solution of ammonium fluorosilicate preparation (GFA), washed, dried and calcined. This extrudate contains 0,048 mmol N+/g of extrudate. Then impregnate 47,96 g of extrudate to the Nickel content of about 0.7 wt. % by impregnation of the pore volume within approximately 15 minutes with an aqueous solution (30,74 ml)containing 1.68 g of nitrate salts of Nickel, Ni(NO3)2*6N2O. the pH of the races the thief is approximately equal to 4. The extrudate was washed, dried and calcined in the regime of accelerated drying: temperature increase with the speed of 15°C/min to 180°and maintain this temperature for 10 min; again increase the temperature at a speed of 30°C/min to 300°C; hold at this temperature for 15 minutes

Thereafter, the extrudate is cooled to room temperature. The molar ratio between Nickel cations and adsorption centers present in the extrudate, is 5.0. You get a good distribution of Nickel.

The generalization of the results obtained in the examples given in the table. In the comparative example And obtained satisfactory distribution of metal using hydroxide tetraammineplatinum and slow drying. When using accelerated mode instead of drying slow drying mode, as shown in the comparative example, it was found that the complex hydroxide tetraammineplatinum does not decompose. When this catalyst is subsequently activated in a reducing atmosphere, there is a migration of platinum on the outer surface of the catalyst, which leads to unacceptable loss properties of the catalyst. Examples 1 and 2 show that it is possible to use accelerated drying and at the same time achieve complete decomposition of the complex, as well as good distribution of the metal, when according invented the Yu uses nitrate complex of a metal of group VIII.

1. The method of impregnation of the metal of group VIII of the extrudate molecular sieve with a binder material in which the binder material is a refractory oxide material with low acidity, almost not containing aluminum oxide and in which the molecular sieve is in the protonated form, characterized in that exercise a) impregnation of the porous volume of the extrudate molecular sieve with a binder material with an aqueous solution of nitrate of a corresponding metal of group VIII with a pH of from 3.5 to 7, in which the molar ratio between the metal cations of group VIII in the solution and the number of adsorption centers present in the extrudate, is equal to or greater than 1,

b) drying the extrudate molecular sieve with a binder material obtained in stage a).

2. The method according to claim 1, characterized in that the ratio between cations of a metal of group VIII and the number of adsorption centers is from 1 to 20.

3. The method according to claim 1 or 2, characterized in that the number of adsorption centers in the extrudate molecular sieve with a binder material is reduced to the impregnation of the metal of group VIII using dialuminium processing.

4. The method according to claim 3, characterized in that dialuminium treatment includes contacting the extrudate molecular sieve with a binder material with a solution of ammonium fluorosilicate preparation.

5 the Method according to any one of claims 1 to 4, characterized in that the metal of group VIII is a Ni, Pt or Pd.

6. The method according to any one of claims 1 to 5, characterized in that the nitrate salt of the metal of group VIII is a Ni(NO3)2·6N2O, PT(NH3)4(NO3)2or PD(NH3)4(NO3)2.

7. The method according to any one of claims 1 to 6, characterized in that the molecular sieve is a zeolite of the MFI type, TON, MTT or MTW.

8. The method according to any one of claims 1 to 7, characterized in that the binder material is a silicon dioxide.

9. The method according to any one of claims 1 to 8, characterized in that stage b) is carried out in a regime of accelerated drying with a duration of less than 90 min, and the temperature was raised from room temperature up to more than 200° C.



 

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FIELD: petroleum processing catalysts.

SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.

EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.

40 cl, 2 tbl, 19 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides reforming catalyst containing Pt and Re on oxide carrier, in particular Al2O3, wherein content of Na, Fe, and Ti oxides are limited to 5 (Na2O), 20 (Fe2O3), and 2000 ppm (TiO2) and Pt is present in catalyst in reduced metallic state and in the form of platinum chloride at Pt/PtCl2 molar ratio between 9:1 and 1:1. Contents of components, wt %: Pt 0.13-0.29, PtCl2 0.18-0.04, Re 0.26-0.56, and Al2O3 99.43-99.11. Preparation of catalyst comprises impregnation of alumina with common solution containing H2PtCl6, NH4ReO4, AcOH, and HCl followed by drying and calcination involving simultaneous reduction of 50-90% platinum within the temperature range 150-550оС, while temperature was raised from 160 to 280оС during 30-60 min, these calcination conditions resulting in creation of reductive atmosphere owing to fast decomposition of ammonium acetate formed during preparation of indicated common solution.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 3 ex

FIELD: hydrocarbon conversion catalysts.

SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.

EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

FIELD: alternate fuel manufacture catalysts.

SUBSTANCE: invention relates to generation of synthesis gas employed in large-scale chemical processes such as synthesis of ammonia, methanol, higher alcohols and aldehydes, in Fischer-Tropsch process, and the like, as reducing gas in ferrous and nonferrous metallurgy, metalworking, and on gas emission detoxification plants. Synthesis gas is obtained via catalytic conversion of mixture containing hydrocarbon or hydrocarbon mixture and oxygen-containing component. Catalyst is a complex composite containing mixed oxide, simple oxide, transition and/or precious element. Catalyst comprises metal-based carrier representing either layered ceramics-metal material containing nonporous or low-porosity oxide coating, ratio of thickness of metallic base to that of above-mentioned oxide coating ranging from 10:1 to 1:5, or ceramics-metal material containing nonporous or low-porosity oxide coating and high-porosity oxide layer, ratio of thickness of metallic base to that of nonporous or low-porosity oxide coating ranging from 10:1 to 1:5 and ratio of metallic base thickness to that of high-porosity oxide layer from 1:10 to 1:5. Catalyst is prepared by applying active components onto carrier followed by drying and calcination.

EFFECT: increased heat resistance and efficiency of catalyst at short contact thereof with reaction mixture.

13 cl, 2 tbl, 17 ex

FIELD: polymer production and polymer production catalysts.

SUBSTANCE: invention relates to synthesis of catalysts for production of cis-polybutadiene and butadiene/isoprene cis-copolymer, which can be employed in synthetic rubber industry. Task of invention resides in providing a novel method for synthesis of high-activity catalytic component, in particular neodymium neodecanoate, by reaction of neodymium oxide with neodecanoic acid in presence of metal chloride catalysts characterized by low acidity enabling conduction of process in stainless steal apparatuses and so making it possible to exactly controlling molar ratio of neodymium neodecanoate to free neodecanoic acid and water. Catalytic complex is formed by mixing neodymium neodecanoate-based catalytic component with butadiene, triisobutylaluninum, and diisobutylaluninum hydride in hydrocarbon solvent. Polymerization of butadiene or copolymerization of butadiene with isoprene is carried out in presence of thus formed catalytic complex in hydrocarbon solvent.

EFFECT: increased percentage of cis-1,4 units in polybutadiene or butadiene/isoprene copolymer and narrowed polymer or copolymer molecular weight distribution.

11 cl, 1 tbl, 45 ex

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

FIELD: alternative fuel production and catalysts.

SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.

EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.

6 cl, 2 tbl, 16 ex

FIELD: alternative fuel production and catalysts.

SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.

EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.

6 cl, 2 tbl, 16 ex

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