Gydroprocessing zeolite-containig catalyst with high mesoporosity

FIELD: chemistry.

SUBSTANCE: invention refers to the bifunctional catalyst possessing the hydrogenising as well as acid function. The method for the preparation of the catalyst for hydrocarbon conversion includes: (a) obtaining of complex compounds as precursors of non-crystalline inorganic oxide with mesopores disorderedly connected together; (b) usage of the complex compounds from stage (a) for the preparation of the composite containing zeolite incorporated into inorganic oxide with mesopores disorderedly connected together; (c) incorporation of the at least one metal possessing the hydrogenising function to the composite obtained on the stage (b).

EFFECT: obtaining of the catalyst with enhanced operational versatility for control of the acid and hydrogenising functions.

13 cl, 13 ex, 3 tbl, 5 dwg

 

CROSS-REFERENCE TO RELATED APPLICATIONS

Priority application for the present patent application is U.S. provisional application No. 60/607607, filed September 7, 2004 This application is a partial continuation of simultaneously pending U.S. application No. 11/101858 filed April 8, 2005, which is a divisional application of U.S. application No. 10/313720, filed December 6, 2002, which is a partial continuation of U.S. application No. 09/995227, filed November 27, 2001, now published as U.S. Patent No. 6762143, which is a partial continuation of U.S. application No. 09/390276, filed September 7, 1999, and currently published in U.S. Patent No. 6358486, which claimed priority, all of the above applications and/or patents are incorporated herein by reference.

BACKGROUND of INVENTION

1. The technical field to which the invention relates

The present invention relates to a bifunctional catalyst having as hydrogenation and acidic by function.

2. The prior art related to the invention of

Most modern hydrocarbon processing technologies based on zeolite catalysts. Zeolite catalysts are well known in the relevant region, the STI technique and possess a well-ordered system of pores with uniform pore sizes. However, these materials tend to have either only micropores or mesopores. Micropores are defined as pores having a diameter of less than about 2 nm. The mesopores are defined as pores having a diameter in the range from about 2 nm to about 50 nm.

Because the reactions of hydrocarbon processing is limited by mass transfer, the catalyst with the ideal pore size will facilitate the transfer of reactants to the active sites of the catalyst and the transfer of products outside of the catalyst.

There is still a need for an improved material with functionalized sites in the porous structure for the implementation of processes for the catalytic conversion and/or adsorption of hydrocarbons and other organic compounds.

The INVENTION

The present invention provides a catalyst for the conversion of hydrocarbons, the catalyst contains at least three components (1)at least one element with a hydrogenation function, (2) at least one type of microporous zeolite and (3) a porous, non-crystalline inorganic oxide having disordered connected to each other in the mesopores, and having a reflection x-ray radiation in the range of 2θ between 0.5 and 2.5 degrees.

BRIEF DESCRIPTION of DRAWINGS

The invention described in the following with reference to the drawings, in which:

Figure 1 illustrates x-ray diffraction (PD) of pure zeolite beta (β) and zeolite beta/TUD-1, prepared in Examples 1, 2 and 3;

Figure 2 illustrates misoprostol pure zeolite beta and beta/TUD-1, prepared in Examples 1, 2 and 3;

Figure 3 illustrates x-ray diffraction (PD) for mesoporous material, zeolite MCM-22 and a composite material prepared in Example 4;

Figure 4 illustrates the size distribution of mesopores composite zeolite/TUD-1, prepared in Example 4; and

Figure 5 illustrates x-ray diffraction (PD) of pure zeolite Y and Sample 5 prepared in Example 5.

A DETAILED description of the PREFERRED OPTIONS of the INCARNATION

The catalyst according to the invention has a new composition mainly containing three active components: (1) at least one metal selected from groups VIII, IB, IIB, VIIB and VIB in the periodic table of elements; (2) at least one type of microporous zeolite provides low acid function; and (3) non-crystalline inorganic oxide having disordered connected to each other by mesopores in the range from 1.5 to 25 mm in diameter. The catalyst also optionally may include boron and/or phosphorus as an additional component. For the physical integrity of the catalyst may additionally sodergatsja.

Metal mostly chosen from transition metals, noble metals and their alloys. These metals include titanium, vanadium, zirconium, manganese, zinc, copper, gold, lanthanum, chromium, molybdenum, Nickel, cobalt, iron, tungsten, palladium, rhodium, ruthenium and platinum. Some metals can be placed on the porous surface of the mesoporous inorganic oxide; some of them can be embedded in the structure of the zeolite as Vice atoms of the crystal lattice and/or be placed inside the micropores of the zeolite. Some metals can be placed in the structure of the zeolite in the form of bundles of catalyst.

The metal content in the catalyst, depending on the particular application is in the range of 0.3-30 wt.%, based on the weight of the catalyst. For noble metals is preferable that the content was in the range of 0.2-5 wt.%, and for transition metals is in the range of 3-30 wt.%.

The zeolite described in this document, includes a microporous zeolite entered in noncrystalline porous inorganic oxide. Microporous zeolite can be any of the possible types of microporous zeolites. As some examples zeolite β, zeolite Y (including an ultra-stable zeolite Y" - USY), modernit, zeolite L, ZSM-5, ZSM-11, ZSM-12, ZSM-20, Theta-1, ZSM-23, ZSM-34, ZSM-35, ZSM-48, SSZ-32, PSH-3, MCM-22, MCM-49, MCM-5, ITQ-I, ITQ-2, ITQ-4, ITQ-21, SAPO-5, SAPO-Il, SAPO-37, Breck-6 (also known as EMT), ALPO4-5, etc. Such zeolites are known in the art and many are commercially available. In this invention, the zeolite can be entered in the inorganic oxide or synthesize directly in noncrystalline porous oxide.

The content of zeolite in the catalyst may be in the range of from about less than 1 wt.% up to more than 99 wt.% or any range in between. However, it is preferable that was in the range of from about 3 wt.% up to 90 wt.%, and more preferably from about 4 wt.% up to 80 wt.%. Also is preferred that the catalyst containing the zeolite contained approximately not more than 10 volume percent of micropores.

It is preferable that non-crystalline, porous inorganic oxide was three-dimensional mesoporous inorganic oxide material containing at least 97 volume percent mesopores (i.e., not more than 3 volume percent of micropores), based on micropores and mesopores inorganic oxide material (i.e. without any embedded zeolite), and typically at least 98 volume percent mesopores. This material is described in U.S. Patent No. 6358486 and marked as TUD-1. The preferred method of obtaining porous inorganic oxide is disclosed in U.S. Patent No. 6358486 the American patent application No. 10/764797.

The main chemical composition of the preferred porous inorganic oxide (TUD-1) includes, but is not limited to, silicon dioxide, aluminum oxide, aluminum silicate, titanium oxide, zirconium dioxide, magnesium oxide and combinations thereof. Porous inorganic oxide TUD-1 may further comprise vanadium, zinc, copper, gold, gallium, lanthanum, chromium, molybdenum, Nickel, cobalt, iron, and tungsten.

TUD-1 is a non-crystalline material (i.e., cristallinity confirmed by currently available technologies x-ray diffraction). The average size of the mesopores, as determined from measurements of porosity with nitrogen is in the range of about 2-25 nm. The surface area of the inorganic oxide, as determined using the BET (nitrogen), preferably is in the range of about 200-1200 m2/g Is preferable that the volume of its pore space was in the range of about 0.3-2.2 cm3/year

According to the U.S. Patent 6358486 and U.S. patent application No. 10/764797 mesoporous inorganic oxide is usually prepared by heating a mixture of (1) chemical precursor of an inorganic oxide and (2) exemplary organic reagent, which mixes well with the chemical precursor of oxide or groups of oxides, generated by chemical what Resistencia. The source material is generally amorphous material and may consist of one or more inorganic oxides such as silicon dioxide or aluminum oxide, with additional metal oxides or without them. The silicon atoms may be partially replaced by other metal atoms. These metals include aluminum, titanium, vanadium, zirconium, gallium, boron, manganese, zinc, copper, gold, lanthanum, chromium, molybdenum, Nickel, cobalt, iron, tungsten, palladium, and platinum, but not limited to. These metals can be entered in the inorganic oxide inside the walls of the mesopores and/or on the surface of the mesopores. Additional metals before starting the process optionally can be embedded in the material to obtain a structure that contains mesopores. Also after cooking material cations in the system optionally can be substituted by other ions such as ions of alkali metals (e.g. sodium, potassium, lithium etc).

Organic exemplary reagent mesoporous organic compound is typically a glycol (a compound that includes two or more hydroxyl groups such as glycerin, diethylene glycol, etilenglikol, tetraethylene glycol, propylene glycol, etc. or element(s) of the group consisting of triethanolamine, triisopropanolamine, sulfolane, Tetraethylenepentamine and dibenzoate IER is alpicola. It is preferable that the organic exemplary agent had a boiling point of at least about 150°C.

For the introduction of zeolite in a porous inorganic oxide in U.S. Patent 6762143 and U.S. patent publication describes the preferred technology. From pre-prepared zeolite and/or pre-treated zeolite created aqueous suspension by mixing with water. Then the suspension is weighed with an inorganic oxide or a chemical precursor of the inorganic oxide and at least one mesoporous organic compound with the formation of the mixture. It is preferred that the mixture formed a gel when maintaining and/or stirring at a certain temperature from room temperature to 100°C and/or drying at a temperature of 60-120°C. Then the gel is heated to a temperature of 140-200°C over a period of time sufficient for the formation of mesoporous inorganic oxide structure. Finally, the organic pore-forming agent is removed by extraction or extraction with calcination to obtain compounds containing zeolite embedded in a non-crystalline, porous inorganic oxide.

In addition, U.S. patent application No. 10/764797 discloses a method of preparation of non-crystalline Pori is that the inorganic oxide by the use of complex compounds. Complex compounds, such as, for example, salitran, lumatron, titantron and, especially, the silicon-triethanolamine, aluminum-triethanolamine and a mixture thereof, can be used as a chemical precursor of noncrystalline porous inorganic oxide. Following the techniques described in U.S. Patent No. 6762143 and in U.S. patent application 2004/0138051, it is possible to obtain a composition containing zeolite embedded in a non-crystalline, porous inorganic oxide (TUD-1).

The above-mentioned metal having a hydrogenation function, can be introduced into the catalyst at various stages of preparation of the catalyst. After preparation of the composite containing zeolite in non-crystalline, porous inorganic oxide (designated as zeolite/TUD-1), the metal can be downloaded by conventional impregnation and ion exchange. The metal can also be entered in the zeolite before the introduction of zeolite in a porous inorganic oxide (TUD-1) by impregnation or ion exchange. In practice, the zeolite/TUD-1 is preferred to shape him using some binders such as alumina. After shaping the catalyst in the catalyst can enter the metal.

The composite zeolite/TUD-1 is impregnated with at least one solution containing at least one element from group VIB, VIIB, IB, IIB and VIII. Sources in the form of the element is in group VIB, you can use well-known to specialists in this field of technology. Examples of sources containing molybdenum and tungsten, are the oxides and hydroxides of molybdenum-containing acid and tungsten-containing acids and their salts, in particular ammonium salts such as ammonium molybdate, heptamolybdate ammonium, ammonium tungstate, phosphomolybdenum acid, phosphomevalonate acid and their salts, criminalistica acid, kremneva.liliya acid and their salts. It is preferred to use oxides and ammonium salts such as ammonium molybdate, heptamolybdate ammonium and metabolomic ammonium.

Sources in the form of elements of groups VIII, VIIB, IB and IIB, which can be used are well known to specialists in this field of technology. Examples of sources containing base metals, are nitrates, sulfates, phosphates, halides, for example chlorides, bromides and fluorides, and carboxylates, for example acetates and carbonates. Examples of sources containing precious metals are the halides, for example chlorides, nitrates, acids, such as platinochloride acid, and oxychloride, such as ammoniacal ruthenium oxychloride.

The catalysts obtained in the present invention, created in the form of grains of different shapes and sizes. They are usually used in the form of C is indecency or multipartite extrudates (for example, two, three or Chetvertaya) with straight or twisted shape, but they can also be obtained and used in the form of compressed powder, tablets, rings, balls or disks.

The catalyst can be used in the hydrocracking, hydrobromide and hydroisomerization in which all the catalysts are bifunctional, combining an acid function and a hydrogenation function. In some processes it is necessary to balance these two functions. Hydrogenation function provides a metal selected from transition metals or noble metals. Entered the zeolite provides the acid function. Noncrystalline porous oxide TUD-1 can provide an acid function and/or hydrogenation function depending on the chemical composition of the oxide. For example, the porous oxide is a mixed oxide oxide of silicon and aluminum, and thus provides an acidic function. The porous oxide is a silicon dioxide containing Nickel and molybdenum; it provides a hydrogenation function. In addition, the porous oxide can not deliver either acid or hydrogenation function, for example, if the porous oxide is a pure silicon dioxide. Thus, this new catalyst has a high degree of flexibility to adjust the acidic functionality and hydrogenation functions.

Another important feature of this catalyst provides high mesoporosity through the use of non-crystalline porous oxide that significantly increase the mass transfer and, consequently, increases the efficiency of the catalyst. For most liquid-phase processes interparticle mass transfer limitations reduce the use of the catalyst and the overall efficiency of the catalyst. Increased mesoporosity can improve the overall efficiency of the catalyst. Moreover, many of the treatment processes used heavy oil of the reaction mixture, which require large pores to facilitate the penetration of large molecules into the particles of the catalyst and out of them. Oil the reaction mixture may include, for example, mediafilesource residual oil, neasfaltirovanyj residues of oil, bitumen from oil Sands, shale oil and polsterdusel fluid. As such, non-crystalline porous oxide TUD-1 with the size of the mesopores 1.5 to 30 mm, may satisfy the requirements enhance mass transfer.

In addition, non-crystalline porous oxide contains not only tunable mesopores, but also contains an unordered interconnected mesopores. As described in U.S. Patent No. 6358486, its structure with disordered connected to each other by mesopores differs from other mesoporous materials such as MCM-41. Disordered interconnected mesopores reduce the likelihood of clogging of pores compared to materials with one - or two-dimensional pore system. Thus, the new catalyst will have the advantage of durability from the perspective of decontamination clogging the pores.

In the process of hydrocracking balance between the acid and hydrogenation functions is a fundamental parameter that affects both the activity and selectivity of the catalyst. A weak acid function and a strong hydrogenation function lead to catalysts with low activity, which typically requires a high reaction temperature (390°C or above) and low space velocity (LHSV (hourly volumetric rate of fluid) is usually 2 h-1or below), but typically, such catalysts have a very good selectivity for middle distillates. On the contrary, a strong acid function and a weak hydrogenation function lead to a very active catalysts, but the selectivity for middle distillates is worse; this combination of catalyst also may adversely affect the stability against aging. Research for the respective catalysts, thus, obkatyvalisj around the correct selection of each of these functions to regulate the balance of activity/selectivity/stabiles and catalyst.

To obtain good selectivity for middle distillates by hydrocracking is preferred that the catalyst as a non-crystalline porous material contained a mixture of silica and alumina contained zeolites selected from zeolite Y, ZSM-5, zeolite β, MCM-56 and/or MCM-22, and contains metals selected from group VIII and/or VIB of the periodic table. Also is preferred that in the presence of high content of heteroatomic poison in raw materials and certain metals of groups VIB and VIII present in the form of sulfides or oxysulfides.

One known method of sulfatirovnie, which is well known to experts in the art, consists in heating in the presence of hydrogen sulphide (pure or, for example, in the flow of the mixture of hydrogen and hydrogen sulfide or nitrogen and hydrogen sulfide) to a temperature in the range 150°C-800°C, preferably in the range 250°C-600°C, usually in the reaction zone of the moving layer.

The conditions of the hydrocracking process (e.g., temperature, pressure, circulation rate of hydrogen and the flow rate) can vary widely depending on the nature of the raw materials, the quality of the desired products and equipment suitable for cleaning. Temperature, as a rule, is more than 200°C, typically in the range 250°C-480°C. the Pressure is more than 0.1 MPa, usually more than 1 MPa. Count the number of hydrogen is a minimum of 50 liters of hydrogen per liter of feedstock, usually in the range 80-5000 liters of hydrogen per liter of feedstock. Hourly space velocity is typically in the range of 0.1 to 20 volumes of feedstock volume of catalyst per hour. The products of the hydrocracking may include, for example, middle distillates with a boiling point in the range of about 150°C to 400°C, diesel and lubricating base oil.

As a rule, hydroisomerization catalyst, for example, is designed for product improvement Fischer-Tropsch (disclosed in U.S. Patent No. 6570047), contains one or more components with a catalytic metal of group VIII deposited on a substrate of an acidic metal oxide, to obtain a catalyst hydrogenation function and an acid function to hydroisomerization hydrocarbons. Conditions hydroisomerization usually include a temperature of from about 150°C to about 500°C, a pressure from about 1 bar to about 240 bar and LHSV of about 0.1 to 20 h-1. At relatively low temperatures isomerization, for example temperatures in the reactor for the synthesis of hydrocarbons, the catalytic metal component may include a noble metal of group VIII, such as Pt or Pd, preferably Pt. However, at elevated temperatures, which can be used in the process according to the invention, it is preferable that the catalytic metal is a component comprised of one or more cheap, base metals of group VIII, such as Co, Ni and Fe, which can usually include a promoter and a catalyst in the form of a metal oxide of group VIB (e.g., Mo or W). The catalyst may also contain a metal of group IB, such as copper, as an inhibitor hydrogenolysis. To increase the solubility of metals and to promote overall stability, you can also add phosphorus.

Kekirawa and hydrogenation activity of the catalyst is determined, as is well known, its specific composition. The present invention relates to the preferred composition of the catalyst containing a catalytically active metal, such as cobalt and molybdenum, an oxide substrate or a carrier comprising silica, alumina, a mixture of oxides of silicon and aluminum, a mixture of silica, alumina and phosphate, titanium dioxide, zirconium dioxide, vanadium dioxide, and other oxides of metals of groups II, IV, V or VI, as well as acidic zeolite such as zeolite Y (including USY)zeolite β and ZSM-5.

The following examples illustrate the present invention without limiting its scope in each case.

EXAMPLE 1

This example illustrates the introduction of zeolite β in silica TUD-1. First, 4.6 parts of calcined zeolite β with molar concentration of SiO2/Al2O3equal to 75, and the average size of castic,2 μm were diluted 51 parts of water with the formation of the suspension and subjected to stirring for 30 minutes. Then to the suspension while stirring there were added 23 parts of triethanolamine. After continuous stirring for 30 minutes was added 63.5 parts of tetraethylorthosilicate ("TEOS"). After stirring for 30 minutes the mixture was Pocatello added 12.6 parts of an aqueous solution (35%) of the hydroxide of tetraethylammonium. After stirring for approximately 2 hours, the mixture turned into a thick non-leaking gel. This gel was within 24 hours is maintained at room temperature in a stationary mode. Then the gel was dried for 24 hours in air at 100°C. the Dried gel was transferred into an autoclave and subjected to hydrothermal treatment at 180°C for 4 hours. Finally, it was calcined at 600°C in air for 10 hours with heating rate 1°C/min. x-ray diffraction x-ray analysis of the resulting product is designated as Sample 1, shown in figure 1, clearly shows two characteristic peaks of zeolite β. In the final composite, there are about 20 wt.% zeolite β. The nitrogen adsorption revealed a surface area of the sample, equal to about 730 m2/g, and pore volume equal to about 1.08 cm3/year Distribution of mesopores of Sample 1 according to the dimensions shown in figure 2.

EXAMPLE 2

Used here zeolite β is the same as in Example 1. first of 12.2 parts of zeolite β were diluted 51 parts of water with the formation of the suspension and subjected to stirring for 30 minutes. Then to the suspension while stirring there were added 23 parts of triethanolamine. After continuous stirring for 30 minutes was added 63.5 parts of TEOS. After stirring for 30 minutes the mixture was Pocatello added 12.7 parts of an aqueous solution (35%) of the hydroxide of tetraethylammonium. Then followed the same procedure as described in Example 1. X-ray diffraction x-ray analysis of the sample obtained after calcinations (corresponding to Sample 2), depicted in figure 1, clearly shows two characteristic peaks of zeolite β. In the final composite, there are about 40 wt.% zeolite β/TUD-1. The nitrogen adsorption revealed a surface area of the sample, approximately 637 m2/g, and pore volume equal to about 1,cm3/year Distribution of mesopores sample size is shown in figure 2.

EXAMPLE 3

Was used in the same zeolite β and the same procedure as described in Example 1, except the amount of substance. It was 9.2 parts of zeolite β, 17 parts of water, 7.6 parts of triethanolamine, 21.2 parts of TEOS and 4.2 parts of an aqueous solution (35%) of the hydroxide of tetraethylammonium. The final product, designated as Sample 3, was characterized using XRD and adsorption gas. His chest x-ray diffraction the x-ray also is bcii, presented in figure 1, clearly shows two characteristic peaks of zeolite β. Zeolite β in the final composite was approximately 60 wt.%. The nitrogen adsorption revealed a surface area of the sample, approximately 639 m2/g, and pore volume equal to approximately 0,97cm3/year Distribution of mesopores sample size is shown in figure 2.

EXAMPLE 4

This example illustrates the introduction of MCM-22. First, 2.4 parts of the synthesized zeolite MCM-22 with the molar concentration of SiO2/Al2O3equal to 6.4, and an average particle size of 2.5 μm were added to 10.5 parts of water with the formation of suspensions and were subjected to stirring for 30 minutes. Then during mixing to the above suspension was added 9.2 parts of triethanolamine. After continuous stirring for 30 minutes was added 12.7 parts of TEOS. After stirring for 30 minutes the mixture was Pocatello added 2.56 parts of an aqueous solution (35%) of the hydroxide of tetraethylammonium. After stirring for approximately 2 hours, the mixture turned into a thick layer of non-leaking gel. This gel was within 24 hours is maintained at room temperature in a stationary mode. Then the gel was dried for 24 hours in air at 98°C. the Dried gel was transferred into an autoclave and subjected to hydrothermal treatment is at 180°C for 4 hours. Finally, it was calcined at 600°C in air for 10 hours with heating rate 1°C/min

X-ray diffraction x-ray analysis of the resulting product, designated as Sample 4 and is shown in the top graph in figure 3, clearly shows the characteristic peaks of zeolite MCM-22 (middle graph) and mesoporous material (the lower graph). In Sample 4, there are about 40 wt.% zeolite MCM-22, and elemental analysis confirmed this value is based on the aluminum content, given the absence of aluminum in the mesoporous material containing silicon. The nitrogen adsorption revealed a surface area of the sample, approximately 686 m2/g, and pore volume equal to approximately 0,82 cm3/year Distribution of mesopores size figure 4 is centered around 10 nm. Adsorption of argon showed a distribution of micropores in size, centred around 0.5 nm.

EXAMPLE 5

An ultra-stable zeolite Y (USY), containing SiO2/Al2O3with the molar concentration of 14.8 and surface area 606 m2/g, was introduced into the aluminium-containing mesoporous material. First, 2.9 parts of an ultra-stable zeolite Y were diluted in of 17.0 parts of water with the formation of the suspension and subjected to stirring for 30 minutes. Then during mixing to the above suspension was added 12 parts of triethanolamine. After continuous stirring for 30 minutes, the stirring was added to another mixture containing 171,4 parts TEOS and 28 parts of aluminum isopropylate. After additional stirring for 30 minutes, to the mixture were Pocatello added 34 parts of an aqueous solution (35%) of the hydroxide of tetraethylammonium. After stirring for approximately 2 hours, the mixture turned into a thick layer of non-leaking gel. This gel was within 24 hours is maintained at room temperature in a stationary mode. Then the gel was dried for 24 hours in air at 100°C. the Dried gel was transferred into an autoclave and subjected to hydrothermal treatment at 180°C for 4 hours. Finally, it was calcined at 600°C in air for 10 hours with heating rate 1°C/min Final material was designated as Sample 5.

X-ray diffraction x-ray analysis of the Sample 5 is shown in the upper graph in Figure 5, clearly shows two characteristic peaks of zeolite Y and mesostructured material. The bottom graph depicts the x-ray diffraction x-ray analysis of zeolite Y. In the final composite, there are about 5 wt.% zeolite Y. Adsorption of nitrogen showed the surface area of the sample, approximately 694 m2/g, and pore volume equal to approximately 1.1 cm3/year

p> EXAMPLE 6

This example illustrates the extrusion of the catalyst using alumina (aluminum oxide) as a binder. Proton form (i.e. H+) Sample 5 was obtained by ion exchange, by mixing one part of the Composite with 5 ten parts of 1-normal solution of ammonium nitrate at 60°C for 6 hours under stirring. The solid material was filtered, washed and dried at 110°C to obtain a white powder. After the second ion exchange solid material was calcined in air at 550°C for 6 hours.

To ensure catalyst eight parts of H+-Sample 5 were mixed with two parts of aluminum oxide in the form of Nyacol. The mixture was subjected to extrusion to obtain a cylindrical shape with a diameter of 1.6 mm Extrudate was dried and calcined at 550°C for 4 hours. Finally, was obtained extrudate containing about 4 wt.% USY, 76 wt.% Al-containing non-crystalline porous oxide and 20 wt.% aluminum oxide.

EXAMPLE 7

This sample demonstrates the preparation of a chemical precursor of silicon dioxide - triethanolamine complex of silicon dioxide. First 250 parts of silica gel, 697 parts of triethanolamine (tea) and 286 parts of ethylene glycol (EG) were loaded in a flask equipped with condenser. After a good mixing of the contents of the flask, milling eskay stirring the mixture during the stirring was heated to 200-210°C. With this setup was able to remove most of the water generated during the reaction along with a small amount of AG from the top of the condenser. Meanwhile, a large part of the EG and the tea remained in the reaction mixture. After about six hours, the heating was discontinued and the reaction mixture was collected after cooling to 55°C. This reaction mixture was slightly brown and was designated as triethanolamine complex of silicon dioxide.

EXAMPLE 8

This example illustrates the preparation of zeolite/TUD-1 using triethanolamine complexes of silicon dioxide as a source of silicon dioxide. Suspension consisting of 99 parts of zeolite Y (CBV-500) and 300 parts of water, was loaded in a grinding device for grinding in a liquid medium. After 30 minutes of grinding at 3000 rpm suspension was collected for the introduction of zeolite in a silica TUD-1. 206 parts of the suspension (measurements which revealed a 20 wt.% zeolite Y) were mixed with 217 parts of the complexes obtained in Example 7 with stirring. After 30 minutes, the mixture formed a thick layer of gel which was then dried at 90°C for 24 hours. The dried gel was transferred to an autoclave and heated to 180°C and left there for 6 hours. Finally, the gel was calcined at 600°C for 10 hours in air, and as a result he PR is turned back to the white powder.

The final composite zeolite/TUD-1 containing 45 wt.% zeolite. Adsorption of gaseous nitrogen showed that the surface area by BET was approximately 560 m2/g, total pore volume of 1.2 cm3/g and the average size of the mesopores is approximately 5.7 nm.

EXAMPLE 9

This example shows the implementation of the metals in the catalyst. The extrudate obtained in Example 6, was further exploited by impregnation of Ni and W. Five (5) parts of an aqueous solution of Nickel nitrate (14 wt.% Ni) was mixed with 8.4 parts of a solution of metavolume ammonium or 39.8 wt.% W) in terms of mixing. The mixture is then diluted with 9 parts of water under the conditions of mixing. 12.5 parts of the extrudate obtained in Example 6, has infiltrated the above solution of Ni/W, dried at 118°C for 2 hours and probalily at 500°C for 2 hours. The resulting modified extrudates containing 4.0 wt.% Ni and 18.7 wt.% W.

EXAMPLE 10

This example illustrates the preparation of a 0.9 wt.% palladium and 0.3 wt.% platinum/zeolite-TUD-1 at the beginning of humidity. Zeolite/TUD-1 obtained in Example 2 was impregnated with an aqueous solution containing 0.42 part of the nitrate tetraammineplatinum, 12.5 parts of an aqueous solution of nitrate tetraamminepalladium (5% Pd) and 43 parts of water. Impregnated zeolite/TUD-1 was kept at room temperature for 5 hours before drying at 90°C for 2 hours. The dried Mat is real then progulivali in air at 350°C for 4 hours with a heating rate of 1°C/min The dispersion of the noble metal was measured using CO chemisorption; then the powder was recovered in the flow of hydrogen at 100°C for 1 h followed by heating to 350°C at 5°C/min and held at this temperature for 2 hours For metal was measured 51%of the variance, taking into account the stoichiometric ratio of Pt:CO = 1.

EXAMPLE 11

This example illustrates the preparation of the catalyst of 0.90 wt.% iridium/zeolite/TUD-1 at the beginning of humidity. 0,134 parts of chloride of iridium (III) were dissolved in 5.3 parts of deionized water. This solution was added to 8 parts of zeolite/TUD-1 obtained in Example 4 with the mixture. The powder was dried at 25°C.

To measure dispersion using chemisorption of CO powder was then restored in a stream of hydrogen at 100°C for 1 h followed by heating to 350°C at 5°C/min and held at this temperature for 2 h CO Chemisorption showed 78%of the variance for the metal, taking into account the stoichiometric ratio Ir:CO = 1.

EXAMPLE 12

This example illustrates the use of the catalyst obtained in Example 9 as a hydrocracking catalyst, which is designed to assess the selectivity of middle distillates by hydrocracking. This assessment is carried out in a flow reactor with presulfiding agent (in the standard way) the BL is using as raw material hydrogenated heavy vacuum gas oil. This reactor operates with an hourly volume rate of fluid equal to 1.5 kg/l·h, the total pressure of 140 bar (partial pressure of H2S, is equal to 5.5 bar, and the partial pressure of ammonia equal to 0,075 bar) and the ratio of gas/raw materials equal to 1500 NL/kg Properties of the raw materials shown in Table 1.

Table 1
Properties of hydrogenated heavy vacuum gas oil
Distillation (D1160):
IBP (initial boiling point),
°C (vol. %)
345
10%402
30%441
50%472
70%508
90%564
EP (effective pressure)741
KV @ 100°C, cst8,81
Carbon, wt.%86,6
Hydrogen, wt.%the 13.4
The total amount of sulfur, m is S.% 0,008
Total nitrogen, ppm16,1

The selectivity for middle distillates (for example, when the range of the boiling point of 175°C-345°C) determined in a clean conversion components in 65 wt.%. Selectivity, suddenly, reaches to 72.6 wt.%.

EXAMPLE 13

This example illustrates the increase in the yield of lubricating oil and the viscosity index. The composite zeolite/TUD-1 obtained in Example 6, impregnated with nitrate tetraammineplatinum as described in Example 9, and the final catalyst contains about 0.6 wt.% Pt. Normal, besmislennoye paraffin raw material has a composition shown in Table 2 below. This obespylenny paraffin obtained from solvent (MEK - methyl ethyl ketone (MEK)), deparaffinizing neutral oil, 300 SUS (65 cst)received from Arab light crude oil. The total liquid product obtained in stage hydrocracking, then subjected improvement and hydroisomerization by processing in weakly acidic catalyst Pt/zeolite β/TUD-1, obtained for the effective hydroisomerization and transformation of much of the unreacted paraffin in a very high quality engine oil with very high viscosity index, containing essentially all of isoparaffin hydrocarbons, mainly branched. Paraffin shared idci product is treated catalyst at a partial pressure of H 2equal to 400 psia (absolute pressure in pounds per square inch), 2500 SCF (standard cubic feet) of hydrogen and hourly volume velocity LHSV of 0.5, at a range of degrees of conversion. The total liquid product is then distil to the nominal boundaries of separation distillation fraction equal to 700° F+. Paraffin precipitation then deparaffinized in a solvent to obtain lubricating oils, to increase the yield of lubricating oil. Table 3 contains the results of these experiments using the zeolite-containing catalyst hydrocracking.

Table 2
Properties bezmashinnogo paraffin
Density, °API*39,2
Hydrogen, wt.%14,04
Nitrogen, ppm9
Sulfur, wt.%0,01
KV @ 100°F, cst6,294
KV @ 300° F, cst3,15
Pour point, °F120
Oil in paraffin, D32353,1
* - degrees American petroleum Institute

Simulated distribution D2887
Wt. %°F
0,5759
5811
10830
20860
30878
40899
50917
60938
70959
80983
901014
951038

Table 3
Isomerization subjected to hydrocracking bezmashinnogo paraffin with a low conversion rate of the catalyst Pt/zeolite β/TUD-1
1 2345
The reactor T, °F-691632638678
700°F - Conversion,
wt.%
(Full)
1823,322,5a 21.58,9
The properties of the solvent deparaffination oil
KV @ 40°C, cst19,0418,0523,222,3323,07
KV @ 100°C, cst4,4574,2995,1955,045,089
The viscosity index153152164162157
Pour point, °F05 15105
Index viscosity @ 0°F fluidity151149158159153
Sim Dist(5% share)674557732705623
Composition, wt.%
Waxes9297938991
Mononitratee hydrocarbons50322
Polinaftenous hydrocarbons21464
Aromatic hydrocarbons1203 3
The output of lubricating oil, wt.%
(Besmislennoye paraffin feedstock)
31,749,442,350,153,8
Conversion of paraffin, %47,168,961,470,191,2

Although the description above contains many specifics, these specifics should be interpreted not as limitations of the invention, but only as explanations examples of the preferred options of the incarnation. Specialists in the art can envision many other variants of embodiments within the scope and essence of the invention defined attached by the claims.

1. A method of producing a catalyst for the conversion of hydrocarbons, including:
(a) obtaining the complex compounds as precursors for non-crystalline inorganic oxide with mesopores, unordered connected to each other;
(b) the use of complex compounds from step (a) to obtain a composite material containing zeolite embedded in a non-crystalline inorganic oxide with mesopores, newpor docendo connected to each other;
(c) introducing the composite obtained in stage (b)at least one metal having hydrogenation function.

2. The method according to claim 1, in which the mentioned complex compound selected from the group consisting of salitran, lumatron, titantron and their combinations.

3. The method according to claim 1, wherein the zeolite is selected from the group consisting of zeolite β, zeolite Y, ZSM-5, MCM-22, MCM-36, modernica, zeolite L, ZSM-11, ZSM-12, ZSM-20, Theta-1, ZSM-23, ZSM-34, ZSM-35, ZSM-48, SSZ-32, PSH-3, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-4, ITQ-21, SAPO-5, SAPO-11, SAPO-37, Breck-6 and ALPO4-5.

4. The method according to claim 1, wherein the metal is selected from groups VIII, IB, IIB, VIIB and VIB of the Periodic system of elements.

5. The method according to claim 1, including additional stage d) contacting a catalytically effective amount of catalyst, obtained in stage C), with raw materials containing at least one hydrocarbon component.

6. The method according to claim 5, in which stage (d) comprises a reaction selected from the group consisting of hydrocracking, hydrobromide and hydroisomerization.

7. The method according to claim 5 or 6, in which the mentioned raw materials includes oil fraction and reaction conditions are sufficient for the implementation of the hydrocracking fraction to obtain a relatively clarified hydrocarbon product.

8. The method according to claim 7, in which is mentioned the oil phase contains at least one component having the point is andsinging above about 260°C.

9. The method according to claim 7, in which is mentioned the oil phase contains at least one component having a boiling point above about 290°C.

10. The method according to claim 7, in which is mentioned the oil phase contains at least one component having a boiling point above about 340°C.

11. The method according to claim 10, in which is mentioned the oil phase further comprises at least one component selected from the group consisting of nudeasian oil residues, deasphalting oil residues, bitumen from oil Sands, shale oil and polsterdusel liquid.

12. The method according to claim 7, in which the mentioned relatively clarified hydrocarbon product comprises a component selected from the group consisting of component a middle distillate having a boiling point in the range of 150-400°C, diesel and lubricating base oils.

13. The method according to claim 6, in which the conversion of the hydrocarbon component is implemented by hydroisomerization and the reaction conditions including a temperature from about 150°to about 500°C., a pressure from about 1 bar to about 240 bar, and watch the volumetric rate of fluid from about 0.1 to about 20.



 

Same patents:

FIELD: oil and gas industry.

SUBSTANCE: invention refers to method for simultaneous making medium fractions and lubricant bases from synthetic paraffin mixtures, including hydrocracking stage (i) and distillation of product of stage (i), where hydrocracking involves addition of solid bifunctional catalyst including: (A) acidic carrier consisting of catalystically active porous solid substance, including silicon, aluminium, phosphorus and oxygen interlinking so that to form mixed amorphous solid substance, characterised by nuclear ratio Si/Al within 20 to 250, ratio P/Al at least 0.1, but lower that 5, total porous amount within 0.5 to 2.0 ml/g, average pore diameter within 2 nm to 40 nm and specific surface area within 200 to 1000 m2/g; (B) at least one metal with hydrogenation-dehydrogenation activity, selected from groups with 6th on 10th of Periodic systems and distributed over specified carrier (A) in amount within 0.05 to 5 wt % relative to total mass of catalyst.

EFFECT: development of method for simultaneous making medium fractions and lubricant bases from synthetic paraffin mixtures.

25 cl, 26 ex, 5 tbl, 2 dwg

FIELD: technological processes; chemistry.

SUBSTANCE: method involves reaction of raw material containing organic component with a catalyst composition. Processing method is selected out of alkylation, acylation, hydrotreatment, demetallisation, catalytic deparaffinisation, Fischer-Tropsch process and cracking. Catalyst composition includes mainly mesoporous silicon dioxide structure containing at least 97 vol.% of pores with size in the interval from ca. 15 Å to ca. 300 Å, and at least ca. 0.01 cm3/g of micropores. Mesoporous structure features at least one catalytically and/or chemically active heteroatom in amount of at least ca. 0.02 mass %, selected out of a group including Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W and their combinations. The catalyst composition radiograph has one 0.3° to ca. 3.5° peak at 2θ.

EFFECT: highly efficient method of organic compound processing in the presence of catalyst composition without zeolite.

20 cl, 31 ex, 17 tbl, 22 dwg

FIELD: petrochemical processes and catalysts.

SUBSTANCE: middle distillates are obtained, in particular, from paraffin charge prepared by Fischer-Tropsch synthesis wherein hydrocracking/hydroisomerization catalyst is utilized including at least one hydrocracking/hydroisomerization element selected from group constituted by group VIII metals, non-zeolite silica-and-alumina-based carrier (more than 5% and less than or equal to 95% SiO2) and having: average pore size measured by mercury porometry within a range 20 to 140 Å; total pore volume measured by mercury porometry 0.1-0.6 mL/g; total pore volume measured by nitrogen porometry 0.1-0.6 mL/g; specific surface BET between 100 and 550 m2/g; pore volume for pores with diameter above 140 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 160 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 200 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 500 Å measured by mercury porometry less than 0.01 mL/g; x-ray diffraction pattern containing at least principal characteristic lines of at least one transition aluminum oxides (alpha, rho, chi, eta, kappa, teta, and delta). Processes of obtaining middle distillates from paraffin charge obtained ny Fischer-Tropsch synthesis (options) using above indicated procedure are also described.

EFFECT: improved catalytic characteristics in hydrocracking/hydroisomerization processes and improved quality and yield of middle distillates.

18 cl, 6 dwg, 3 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention refers to noble-metal catalyst, to method for making and application thereof. There is disclosed method for making noble-metal catalyst for hydrocarbon conversion, involving the stages as follows: a) preparation of the carrier containing zeolite, chosen from zeolites with medium and large pores and acid sites, at temperature within 423 to 1173 K and optional carrier modification; b) deposition of noble metal chosen from platinum, palladium, ruthenium, rhodium, iridium and their mixtures and combinations, by gas-phase deposition including evaporation of noble metal precursor chosen from β-diketonates and metallocenes, and interaction with the carrier, and c) heat treatment in oxidising or reducing environments. There is disclosed application of noble-metal catalyst produced by the method described above, in ring opening, isomerisation, alkylation, hydrocarbon reforming, dry reforming, hydrogenation and dehydrogenation, and preferentially, in ring opening of naphthenic molecules. Additionally, there is disclosed method for making medium diesel fuel distillate by introducing raw medium distillate into the reactor wherein it reacts at temperature 283-673 K and under pressure 10-200 bar with hydrogen with added noble-metal catalyst produced as described above until ring opening of naphthenes with two or more rings completed to produce isoparaffins, n-paraffins and mononaphthenes within medium distillate.

EFFECT: production of catalyst with improved selectivity for hydrocarbon conversion.

16 cl, 5 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: said invention relates to method for improvement of loss of mobility temperature of hydrocarbon material obtained by Fischer-Tropsch synthesis, in particular to satisfactory-yield conversion of material with high temperature of mobility loss, at least one fraction of which has low mobility loss temperature and high viscosity index for base oil. Method implies utilisation of dewaxing catalyst, which contains at least one zeolite (molecular sieve) chosen from a group of TON type zeolites (Theta-1, ZSM-22, ISI-1, NU-10 and KZ-2), and at least one ZBM-30 zeolite, at least one inorganic porous matrix, at least one hydrogenating/dehydrogenating element, preferentially from group VIB and group VIII of periodic table.

EFFECT: improved loss of mobility temperature for hydrocarbon material obtained by Fischer-Tropsch synthesis.

14 cl, 7 ex, 1 dwg

FIELD: physics.

SUBSTANCE: dewaxing procedure of raw material produced by Fischer-Tropsch method implies that processed raw materials contact with catalyst containing at least one zeolite ZBM-30, synthesised with triethylene tetramine, at least one hydrogenating- dehydrogenating element preferably selected from elements of group VIB and group VIII of periodic table, and at least one inorganic porous matrix.

EFFECT: good recovery of raw material, raised pour point.

13 cl, 5 ex, 1 dwg

FIELD: technological processes; chemistry.

SUBSTANCE: method involves reaction of raw material containing organic component with a catalyst composition. Processing method is selected out of alkylation, acylation, hydrotreatment, demetallisation, catalytic deparaffinisation, Fischer-Tropsch process and cracking. Catalyst composition includes mainly mesoporous silicon dioxide structure containing at least 97 vol.% of pores with size in the interval from ca. 15 Å to ca. 300 Å, and at least ca. 0.01 cm3/g of micropores. Mesoporous structure features at least one catalytically and/or chemically active heteroatom in amount of at least ca. 0.02 mass %, selected out of a group including Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W and their combinations. The catalyst composition radiograph has one 0.3° to ca. 3.5° peak at 2θ.

EFFECT: highly efficient method of organic compound processing in the presence of catalyst composition without zeolite.

20 cl, 31 ex, 17 tbl, 22 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to production of lubricating material characterised by dynamic viscosity at -35°C, lower than 5000 cpz, as a result of fulfilling the following stages: a) introduction of feedstock containing more than 50 weight % of paraffin, in presence of hydrogen in contact with catalyst containing component based on metal of group VIII applied on carrier based on refractory oxide, and b) introduction of product of stage (a) in contact with catalyst composition, which contains noble metal of group VIII, binder and crystals of zeolite belonging according to its type, to MTW, obtaining product characterised by lower flow temperature in as compared to that of stage (b) product and index of viscosity higher than 120, and c) adding to base oil obtained at stage (b) of additive for reduction of flow temperature.

EFFECT: production of lubricating material characterised by dynamic viscosity at -35°C.

21 cl, 5 dwg, 3 tbl, 3 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: middle distillates are obtained, in particular, from paraffin charge prepared by Fischer-Tropsch synthesis wherein hydrocracking/hydroisomerization catalyst is utilized including at least one hydrocracking/hydroisomerization element selected from group constituted by group VIII metals, non-zeolite silica-and-alumina-based carrier (more than 5% and less than or equal to 95% SiO2) and having: average pore size measured by mercury porometry within a range 20 to 140 Å; total pore volume measured by mercury porometry 0.1-0.6 mL/g; total pore volume measured by nitrogen porometry 0.1-0.6 mL/g; specific surface BET between 100 and 550 m2/g; pore volume for pores with diameter above 140 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 160 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 200 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 500 Å measured by mercury porometry less than 0.01 mL/g; x-ray diffraction pattern containing at least principal characteristic lines of at least one transition aluminum oxides (alpha, rho, chi, eta, kappa, teta, and delta). Processes of obtaining middle distillates from paraffin charge obtained ny Fischer-Tropsch synthesis (options) using above indicated procedure are also described.

EFFECT: improved catalytic characteristics in hydrocracking/hydroisomerization processes and improved quality and yield of middle distillates.

18 cl, 6 dwg, 3 tbl, 5 ex

FIELD: hydrocarbon conversion processes and catalysts.

SUBSTANCE: invention, in particular, relates to selectively upgrading paraffin feedstock via isomerization. Catalyst comprises support and sulfated oxide or hydroxide of at least one of the elements of group IVB deposited thereon; a first component selected from group consisting of consisting of lutetium, ytterbium, thulium, erbium, holmium, and combinations thereof; and a second component comprising at least one platinum-group metal component. Catalyst preparation process comprises sulfating oxide or hydroxide of at least one of the elements of group IVB to form sulfated support; depositing the first component onto prepared support; and further depositing the second component. Invention also relates to hydrocarbon conversion process in presence of above-defined catalyst.

EFFECT: improved catalyst characteristics and stability in naphta isomerization process to increase content of isoparaffins.

13 cl, 2 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: catalyst carrier contains 10-98% by weight of titanium dioxide (mainly in anatase form) and 2-90% by weight of kieselgur.

EFFECT: increase of the erosion stability, decrease of the abrasion losses.

2 cl, 4 tbl, 4 ex

FIELD: technological processes.

SUBSTANCE: invention is related to the field of chemistry and may be used to produce synthetic gas. Hydrocarbon raw materials mixed with water vapor are passed through heated pipes of reactor, inside of which catalyst is installed in the form of layer of granules including nickel, at that sections of peripheral granules surfaces are in direct heat-conducting connection with internal surfaces of pipe walls. Granules are arranged in the form of balls with cylindrical channels, at that diametre of ball is selected in the interval of 1.0·10-3-2.0·10-3 from the height of catalyst layer, and diametre of channel - in range of 0.1-0.5 from diametre of ball. Content of nickel in balls makes 9-25 wt % in terms of nickel monoxide. Alumina is used as base of ball material.

EFFECT: invention makes it possible to increase process efficiency.

3 cl, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention refers to making heat-resistant sulphocation catalysts. There is disclosed method for making heat-resistant sulphocation catalysts containing aromatic rings chemically combined with solid polymer base, at least two groups -SO2OH, by sulphonation of aromatic rings of polymer base followed by desulfonation at higher temperature of those aromatic rings having only one group -SO2OH whereat heat-resistant polymer base is sulphonated, while aromatic rings are sulphonated in two or more stages with gradually increasing sulphonation hardness. The first stage involves soft sulphonation with aqueous sulphuric acid solution concentrated 95 wt % and more at temperature 90°C and less, preferentially 70°C and less. The last stage implies sulphonation with aqueous sulphuric acid solution concentrated 90 wt % and more or with oleum with SO3 concentrated 1 to 30 wt % higher than chemically combined in acid. The catalyst is sequentially washed by dissolved sulphuric acid solution, then by water. Thereafter it contacts at temperature 150 to 200°C with an inert solvent not containing groups neutralising -SO3OH groups and introduced in amount required to remove groups -SO2OH from the aromatic rings containing one group -SO2OH only.

EFFECT: making heat-resistant catalyst of required dimension and/or shape.

8 cl, 1 tbl, 5 ex

FIELD: mechanics.

SUBSTANCE: invention relates to heterogeneous catalytic reactors designs. The catalytic reactors include inlet, outlet and reactor wall. Inner volume of rector accommodates framed structure located along reactor axis and rector containment structure being located near reactor wall. Both structures are different from each other to ensure catalysis and heat transfer process. In order to allow fluid hitting against reactor wall, type 1 devices are implemented on the framed structure to direct fluid in centrifugal direction. To enable fluid out-flowing from reactor wall while it flows from reactor inlet to its outlet, type 2 devices are available in the framed structure.

EFFECT: effective heat transfer in reactor volume, especially near catalytic reactor walls or other solid wall being in cross section.

37 cl, 8 dwg

FIELD: metallurgy.

SUBSTANCE: invention relates to metallurgy field, particularly to receiving of steel sheet and foil with high content of aluminium by method of flow line production with low cost. On at least one surface of basic steel sheet, containing aluminium in amount from 3.5 up to less than 6.5 wt %, it is applied aluminium or aluminium alloy for receiving of laminated material. It is subject to cold working for giving of operating voltage and diffusive heat processing. It is received steel sheet, containing from 6.5 up to 10 wt % of aluminium, allowing texture with crystal plane aggregate α-Fe {222}, compound from 60 up to 95%, and/or planes {200}, compound from 0.01 up to 15%, relative to surface of steel sheet. Sheet is subject to additional cold rolling with receiving of foil.

EFFECT: treatability improvement, that provides receiving of products of different forms without additional operations.

21 cl, 2 dwg, 6 tbl, 7 ex

FIELD: chemistry.

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

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

23 cl, 14 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: present invention concerns the salts containing bis(trifluoromethyl)imide anions and saturated, partially or completely unsaturated heterocyclic cations, method of production and application thereof as ionic liquids.

EFFECT: production of new salts to be used as ionic liquids.

19 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to catalyst compositions containing zeolite and inorganic binding agent with particular mechanical characteristics porosity and characteristics, and available as a catalysts in industrial fixed-bed catalytic reactors. There is disclosed composition containing zeolite and inorganic binding agent, where zeolite has crystal structure with holes formed by 12 tetrahedrons, while binding agent is aluminium γ-oxide. Herewith the composition described above is characterised by pore space derived from summing up mesoporous and macroporous components found in the specified catalyst composition, exceeding or equal 0.7 cm3/g, and at least 30% of said pore space volume consist of pores of diameter exceeding 100 nanometres. Additionally there are disclosed method of preparing catalyst composition specified above, method of aromatic hydrocarbon transalkylation involving aromatic hydrocarbon contacting to one or more polyalkylated aromatic hydrocarbon with the said catalyst composition added. Besides, there is disclosed method of preparing monoalkylated aromatic hydrocarbons involving: a) aromatic hydrocarbon contacting to C2-C4- olefin with acid catalyst added in such alkylation conditions, that reaction is enabled, at least partially in liquid phase, b) product separation to fraction containing aromatic hydrocarbon, fraction containing monoalkylated aromatic hydrocarbon, fraction containing polyalkylated aromatic hydrocarbons, and fraction containing heavy aromatic hydrocarbons, c) fraction containing polyalkylated aromatic hydrocarbons contacting to aromatic hydrocarbon with the said catalyst added, in such transalkylation conditions, that reaction is enabled, at least partially in liquid phase.

EFFECT: improved catalyst performance, both concerning its durability and productivity, improved mechanical characteristics of the catalyst, such as crushing strength and abrasion resistance, ensured high yield and high efficiency of transalkylation.

40 cl, 1 tbl, 6 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention refers to chemical industry, specifically to catalysts and methods of light hydrocarbon conversion and can be used in petrochemical, an oil-refining industry for producing catalysts and managing process of synthetic gas production. Catalyst is two-phase product having ferric aluminide Fe3Al as master phase and free ferric phase in amounts 90-95 wt % and 5-10 wt % respectively. The catalyst is produced by self-propagating high-temperature synthesis, probably with mechanical preactivation of exothermic mixed powder and is used in method of light hydrocarbon carbon-dioxide conversion.

EFFECT: catalyst is characterised with high catalytic activity, thermal conductivity, mechanical strength, thermal stability, corrosive medium resistance thus improving productivity of light hydrocarbon carbon-dioxide conversion, including eg methane, is made of cheap, commonly used metals.

2 cl, 2 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: there is disclosed selective oxidation catalyst of gas hydrogen sulphide to element sulphur on carbon carrier containing natural ferric oxide. Herewith catalyst is additionally introduced with ferric oxide in amount 0.5-2.0 wt % and magnesium oxide in amount 0.1-0.5 wt % on metal basis. Substrate is high-ash microcellular carbon carrier made of low-caking fossil coal by crushing, water granulation, drying, carbonisation in inert medium, and gas-vapour activation. Besides, there are described method of catalyst production and method of gas desulphurisation.

EFFECT: production of new catalyst ensuring comprehensive adsorption catalytic removal of hydrogen sulphide in gas, improved engineering-and-economical performance ensured with temperature reduction, higher sulphur content and catalyst service life.

5 cl, 2 tbl, 31 ex

FIELD: chemistry.

SUBSTANCE: described is catalyst for isomerisation of xylols, which includes in wt %: zeolite ZSM-5 - 10-35, calcium 0.05-1.0, calculated per zeolite, sodium 0.05-0.12, calculated per zeolite, aluminium oxide - the remaining part. Also described is method of preparing said catalyst, which includes mixing of aluminium hydroxide with zeolite ZSM-5, processing of obtained mixture with water solutions of calcium and, possibly, sodium compounds, with following forming and burning of obtained extrudates.

EFFECT: ensuring of xylol isomerisation until equilibrium composition of isomer is achieved, reduction of xylol loss at isomerisation temperature 400-460°C, increase of level of ethyl benzene, n-Nona and cumene conversion.

3 cl, 1 tbl, 9 ex

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