Alumina composites with large pore volume and large surface area obtained from aluminum oxide trihydrate, methods from preparation thereof and use

FIELD: inorganic compounds technologies.

SUBSTANCE: invention provides porous composite particles containing alumina component and residue of at least one additional crystal growth inhibitor component dispersed within alumina component, wherein indicated composite particles have (A) specific surface area at least 80 m2/g; (B) average nitrogen-filled pore diameter 60 to 1000 Å; (C) total nitrogen-filled pore volume 0.2 to2.5 cm3/g and (D) average particle size 1 to 15 μm, and where, in indicated composite particles, (i) alumina component contains at least 70 wt % of crystalline boehmite with average crystallite size 20 to 200 Å, γ-alumina obtained from indicated crystalline boehmite, or mixture thereof; (ii) residue of additional is obtained from at least one ionic compound containing ammonium, alkali metal, alkali-earth metal cation, or mixtures thereof and wherein anion is selected from group comprising hydroxyl, silicate, phosphate, sulfate, or mixtures thereof and is present in composite particles in amounts between 0.5 and 10 % of the summary weight of alumina and additional components. Invention also provides a method to obtain composite particles, agglomerated particles prepared therefrom, and a method for hydroprocessing of petroleum feed using above-mentioned agglomerates.

EFFECT: avoided unnecessary calcination before addition of metals to increase average pore size and use of organic solvents for azeotropic removal of water.

36 cl, 2 tbl, 22 ex

 

The SCOPE of the INVENTION

This invention relates to particles of a composite oxide of aluminum with a large pore volume and large surface area, methods for their preparation, the agglomerates obtained from them caused the catalysts; and to methods of using these catalysts.

BACKGROUND of the INVENTION

The prior art relating to the porous particulate alumina derived from these molded object catalysts, carriers, imprintirovannymi various catalytically active metals, compounds of metals and/or promoters, and to the different use of such impregnated media as catalysts, is wide and relatively well developed.

While the prior art shows a continuous modification and improvement of such particles, carriers and catalysts to improve their catalytic activity, and while in some cases highly desirable activity have indeed been achieved, the industry continues to exist a need for improved catalytic media and derived catalysts which have improved activity and durability together with a desirable balance of morphological properties.

Aluminum oxide is useful for different about the t, use, including carriers for catalysts and catalysts for chemical processes, catalytic nozzles for automotive mufflers and similar. In many of these applications it is desirable to add a catalytic material, such as metal ions, thin-dispersed metals, cations, etc. to aluminum oxide. The level and distribution of these metals on the media, as well as the properties of the media are key parameters that affect the complex nature of catalytic activity and durability.

Aluminium oxide is useful for catalytic use, still received a variety of ways, such as hydrolysis in water of alkoxides of aluminum, the deposition of aluminum oxide from alum, means on the basis of sodium aluminate and similar. Generally speaking though the aluminum oxide from the data sources can be used for catalytic media, such use has certain limitations.

This is due to the fact that is used in chemical reactions supported catalysts morphological media properties, such as surface area, pore volume and distribution of pore sizes, which include a total pore volume are very important. These properties serve as a means of influencing the nature and concentration of active catalytic centers, diffuse Pat tern of the Yu reactant to the active catalytic center, the diffusion of products from the active sites and the lifetime of the catalyst.

In addition, the media and its dimensions also affect the mechanical strength, density and characteristics of fill of the reactor, each of which is important for commercial use.

Hydrogenating catalysts for oil refining represent a huge share deposited on alumina catalysts are in commercial use. The use of hydroperiod covers a wide range of types of raw materials and working conditions, but has one or more General purpose, namely the destruction of containing heteroatoms impurities (sulfur, nitrogen, oxygen, metals), the increase in N/s relationships in foods (thus reducing the aromaticity, the density and/or carbon residues) and cracking carbon bonds to reduce the boiling range and average molecular weight.

More specifically, it is well known the use of series reactors with pseudocyesis layer containing a catalyst having improved efficiency and stable activity, desulfurization and demetilirovanie metal-containing heavy hydrocarbon fractions.

If you increase the oil industry share more than the heavy, low-quality crude oil in the raw materials that should be recycled, there is a growing need in the way of treatment fractions, with whom containing a series of increasingly high levels of metals, asphaltenes and sulfur.

It is well known that in crude oils and other heavy petroleum hydrocarbon fractions, such as petroleum residues, hydrocarbon fractions obtained from bituminous sand, and hydrocarbon fractions derived from coal, there are various ORGANOMETALLIC compounds and asphaltenes. The most common (frequent) metals, which can be found in such hydrocarbon streams are Nickel, vanadium and iron. Such metals are very harmful for various operations, oil refining, such as hydrocracking, hydrodesulfurization and catalytic cracking. Metals and asphaltenes cause clogging of the pores of the catalytic layer and reduce the life of the catalyst. Various metal deposits on the catalyst lead to poisoning or deactivation of the catalyst. Moreover asphaltenes tend to reduce the susceptibility of hydrocarbons to desulphurization. If a catalyst such as the catalyst desulfurization or a fluidized bed of the catalyst for cracking, exposed to hydrocarbon fraction, which contains metals and asphaltenes, the catalyst is rapidly deactivated and require premature replacement.

Although the known methods of Hydrotreating a heavy hydrocarbon fractions, including, but not limited to, heavy oil, with aborigional oil and petroleum hydrocarbon residues, the use of catalytic processes with stationary layer to convert this material without appreciable deposition of asfalto and clogging of the reactor and with the efficient removal of metals and other contaminants, such as sulfur compounds and nitrogen compounds, is not normal, because the catalysts are usually not able to maintain the activity and performance.

Thus, certain processes of hydroconversion most effectively carried out in the system with pseudocyesis layer. In pseudocyesis layer preheated hydrogen and the remainder are received in the lower part of the reactor, which has a thermal balance plus internal recirculation suspended in the liquid phase of the catalyst particles. Recent developments have included the use of powdered catalyst, which can be suspended without the need for recirculation of the liquid. In this system, part of the catalyst is continuously or periodically removed in a series of cyclones and to maintain activity add fresh catalyst. Roughly speaking in the system with pseudocyesis layer change every day about 1 wt. % loading of the catalyst. Thus, the total activity of the system is the weighted average activity of the catalyst, changing from a fresh catalyst to very with Arago, i.e. deactivated.

In General, it is desirable to develop a catalyst with the highest possible surface area to provide a maximum concentration of catalytic centers and activity. However, the surface area and pore size are obetovannye within practical limits. When the catalyst is aging and sent for diffusion requires a fairly large pores, large pores have a lower surface area.

More specifically, the developer is faced with competition considerations often dictate the balance of the morphological properties of a given media, and obtained from them the catalysts.

For example, it is recognized (see, for example, U.S. patent No. 4497909)that while the pores having a diameter less than 60 angstroms (within the area, which is called here the area of micropores), have the effect of increasing the number of active centers in certain hydrogenation catalysts based on silica/alumina, these same centers first clogged Cox, causing a reduction in activity. Similarly further recognized that when such catalysts have more than 10% of the total pore volume occupied by pores having a diameter greater than 600 angstroms (within the area, which is called here the area of the macropores), mechanical crushing strength decreases, as well as and the activity of the catalyst. Finally it is recognized that for certain catalysts based on silica/alumina maximization of pores having a diameter between 150 and 600 angstroms (approximately within the region, which is called here the area of mesopores), is desirable for the appropriate activity and durability of the catalyst.

Thus, while the increased surface area of the catalyst will increase the number of active centers, the increase in surface area leads to increase the proportion of pores in the area of micropores. As shown above, the micro pores are easily clogged with coke. In short increase surface area and maximize the mesopores are antagonistic properties.

Moreover, the surface area should not only be high, but it must also remain stable when exposed to conditions of conversion, such as high temperature and humidity. Therefore, the search continues for hydrothermally stable, with a large pore volume and large surface area of the alumina suitable as a catalyst carrier.

One of the results of this search are offered in related and assigned patent application U.S. serial No. 09/467742, filed December 21, 1999 (Doket No. W-9433-01). In this patent application describes the composite particles containing b is mit and is able to swell the clay. Such particles of the composite using activated alumina as the source of aluminum oxide, which is subjected to repeated hydration and convert the boehmite in the presence able to swell clay. While this method and received it the product has many advantages, activated alumina is a relatively expensive raw material. Activated alumina can be obtained by rapid calcination of gibbsite. So would be even more favorable to directly obtain a boehmite with a high pore volume, high surface area, using gibbsite as the primary source material. One of the obstacles to the implementation of this goal is the desire of gibbsite to form large crystallites (e.g., about 500 angstroms) during its transformation into boehmite. Large crystallites lead to a product with a low volume of pores with the desired surface area.

Thus, the continued search not only ways to get besicovich products with high surface area and pore volume, but also accomplish this in an effective manner from the point of view of cost. The present invention was developed in response to this search.

U.S. patent number 5728184 aimed at a method of manufacturing a polycrystalline ceramic materials on the basis of the e alpha-alumina by obtaining dispersions of boehmite and a source of silicon dioxide, hydrothermal processing of dispersion, converting the dispersion into a precursor of a ceramic material on the basis of alpha-alumina and calcining the precursor. Not necessarily in this method can be used nucleating material (sometimes referred to as a material of the seed) in order to reduce the size of the crystallites of alpha alumina and to increase the density and strength of the resulting ceramic material. Described nucleating materials include alpha-Al2About3and alpha-Fe2O3. In column 3, line 25, and further describes that "nucleating material" refers to material which increases the conversion of intermediate alumina to alpha-alumina. Thus, this patent uses as raw material boehmite and boehmite converts to alpha-alumina. The opposite way of the claimed present invention is based on a mixture of three-hydrate of aluminum oxide, a component of the seed of aluminum oxide, for example, activated alumina, and inhibitors of the growth of crystals (also referred to here IRRC) to obtain a boehmite having certain morphological and crystallographic properties, which typically converted into gamma-alumina by calcination. Moreover in the above-mentioned patent n is what is not said about the properties of the pores of the resulting product.

U.S. patent 4797139 describes a method of producing gel microcrystalline boehmite hydrothermal treatment of gibbsite in the presence of nucleating boehmite at temperatures less than 200°and With pressures less than 200 psi (˜1379 kPa). Indicates that the conversion of gibbsite in microcrystalline boehmite slows additives, such as phosphates or fluorides, and that should be avoided such additives (column 2, lines 53 and subsequent). The process is carried out at a pH of about 5 or below, or alternatively at pH 8 or above. To get the desired microcrystalline boehmite, the size of the seed should be less than 200 angstroms in quantities of at least 7.5 wt.% relative to the precursor boehmite. However, if it is desirable to maximize the surface area, and you must use the boehmite in the manufacture of porous gamma-alumina for catalytic use, then used the seed of boehmite has a size of less than 100 angstroms and preferably less than 50 angstroms (column 3, lines 34 and following). In addition, if the microcrystalline beketovy the product is ultimately used to obtain a ceramic mixture of alpha-alumina, a seed crystal alpha-alumina submicron size to facilitate uniformity of conversion of microcrystalline boehmite to alpha alumina is desirable to mix with websiteweb source material during aging in an autoclave (column 3, lines 51 and following). With boehmite after exposure in an autoclave or a precursor boehmite to aging in an autoclave can be mixed in a variety of additives such as magnesium oxide, which act as inhibitors of crystal growth (column 1, lines 47 and following). The opposite way claimed in the present invention is based on the average particle size of all solid components in the dispersion, which ultimately kept in the autoclave, typically equal to from about 0.1 to 15 microns (i.e., from 1000 to about 150,000 angstroms)to get believie composites with high surface area and high pore volume, which is typically converted into gamma-alumina by calcination.

U.S. patent 4623364 describes alumina abrasives derived from gels of aluminum oxide, which form particles of alpha-alumina submicron in size from 0.2 to 0.4 micrometer). Abrasives are made by vibropomiar gel with grinding medium aluminum oxide. It is assumed that the grinding introduces material from the grinding representing the alumina in the gel of aluminum oxide, which affects the formation of nuclei of crystallization of alpha-alumina during firing (column 5, lines 55 and following). The described grinding medium containing about 90 wt.% alpha-aluminum oxide containing in the art SiO 2, MgO and Fe2O3. Before or after gelation to the aluminum oxide may be added various additives, such as about 5 wt.% MgO. However, MgO is present in the product in the form of spinel (magnesium aluminate: MgAl2O4), which surrounds the unreacted alpha-aluminium oxide (column 6, line 60). To withstand the gel can be added inhibitors of the growth of grains, such as SiO2, Cr2About3, MgO and ZrO2. The purpose of this patent can be considered as the production of alpha alumina transformation of gamma-alumina of gel alumina to alpha-alumina at lower temperatures, for example at 1090°in the presence of the seed relative to 1190°in the absence of priming (column 6, lines 40 and later).

Opposite of the purpose of the present invention is to obtain boehmite, but not alpha-alumina by using a dose of activated alumina in combination, at least one of IRRC.

U.S. patent 4069140 describes the material carrier having a high pore volume equal to at least 0.8 cm3/g with the main part of the volume of pores having an average effective pore more than 100 angstroms and transport pores having radii of more than 1000 angstroms. Suitable carrier materials described in column 6, line 55, and further include SEB is aluminum oxide, which contains a mixture of boehmite and amorphous water aluminum oxide. In column 7, lines 15 and subsequent further revealed that the medium may contain various fillers, including aluminum oxide, silicon dioxide, amorphous silica/alumina, crystalline aluminosilicates, carbon, starch, cellulose fibers, and mixtures thereof. In the patent there is no description of crystallite size of boehmite and he, as it turns out, does not describe the sharing of gibbsite and the seed of activated alumina or boehmite) to obtain the claimed belitovogo product.

U.S. patent 4097365 describes heterogeneous composites of the joint gel, silica-alumina in a matrix consisting mainly of gel alumina. It is assumed that the silicon dioxide heterogeneously dispersed in the basis of aluminum oxide in the form of enriched silicon dioxide, joint gel, silica-alumina or grafted copolymer, and that the basis of aluminum oxide provides a matrix in which the dispersed fine particulate composite of silica-alumina. Heterogeneously dispersed enriched silicon dioxide joint gel silica-alumina differs from the homogeneous joint gel. It should be noted that the silicate inhibitors of the growth of the size of the crystals used is used in the claimed in the present invention, are not joint gels of silica-alumina.

U.S. patent 5178849 describes a method of obtaining colloidal boehmite, which consists in obtaining a slurry of hydrate of aluminum oxide having low dispersibility, the acidification of the suspension to a pH of about 3.5 or lower, to partially dissolve the hydrate of aluminum oxide, but not enough for its complete dissolution, and then the digestion acidified mixture at a temperature of from about 150 to 200°at a pressure of about 5 to 20 atmospheres (e.g., soaking in the autoclave), to obtain a colloidal boehmite. Preferable use of boehmite as starting substances can be used alumina trihydrate (gibbsite) (column 2, line 27). Can be added inhibitors of grain growth, such as silicon dioxide. The boehmite can be added to the materials of the seed, in order to increase the conversion of boehmite to alpha alumina, or alumina trihydrate (the precursor boehmite) to facilitate the formation of boehmite precursor boehmite. The seed material may be added before or after the hydrothermal treatment. Typically the seed material will have a particle size less than 1 micron (column 3, line 55). Materials seed for the conversion of boehmite to alpha alumina include submicron alpha alumina, and oxide trehu entogo iron (column 3, line 42). Materials seed for the conversion of the precursor boehmite in the boehmite include submicron boehmite (column 3, lines 46 and following). The method according to the present invention does not use an acid digestion of this type, as described in the present patent, and does not create colloidal boehmite. The aforementioned patent does not describe the combination of activated alumina and gibbsite, which converts to crystalline boehmite having a certain size of the crystallites in the presence of an inhibitor of the growth of the size of the crystals, such as silicate, phosphate or sulfate.

U.S. patent No. 5114895 describes the composition of the layered clay, homogeneous dispersed in a matrix of inorganic oxide, so that the clay layers are completely surrounded by the matrix of inorganic oxide. The matrix is an inorganic oxide selected from aluminum oxide, titanium oxide, silicon dioxide, zirconium oxide, P2O5and mixtures. Suitable clays include bentonite, thick, Laponite™, vermiculite, montmorillonite, kaolin, palygorskite (attapulgite), hectorite, chlorite, beidellite, saponite and nontronite. To get the clay, homogeneous dispergirovannoyj in a matrix of inorganic oxide, the precursor of the inorganic oxide dispersed in the form of Zola or Hydrosol and spend gelation in the presence of clay. While widely about anywayse the clay content of 5 to 70 mass. %examples use at least 30 wt. % clay. In addition, does not describe any property then or the resulting product.

Registered invention № H-189 summarizes various methods for producing boehmite. More specifically gibbsite is boiled with acid, such as nitric acid, and the resulting material is neutralized with alkali, and the resulting gel-like mass is then subjected to artificial aging and digitalout for several hours at temperatures of about 80°C. the Seed crystal alpha-alumina may be added before, during or after hydrolysis without any difference in the final product. Opposite activated alumina typically exists in the "Chi"and "Rho"-forms.

U.S. patent 3392125 aimed at producing alpha-alumina partial calcination, i.e. rapid annealing of three-hydrate of alumina (gibbsite) at a temperature of more than 800°, for "Chi"and "Rho"-forms, which are also known as activated alumina. Activated alumina is then subjected to re-hydrate and its main part is converted into a phase of aluminum oxide, representing boehmite, pseudoboehmite or mixture and then calcined at a temperature of more than 1000°C. Additional patents that describe the obtaining of boehmite Gibb the ITA, include U.S. patent No. 4117105; 4344928; 4716029; 4994253 and 5063033.

U.S. patent 4276201 describes a catalytic carrier, comprising agglomerates of alumina and 10% or less of silicon dioxide. Not necessarily in the media can be included smaller amounts of other refractory oxides. Agglomerates of aluminum oxide is produced by the contact of the aqueous gel of aluminum oxide with an organic liquid which is essentially immiscible with water at the ratio of organic liquid contained in the gel water, so that only part of the water is removed from the aqueous gel of alumina before drying of the gel. You can then apply a number of techniques to spend the agglomerating such as the location of the gel in a rotary film evaporator and the evaporation of the liquid phase with continuous stirring. Agglomerated alumina is then calcined.

U.S. patent 4886594 describes a catalytic composition for Hydrotreating, comprising hydrogenating component comprising essentially a metal component where the metal is selected from group VIB, and phosphor component is mounted on the surface of a carrier containing a porous refractory inorganic oxide and not containing zeolite.

U.S. patent No. 4981825 relates to the composition of the particles of the inorganic metal oxide (e.g. SiO2and clay, where the oxide particles on there who have separated from each other by the particles of clay. Suitable clays include Laponite™. Describes the ratio of the metal oxide/clay is from 1:1 to 20:1, preferably from 4:1 to 10:1). The composition of the subject invention, is obtained from Zola inorganic oxide having a particle size of from 40 to 800 angstroms (from 0.004 to 0.08 microns). The particle size in the final product depends on the size of the particles in the original ash, although the final particle size is not reported. Critical that the particles of metal oxide and clay have opposite charges, so they will be attracted to each other, so that the clay particles inhibit the aggregation of particles of metal oxide. Thus, it is described that the clay particles are positioned between the particles Zola. Regulation of charges on two different types of particles is determined by the pH of Zola. the pH of the inorganic oxide is controlled by adding acid so that it is below its isoelectric point, whereby induce a negative charge on the particles of inorganic oxide. While described that suitable inorganic oxides of the metals include Al2O3any of the embodiments of the invention with the use of Al2O3not shown. So the "translation" of this concept on Al2O3is not without difficulties. For example, the isoelectric point of the Al2O3is y Lochem pH, equal to about 9. However, Sol Al2O3is formed only at a low pH of less than about 5. If the pH exceeds about 5, Sol Al2O3will be deposited from the dispersion or primarily will never be formed. On the contrary, sols SiO2should not be sour. Therefore, while any point below the isoelectric point acceptable to the sols of SiO2it is not fair for the sols of Al2O3. On the contrary, it is necessary to operate at a pH significantly below the isoelectric point of the Al2O3in the field of pH where the sols are formed of aluminum oxide. Moreover, this patent does not say anything about the size of the crystallites or the properties then the resulting composite and its essence is aimed only at obtaining high surface area. As shown above, the surface area and high pore volume are antagonistic properties.

The opposite way claimed in the present invention uses as a starting Sol Al2O3(which is poorly formed or not formed boehmite) and forms a colloidal solution during the hydrothermal treatment. the pH at which the form claimed in the present invention compounds is too high, so that the Sol was formed during the hydrothermal treatment, and the particles of the initial oxide is of luminia are too big to obtain a homogeneous Sol.

Another area of technology related to various combinations of clays and metal oxides, known as the intercalated clay. Intercalated clay is represented by U.S. patent No. 3803026; 3887454 (see also 3844978); 3892655 (see also 3844979); 4637992; 4761391 (see also 4844790); and 4995964. Intercalated clay or describing their patents typically contain the requirement, namely, that used large ratio of clay:the Sol, and is formed, at least some amount of small pores (<25 angstroms).

U.S. patent 3803026 describes a hydrogel or a suspension of a hydrogel comprising water, a fluorine-containing component, and an amorphous joint gel, comprising the oxides or hydroxides of silicon and aluminum. Amorphous joint gel further comprises an oxide or hydroxide of at least one element selected from magnesium, zinc, boron, tin, titanium, zirconium, hafnium, thorium, lanthanum, cerium, praseodymium, neodymium, phosphorus, and amorphous specified joint gel is present in the hydrogel or suspension of a hydrogel in an amount of 5 to 50 wt.%. the pH of the suspension make equal from 6 to 10, and conditions of conversion to generate the significant amount of crystalline aluminosilicate mineral, preferably in a homogeneous mixture with a significant amount of unreacted amorphous GE joint who I am. The molar ratio of silica/alumina of at least equal to 3:1, and the resulting material is called a synthetic layered crystalline aluminosilicate clay mineral. In column 5, line 39, and further describes that the resulting aluminosilicate can be crushed to particles, grind into powder, the powder is atomized in a hydrogel or a suspension of a hydrogel, which is added to the components selected from the parent compounds, addition of aluminum oxide. The resulting mixture is then dried and activated. Even though the above description, no specific examples of the application of a mixture of silicon dioxide-aluminum oxide with aluminum oxide are not given. Therefore, the source of aluminum oxide, the final aluminum oxide and the amount of each of the materials used are not described.

U.S. patent No. 3887454 (and its main patent 3844978) describes a layered, dioctahedral type claylike material (LDCM), consisting of silicon dioxide, aluminum oxide and containing magnesium oxide included in its structure, in controlled quantities. The preferred clays are montmorillonite and kaolin. In column 6, line 24, and further describes that the clay material can usually be combined with components of the inorganic oxide, such as, inter alia, AMO is PNY alumina. On the contrary, the claimed currently uses composite crystalline aluminum oxide, representing the boehmite. Similar descriptions are found in U.S. patents No. 3892655 and 3844979, except that these later patents related to clay mineral laminated type and trioctahedral structure containing magnesium oxide as component (LTCM), and are illustrated by clay type of saponite.

U.S. patent No. 4637992 is a patent related to the intercalated clay, which uses a colloidal suspension of inorganic oxides and adds to it is able to swell the clay. While specific ranges, illustrating the ratio of clay to inorganic oxide, are not disclosed, it appears that the end product is still referred to as substrate-based clay, which includes an inorganic oxide. Therefore, this suggests that the final material contains mostly clay, but not the overwhelming amount of aluminum oxide and very minor amounts of clay, as in the case of the present invention. See, for example, column 5, lines 46 and subsequent patent '992.

U.S. patent No. 4844790 (isolated from U.S. patent No. 4761391) refers to exfoliating clay, obtained by the reaction, is able to swell the clay with an agent that promotes the formation of columnar structure,which includes aluminum oxide. The ratio of clay to the agent, contributing to the formation of columnar structure is from 0.1:10 to 10:1, preferably between 1:1 and 2:1. However, the essence of a patent is clay containing aluminum oxide and not the aluminum oxide containing less than 10 wt.% the clay. It has been discussed that the metal oxide support separately records of clay and in addition impart acidity, which is responsible for the catalytic activity exfoliating clay. The preferred clay is Laponite™.

U.S. patent No. 4995964 aimed at product obtained by intercalation in capable of expanding clay (hectorite, saponite, montmorillonite) oligomers derived from salts of rare earth metals and, in particular, trivalent rare earth metals, and polyvalent metal cations, contributing to the formation of columnar structures, such as Al3+. Material aluminum oxide is an aluminium-containing oligomer, which is used to make layered columnar structure of the clays. The claimed invention does not use or produces oligomers materials of hydroxides of aluminum.

U.S. patent No. 4375406 describes compositions containing fibrous clay and pre-calcined oxides prepared by obtaining a liquid suspension of clay with pre-calcined oxide, mixing the slurry for the formation of the joint variance and molding and drying of the joint variance. The ratio of the obtained fibrous clay to the composition of the pre-calcined oxide can vary from 20:1 to 1:5. These amounts are significantly higher amounts of clay used in the claimed in the present invention. Moreover fibrous clays such as thick or attapulgite, do not fall into the framework is able to swell clays described here.

A number of patents aimed at different types of aluminum oxide and the methods of its production, namely Re 29605; SIR H198; and U.S. patent№3322495; 3417028; 3773691; 3850849; 3898322; 3974099; 3987155; 4045331; 4069140; 4073718; 4120943; 4175118; 4708945; 5032379 and 5266300.

More specifically, U.S. patent 3974099 directed to a hydrogel of silica/alumina of the joint gels of sodium silicate and sodium aluminate. The essence of this invention is aimed at the deposition of Al2O3the gel silicon dioxide/aluminum oxide, which stabilizes the centers of cracking in relation to hydrothermal deactivation (Column 2, lines 43 and subsequent). The resulting material typically has approximately 38.6% of alumina, if you remove all excess sodium aluminate.

U.S. patent No. 4073718 describes the catalytic basis of aluminum oxide stabilized with silicon dioxide, which is deposited cobalt or Nickel catalyst.

U.S. patent No. 4708945 describes a catalyst for the cracking of silicon dioxide on sennoga on like boehmite surface bonding the porous particles of boehmite and processing them with steam at a temperature over 500° With to induce the reaction of silicon dioxide with boehmite. Typically used 10% silicon dioxide to achieve a surface monolayer of silicon dioxide to improve thermal stability.

U.S. patent No. 5032379 focused on alumina having a pore volume greater than 0.4 cm3/g and a pore diameter in the range from 30 to 200 angstroms. Aluminum oxide is prepared by mixing two different types are able to connect with re-hydration of aluminum oxide to obtain a product having a bimodal pore distribution.

U.S. patent No. 4266300 describes a carrier of aluminum oxide, which is obtained by mixing at least two finely dispersed oxides of aluminum, each of which is characterized by at least one mode of pores, at least one of the ranges (i) from 100000 to 10000 angstroms, (ii) from 10000 to 1000 angstroms, (iii) from 1000 to 30 angstroms.

U.S. patent No. 4791090 describes a catalyst carrier with redispersion size distribution of micropores. Column 4, line 65 describes what can be done two sizes of micropores, mixing different materials having different pore sizes, such as aluminum oxide and silicon dioxide.

U.S. patent No. 4497909 aimed at the media from a silicon dioxide/aluminum oxide, having a silicon dioxide content of about less than 40% by mass, and at least one component nobly what about the metal from group VII of the Periodic table, and where the catalyst contains pores having a diameter of less than 600 angstroms, occupying at least 90% of the total volume of pores, the pores having a diameter of 150 to 600 angstroms, occupying at least about 40% of the total pore volume is formed of pores having a diameter of less than 600 angstroms.

U.S. patent No. 4159969 describes a method for manufacturing agglomerates of aluminum oxide by contact of the aqueous gel of aluminum oxide with an organic liquid immiscible with water, where the amount of the specified fluid is a function of the water in the aqueous gel of aluminum oxide. During or after gelation to the aluminum oxide can add a slight amount of clay, such as bentonite or kaolin, sufficient to increase the strength of the agglomerates. No specific amount of clay is not described and kaolin is not able to swell clay. None of the examples clay does not apply.

The following patents describe various types of clays: U.S. patent No. 3586478; 4049780; 4629712 and PCT publication no WO 93/11069 and WO 94/16996.

The following patents describe various types of agglomerates, which can be obtained from alumina: U.S. patents№3392125; 3630888; 3975510; 4124699; 4276201 (see also 4309278); 4392987 and 5244648.

U.S. patent No. 3630888 describes a catalyst having a structure in which the availability of channels having diameters between about 100 and 1000 Angstrom units,is from 10 to 40% of the total pore volume and in which the availability of the channels, having diameters of more than 1000 Angstrom units, is approximately between 10 and 40% of the total pore volume, while the remaining pore volume is approximately 20% to 80% of micropores with a diameter of less than 100 angstroms.

The following patents describe various operations hydrogenation and the use of these catalysts include U.S. patent No. 3887455; 4657665; 4886594; PCT publication no WO 95/31280.

SUMMARY of INVENTION

The present invention is based on the discovery that when the dispersion and the hydrothermal processing of three-hydrate of aluminum oxide in the presence of controlled quantities of a component of a seed representing dispersed activated alumina, and at least one additional component, representing a growth inhibitor of the size of the crystals, the resulting composite particles containing boehmite, have a small crystallite size, which gives a high surface area, at the same time having a higher pore volume relative to the case of the absence of priming and additional components. These properties are still essentially in the agglomerates, for example in the moulded extrudates (extrudates), obtained from the particles of the composite before and after impregnation (impregnation) of the catalytically active metallic components, such as components, use the e for operations hydroperiod. Obtaining aluminum oxide in the form of high pore volume and high average pore diameter of makes unnecessary the annealing before adding metals to increase the average diameter of the pores. Also becomes unnecessary use of organic solvents for azeotropic removal of water, which is expensive and harmful to the environment.

Accordingly, in one aspect of the present invention proposed a porous composite particles comprising a component of aluminum oxide and at least the remainder of one additional component, representing a growth inhibitor size crystals homogeneously dispersed in the component of aluminum oxide, where these particles of the composite after calcination at 537,8°C for 2 hours) are:

(A) specific surface area equal to at least about 80 m2/g;

(B) an average pore diameter of nitrogen from about 60 to 1000 angstroms;

(C) total pore volume of desorption of nitrogen from about 0.2 to 2.5 cm3/g; and

(D) average particle diameter from about 1 to 15 microns/ and where in said composite particles:

(i) component aluminum oxide includes at least 70 wt.% (a) crystalline boehmite having an average crystallite size from about 20 to 200 angstroms; (b) gamma-alumina, obtained from the specified crystallic the ski boehmite; or (C) mixtures thereof;

(ii) the remainder of the additional component received at least one ionic compound having a cation and an anion, where the cation is selected from the group consisting of the ammonium cation of an alkali metal, cation of the alkali earth metal and mixtures thereof and an anion selected from the group consisting of hydroxyl, silicate, phosphate, sulfate and mixtures thereof and is present in the composite particles in an amount of about 0.5 to 10 wt.% on the combined weight of the component of aluminum oxide and an additional component.

In a further aspect, the present invention proposes a method of obtaining porous particles of the composite, including:

(A) mixing (i) three-hydrate of alumina, (ii) a liquid medium capable of dissolving at least part of the three-hydrate of aluminum oxide under the conditions of the hydrothermal treatment stage, (iii) at least one component of the seed, which represents the activated alumina, and (iv) at least one additional component selected from the group (a) at least one hydroxide, silicate, phosphate or sulfate of an alkaline or alkaline earth metal or ammonium, and (b) is able to swell clays, and mixtures thereof in this way and under conditions sufficient to disperse the three-hydrate of aluminum oxide component and priming of aluminum oxide in the form of cha the TIC in a liquid medium;

(B) hydrothermal treatment of the dispersion obtained in phase And at a temperature and time sufficient to convert the activated alumina and the three-hydrate of alumina in the crystalline boehmite having an average crystallite size from about 20 to 200 angstroms, and to obtain composite particles comprising the remainder of the specified additional component, a uniformly dispersed in the specified crystalline boehmite, suspended in a liquid medium;

(C) separating the liquid medium from the composite particles obtained in stage C.

In a further aspect of the present invention offers caused the catalysts obtained from the above-mentioned agglomerates.

In yet another additional aspect of the present invention, a method for hydroperiod of crude oil using the above-mentioned agglomerates as carriers for hydrogenating catalysts.

DESCRIPTION of the PREFERRED embodiments

Used herein, the term "micropore" refers to pores having a diameter less than 100 angstroms.

Used herein, the term "mesopores" refers to pores having a diameter between 100 and 500 angstroms.

Used herein, the term "macropores" refers to pores having a diameter of more than 500 angstroms.

Used herein, the term "fashion pores" refers to di is a meter long corresponding to the maximum peak, where log differential intrusion (occurrences) of nitrogen or mercury in cm3/g plotted as a function of the differential pore size.

Used herein, the term "total pore volume" means the total volume in cm3/g all time, determined by the method for desorption of nitrogen, a method for permeability of mercury. More specifically, for particles of aluminum oxide, which were not agglomerated (for example, by extrusion), the distribution of pore diameters and pore volume calculated with reference to the desorption isotherm of nitrogen (assuming cylindrical pores) by the BET method, described in the work of S. Brunauer, P. Emmett and E. Teller, Journal of American Chemical Society, 60, pp. 209-319 (1939).

Relatively particles of aluminum oxide, which have been agglomerated, for example, formed into extrudates, the distribution of pore diameters calculated by the formula:

and in accordance with the method for permeability of mercury (described in the work of H.L. Ritter and L.C. Drake, Industrial and Engineering Chemistry, Analytical Edition 17, 787 (1945)), using pressure mercury 1-2000 bar. The permeability of mercury is the method used in the case when the number of pores with a diameter <60 angstroms is small, as in the case of agglomerates.

Total pore volume of a sample of N2represents the sum of the volumes of pores desorption of nitrogen, determined by the method described above for de is orble nitrogen. Similarly, the total pore volume of the sample for mercury represents the sum of the volumes of pores mercury determined by the method described above on the permeability of mercury, using the contact angle 140°C.

The term "surface area" refers here to the specific surface area determined by nitrogen adsorption using the BET method as described above, regardless of whether the sample is in powder or agglomerated form.

All fresh surface area and dimensions of the pores (e.g., pore volume and pore size) was determined on samples that were dried (142° (C)subjected to cation exchange and dried at 142°if used stage exchange, and then calcined at 537,8° (1000° (F) within 2 hours.

All measurements of particle size and size distribution of particles, described here, to determine the Mastersizer instrument company Malvern, which works on the principle of diffraction of the laser beam and well-known experts in the field of particle analysis of small size.

All morphological properties, including mass, such as pore volume (VP, cm3/g) or surface area (PP, m2/g) you must normalize to not containing metal-based (CME).

Samples normalize here do not contain any metal basis in accordance with the following equation:

where X denotes the property of pores, such as OD (in cm3/g) or PP (m2/g);

W = wt.% the metal oxides constituting the catalytic promoter, such as the oxides of Ni, Co and Mo on the catalyst relative to the weight of the porous components of the catalyst. Weight non-porous components, such as non-porous diluents, extruded catalyst not included in the calculations wt.%;

and CME = not containing the metal base.

As shown above, the present invention relates to composite particles of boehmite derived from hydrothermally treated mixture component priming of aluminum oxide, the three-hydrate of aluminum oxide and at least one additional component, representing a growth inhibitor of crystal sizes.

Component of the seed alumina is an activated alumina, which can be prepared in various ways. For example, alumina trihydrate precipitated in the process of Baer, you can chop and quickly ignited. Activated alumina, as described here, is characterized by poor crystalline and/or amorphous structure.

It is assumed that the expression, aluminium oxide with poor crystalline structure" for the purposes of the above method means the aluminum oxide, which is such that it Ren is geostructural analysis gives an x-ray, which only shows one or more of diffused lines corresponding to the crystalline phases of aluminum oxide low-temperature transition, and provides essentially a "hee", "ro", "this", "gamma" and "pseudogamy" phase, and mixtures thereof.

The expression "alumina amorphous structure" refers to aluminum oxide, which is such that its x-ray diffraction analysis does not give any lines, characteristic high (mostly) crystalline phase.

Used here, the activated alumina can usually be obtained by rapid dehydration of aluminum hydroxides, such as bayerite, hydro-argillite or gibbsite, and nordstrandite, or oxyhydroxides aluminum, such as boehmite and diaspore. The dehydrogenation can be performed in any appropriate apparatus and with hot gaseous steam. The temperature at which the gases enter the apparatus, generally may vary from about 400° up to 1200°and the contact time of the hydroxide or oxyhydroxide with hot gases usually is between a fraction of a second and 4-5 seconds.

The resulting product may contain minor, for example, trace amounts of boehmite, Chi, gamma, alpha, and other crystal structures of aluminum oxide, as well as the remains of gibbsite.

The resulting activated alumina tipin is to show the mass loss when heated to 538° C for 1 hour, equal to from about 4 to 12 wt.%.

Specific surface area of activated alumina obtained by the rapid dehydration of hydroxides or oxyhydroxides measured by the conventional BET method, generally varies between about 50 and 400 m2/g and a particle diameter generally equal to between 0.1 and 300 microns and preferably between 1 and 120 microns with an average particle size of typically more than 1 micron, preferably between about 5 and 20, most preferably between about 5 and 15 microns. Loss on obolevanje measured by calcination at 1000°usually varies between 3 and 15%, which corresponds to the molar ratio of N2O/ Al2O3approximately between 0,17 and 0,85.

In a preferred embodiment, use activated alumina produced by rapid dehydration of Bayer hydrate (hydrargillite), which is readily available and inexpensive industrial aluminum hydroxide. Activated alumina of this type are well known to specialists in this field and method thereof have been described, for example, in U.S. patent No. 2915365; 3222129 and preferably 4051072, with column 3, line 6 to column 4, line 7, and the description of these patents is incorporated herein by reference.

Used activated alumina can be used as okovoi or can be treated so to the content of sodium hydroxide, expressed as Na2O, would be less than 1000 parts per million (PPM).

Suitable powdered source material, which is activated aluminium oxide, sold Aluminum Company of America under the trademarks CF-3, CF-2, CF-1, CF-5, CF-7 or SR-100. He also sold by the company Porocel (Little Rock, Arkansas) under the name AR-15.

The most important source of boehmite in the final product is alumina trihydrate. Fits any shape of three-hydrate of alumina, although gibbsite, his alpha form is preferred.

An additional component, which is mixed with the components of the activated alumina and the three-hydrate of aluminum oxide, acts as an inhibitor of growth of the crystals during the hydrothermal treatment. Not being tied to any particular theory, it is believed that the activated aluminum oxide forms a very small seed crystals of boehmite with re-hydration under the influence of an inhibitor of the growth of crystals. At the same time, it is believed that the alumina trihydrate partially soluble in the liquid medium, and believe that under the conditions of the hydrothermal treatment, there is an equilibrium between the dissolved alumina trihydrate and suspended insoluble alumina trihydrate. Thus, further believes what I what boehmite with a small crystallite size obtained from activated aluminum oxide, serves as a small seed crystals on the surface which crystallized boehmite from three-hydrate dissolved aluminum. Large crystallites in the boehmite result in a product with a low volume of pores in the surface area of from about 80 to 200 m2/, it Was found that specific inhibitors of the growth of crystals work in combination with activated alumina under certain conditions to reduce the size of the final crystals of boehmite.

Suitable additional components, representing a growth inhibitor of crystal sizes, which are selected from the group consisting of hydroxides, silicates, phosphates and sulfates of alkali and alkaline earth metals or ammonium, and can swell clays.

Typical examples of alkali metals or alkaline earth metals suitable for use as an inhibitor of the growth of crystals, include lithium, sodium, potassium, cesium, magnesium, calcium, strontium and barium. Among alkali metals and alkaline earth metals mentioned above, preferred are lithium, sodium, potassium, magnesium and calcium. The most preferred metal is sodium.

Typical examples of suitable hydroxides, Selo the different metals or alkaline earth metals include sodium hydroxide, the potassium hydroxide, calcium hydroxide, lithium hydroxide and magnesium hydroxide.

Typical examples of suitable additional components, which are inhibitors of the growth of crystals, among silicates of alkali metals or alkaline earth metals include mono-, di-, tri - and Tetra-substituted silicates of alkali metals including sodium silicate, potassium silicate, magnesium silicate, orthosilicate sodium (Na2SiO3), metasilicate sodium (Na2SiO3), metasilicate and potassium water glass (which is a liquid mixture of various sodium silicates).

Typical examples of suitable additional components, which are inhibitors of the growth of crystals, among phosphates of alkali metals or alkaline earth metals include sodium phosphate dvuhkamernyi, potassium phosphate dvuhkamernyi, sodium phosphate trehzameshchenny, calcium phosphate dvuhkamernyi (ortho), calcium phosphate trehzameshchenny, polymetaphosphate calcium, polymetaphosphate sodium. The preferred phosphates are polyphosphate salts such as pyrophosphates and tripolyphosphate, including duhsasana pyrophosphate salts of alkali metals and chetyrehskatnye pyrophosphate alkali metal salts and mixtures thereof, such as sodium phosphate (Piro) dvuhkamernyi (Na2H P2O7), sodium phosphate (Piro) chetyrehkolenny (Na4P2O7), potassium phosphate (Piro) chetyrehkolenny (K4P2O7), sodium phosphate (Piro) one-deputizing, sodium phosphate (Piro) trehzameshchenny and mixtures thereof. Preferred pyrophosphate salts include sodium phosphate (Piro) one-deputizing, sodium phosphate (Piro) dvuhkamernyi, sodium phosphate (Piro) chetyrehkolenny, potassium phosphate (Piro) chetyrehkolenny and mixtures thereof. The most preferred phosphate salt is sodium phosphate (Piro) chetyrehkolenny.

It is also possible to use ammonium salts with any of the above anion.

Typical examples of suitable additional components, which are inhibitors of the growth of crystals, among sulfates of alkali metals or alkaline earth metals include magnesium sulfate, potassium sulfate, sodium sulfate, lithium sulfate, and mixtures thereof.

Inhibitor of growth of the size of the crystals constituting capable to swell the clay, includes any natural or synthetic layered silicate clay with the ratio of 2:1 clay: a mineral that can be swelling and dispersion, and mixtures thereof. Swelling clays are clays that are able to increase in volume, whose plates are held together by weak and van der Waals forces. Natural swelling clay (as opposed to synthetic swelling clay) typically have a special shape or morphology, so that they show the ratio of length to width is typically more than roughly 2.0, preferably more than approximately 5,0, and the ratio of the length to the thickness of more than about 5.0 and preferably more than approximately 7,0. As a rule, typically more than about 20%, preferably more than about 40% and most preferably more than about 50% of the particles of natural clay will have discussed above, the ratio of the length to the width and length to thickness. In determining these relations for particles with irregular shape length is the straight-line distance between two points on the particle, which most are far from each other, while the width is the distance between two points that are most close to each other. Such clays include sectiony class of clays and their derivatives, subjected to ion exchange (e.g., Na+Li+). Usually shape, subjected to exchange with alkali metals, are preferred due to their increased ability to swell and dispergirujutsja. Also useful are dispersible 2:1 layered silicates such as vermiculite, chetyrehkolesnika mica and tainiolite. Synthetic g the ins, such as Laponite™may show a more spherical shape.

More specifically, the smectites are 2:1 clay mineral, which is the charge of the lattice and characteristically expand when solvation by water and alcohols, most notably ethylene glycol and glycerin. These minerals include layers represented by the General formula:

(M8)IV(M'x)VIO20(OH, F)4

where IV indicates an ion coordinated to four other ions, VI indicates an ion coordinated to six other ions, and x may be from 4 to 6. M usually denotes Si4+, Al3+and/or Fe3+but also includes some other chetyrehmetrovaya ions, such as P5+In3+Ge4+Be2+and similar. M' is usually a Al3+or Mg2+but also includes many shestiletnyaya ions, such as Fe3+, Fe2+, Ni2+, Co2+Li2+and similar. Deficits charge generated by the various substituents in these positions four and six-coordinated cations, are equalized by one or more cations, placed between the structural units. Between these structural units can also be occluded (i.e. captured or sealed) water, associated either with the structure or with cations in the form of a hydrate is th shell. When dehydration (degidroksilirovanie) the above structural units have a repeating distance of about 9 to 12 angstroms as measured by x-ray diffraction analysis. Commercially available natural smectites include montmorillonite (bentonite), beidellite, hectorite, saponite, suconet and nontronite. In addition, commercially available synthetic smectites such as Laponite™, synthetic hectorite, supplied by Laporte Industries Limited.

The smectites are classified into two categories, dioctahedral and trioctahedral, and the difference lies in the number of octahedral sites in the Central layer, which are occupied. This, in turn, is related to the valence of the cation in the Central layers.

Dioctahedral smectites have a Central cations are trivalent, and Vice, which are divalent, whereas trioctadecyl smectites are divalent Central cations with monovalent substituents. Dioctahedral smectites include montmorillonite, beidellite and nontronite, where, for example, montmorillonite has as octahedral cation (M') aluminum and magnesium as Deputy. Trioctadecyl smectites, which are preferred, include hectorite and saponite and synthetic forms, where, for example, hectorite has as the octahedron is ical cation M') magnesium and lithium as Deputy.

Smectite is most favorably used as an inhibitor of the growth of crystals is trioctadecyl smectite clay having a lath-like morphology (i.e. in the form of slats or strips) or spherical shape. However, you can use trioctadecyl smectites with plate or mixed lath-like and lamellar morphology. Examples of suitable clays from trioctahedral smectites are natural saponite and preferably of natural hectorite and synthetic hectorite.

In addition to the above-discussed form is more preferable that the particles of the initial clay consisted of aggregates of randomly oriented plates. In other words, the aggregates that form the clay particles, preferably should contain plates, oriented edge to the edge (g/K) and edge-to-edge (K/K) in addition to the plates, oriented face to face (yoy), which is the main method of platelet aggregation in montmorillonite. Examples of swelling clays, which have a plate with a well-ordered yoy joints and, therefore, are less preferred, are the natural montmorillonite and natural hectorite. Naturally occurring montmorillonite and hectorite are composed of well-oriented monobrush plates, and this form of wealth is prettuy orientation yoy aggregates of plates during air drying.

Most preferred is able to swell the clay for use as an inhibitor of the growth of crystals is synthetic hectorite. Procedures for obtaining synthetic hectorite well known and are described, for example, in U.S. patent No. 3803026; 3844979; 3887454; 3892655 and 4049780, the description of which is incorporated herein by reference.

A typical example of a synthetic hectorite is Laponite™ RD. Clay Laponite™ RD represents processed on a filter press, dried in a tray dryer and crushed in razbivka drum product. Records of clay Laponite™ RD consist of two layers of silicon dioxide, surrounded by a layer of magnesium in the octahedral configuration. Clay Laponite™ RD and other Laponite(s) produces and sells Laport Inorganics, part of the company Laport Industries Limited.

It was found that is important to a particle size of hydrate of aluminum oxide when it is mixed with activated alumina immediately prior to hydrothermal treatment.

A commercially available alumina trihydrate such as gibbsite, will typically consist of large particles with an average size of 100 microns or more.

To be effective in the method according to the present invention, it is important that the average particle size of the three-hydrate of aluminum oxide and activated alumina, which evaluation of the proposed hydrothermal processing separately and/or together, was equal typically from about 0.1 to 15.0 (for example, from 1 to 15, preferably from about 0.1 to 10.0 (for example, from 1 to 10 and most preferably about from 0.3 to 8.0 (for example, from 1 to 8) microns.

This can be done separate grinding of the three-hydrate of aluminum oxide and activated alumina, and the unification of the crushed materials, but it is preferable to mix the alumina trihydrate and activated aluminum oxide with the formation of suspensions and grind suspension in a sand mill to achieve the desired average particle size. An additional component representing a growth inhibitor of the size of the crystals can be added before or after grinding, although if the inhibitor is not fully soluble in the liquid medium, it is preferable to include it in the grinding operation, for example, when the inhibitor of the growth of crystals is a able to swell the clay.

Most preferred is to use a sand mill DRAIS and flowing the slurry through the mill many times. On the first pass typical use of mild conditions to reduce the average particle size of the components of the alumina to the intermediate level, equal to about 5 to 20 microns. When the second pass of the grinding conditions adjusted so that they were tougher reduced by the I speed with which the suspension passes through the mill. Grinding is typically performed at room temperature. Premature rehydration activated alumina boehmite to hydrothermal treatment does not occur during grinding due to the short time grinding equal to from about 0.1 to 2.0 hours, and low temperature grinding, approximately from 20 to 35°C.

Once reached the desired particle size of the active ingredients, containing aluminium, i.e. activated alumina and three-hydrate of alumina, preparing a suspension in a liquid medium of all active ingredients (i.e. activated alumina, three-hydrate of aluminum oxide and an additional component, representing a growth inhibitor of the size of the crystals). The liquid medium should be capable of dissolving at least part of the three-hydrate of aluminum oxide under the conditions of the hydrothermal treatment. The preferred liquid medium is water, preferably mostly water (for example, from 50 to 100 wt.%), most preferably deionized water, although it can be used liquid organic medium, for example, is mixed with water or miscible with water, and/or a mixture of water and an organic medium such as methanol, ethanol or dimethylsulfoxide.

The amount of liquid medium used to obtain the Uspenskii, usually chosen so as to obtain a solids content of active ingredients, equal to about 5 to 30 wt.% relative to the weight of liquid medium and the mass of the active ingredient. If the amount of liquid is too low, the viscosity of the suspension will be too high, resulting in operations such as mixing becomes difficult. On the other hand, if the amount of liquid is too large, will rastrakutas excessive amount of thermal energy during the hydrothermal processing, which is not economical.

In General, the liquid medium and the active ingredients are uniformly mixed or joint grinding, as discussed above, or, if not previously conducted a joint grinding, any conventional method using, for example, a ball mill, an air mixing device, an ultrasonic mixer, a screw mixer, a continuous type or a screw auger. Ball mill can contain any suitable grinding medium, such as a grinding medium of alpha-aluminum oxide or grinding environment of zirconium oxide.

If an additional component, which is the inhibitor of the growth of crystals, is a able to swell the clay, it is dispersed in suspension under conditions which preferably is increased to limit the degree of var is rcnote. Some are able to swell the clay more easily dispersed than the other. If the degree of dispersion achieved by contact with activated alumina and alumina trihydrate is bad, the desired effect on the properties of the pores of the aluminum oxide cannot be achieved or maximized. Accordingly, there could be the necessary steps to bring to the corresponding degree of dispersion, such as grinding (preferably joint grinding with other active ingredients), the regulation of the total content of volatile components and/or the use of a dispersant, such as sodium phosphate (Piro) currentelement (tetrasodium pyrophosphate TSPP or Na4P2O7), which, as it turns out, also works as an inhibitor of growth of crystals.

Can dispergirujutsja clay can pre-dispersing in water, using a mixing device with high shift (for example, Silverson) or other mixing device, such as a solvent Cowles. You can still use the mixer blade type (for example, a mixing device Lightening) with longer times of mixing and/or tank with baffles to increase the offset.

Achieving the appropriate degree of dispersion can swell clay hard number is but to evaluate, but typically, the higher the degree of transparency suspendida environment, the better the dispersion, and a fully transparent environment (when there is only clay) is most preferred. Typically this will occur when the clay particles are colloidal in size, for example less than about 1 micron. The most common way to reduce the clay particles to colloidal size is wet grinding, dry grinding, or both using conventional grinding equipment.

Accordingly, in the absence of a joint grinding the dispersion is able to swell the clay can be performed by mixing the clay with water, preferably under conditions of high shear within the time periods typically from about 5 to 60 and preferably about 10 to 30 minutes. The temperature at which the dispersion is not critical and will typically be in the range of from about 20 to 40°C. it is Important that the water does not contain other minerals, such as deionized water is preferred that affects the ability of clay to dispergirujutsja. Water that contains significant amounts of salts, alkaline earth metal or other cations with large charge may require TSPP to obtain a good dispersion of the clay.

The degree of dispersion increases, e is whether the original clay has a total content of volatile components typically at least 8 and preferably at least 10 wt.% and may be in the range typically from about 8 to 25, preferably about 10 to 20 and most preferably from about 13 to 18 wt.%.

The ratio of the alumina trihydrate: activated alumina in the slurry is controlled so that it was typically equal to about 0.6:1 to 19:1, preferably from about 1:1 to 9:1 and most preferably from about 1.5:1 to 17:1.

The amount of inhibitor of growth of the crystals (IRRC) depends on the desired properties of boehmite. For example, an increase in the level of IRRC will reduce the size of the boehmite crystallites, to increase the surface area and pore volume. Thus, the number of IRRC typically controlled to obtain the mass ratio of activated alumina: inhibitor in suspension, typically equal to about 100:1 to 2:1, preferably from about 50:1 to 5:1 and most preferably from about 20:1 to 5:1. The amount of inhibitor of growth of crystals alternative can be expressed as a typically varying from about 0.1 to 10, preferably from about 0.2 to 8 and most preferably from about 0.4 to 5 wt.% relative to the weight of active ingredients of the suspension, i.e. the components of the three-hydrate of aluminum oxide, activated alumina, IRRC.

More specifically, if IRRC is what alikadam, he will be present in the slurry in amounts of typically from about 0.2 to 8, preferably from about 0.4 to 6 and most preferably from about 0.5 to 5 wt.% relative to the weight of the active ingredients in suspension.

If IRRC is a hydroxide, it will be present in amounts of typically from about 0.5 to 10, preferably about 1 to 8 and most preferably from about 2 to 6 wt.% relative to the weight of the active ingredients in suspension.

If IRRC is a phosphate, it will be present in amounts (including water of hydration) is typically from about 0.1 to 10, preferably from about 0.2 to 8 and most preferably from about 0.4 to 6 wt.% relative to the weight of the active ingredients in suspension.

If IRC is sulfate, it will be present in amounts of typically from about 0.5 to 10, preferably about 1 to 8 and most preferably from about 2 to 6 wt.% relative to the weight of the active ingredients in suspension.

If IRC is able to swell the clay, he will be present in the slurry in amounts of typically from about 0.5 to 8, preferably from about 1 to 6 and most preferably from about 2 to 5 wt.% relative to the weight of the active ingredients in suspension.

If you use a combination of IRRC, the above percentages are still reflect the appropriate amounts of each component in the combination, however, the most preferred range is slightly reduced, because IRRC to some extent will be to liaise with the aim of reducing the crystallite size of the boehmite.

The above number of IRC in suspension, expressed as weight percent of the active ingredients are transferred to the particles of the composite, in which they are embedded.

The hydrothermal treatment is carried out, exposing containing the active ingredients of the suspension, the action of a pressure higher than atmospheric, temperature and time sufficient to convert as three-hydrate of aluminum oxide and activated alumina in a stable crystalline phase of boehmite. From the data of x-ray analysis is that the proportion of aluminum oxide is completely converted to boehmite.

Thus, the temperature will typically be adjusted to approximately 150° (C or higher during the hydrothermal treatment, since the formation of boehmite typically will not occur at temperatures below about 150°C. If applicable, the temperature is too high, for example above approximately 350°C, phase of boehmite can turn into phase α-aluminum oxide over an extended period of time, which is undesirable. Accordingly, it is preferable that the temperature of the hydrothermal treatment supports what was typically between about 150° With 350°and preferably between about 180°, 250°C. Within such a temperature range higher temperatures cause a higher rate of formation phase of boehmite. Moreover hydrothermal treatment at pressures in excess of several hundred atmospheres, can lead rather to the phase of the Diaspora than to the phase of boehmite. The lower limit of the pressure is not critical, yet achieved the target temperature. Time and temperature is adjusted to obtain a complete conversion of gibbsite to boehmite.

Convenient to carry out the hydrothermal treatment in a hermetically closed vessel such as an autoclave.

From the point of view of the foregoing hydrothermal processing will typically be carried out at temperatures which typically can vary from about 150 to 250, preferably from about 170 to 225 and most preferably from about 190 to 210°C for time periods of typically from about 0.1 to 0.4, preferably from about 0.5 to 3 and most preferably about 1 to 2 hours. The heat source is not critical and may include steam, microwave radiation, a microwave with convection heating, electric heating and similar.

The heating preferably is carried out at autogenous pressure, which usually reaches about 10 to 20 atmospheres. Of course, the pressure can be created and the artificial, if it is desired, without changing the essence of the invention. Such pressure may be in the range of from about 5 to 20 atmospheres, but preferably lies in the same range as the pressure autogenic. Used herein, the term " autogenic pressure refers to the pressure in a closed autoclave at a temperature, but does not exclude increased pressure obtained by the introduction of steam or gas in the autoclave for further regulate the total pressure and/or composition in the reaction, or reduced pressure, obtained by etching part of the pair. Accordingly, from the point of view of the foregoing, the pressure may typically vary from about 5 to 20, preferably from about 10 to 16 and most preferably from about 12 to 15 atmospheres.

After completion of the hydrothermal treatment of the suspension is allowed to cool to a temperature of from about 20 to 90°C. Cooling will typically occur with the same speed mixing, as in the excerpt in the autoclave. After cooling is completed, the liquid suspension is removed by conventional means. Such methods include simply drying the suspension by air. Other suitable methods include known from the prior art methods of removing free liquid (e.g. water) from the suspension and obtain a dry product. Examples of such other methods include centrifugual the tion or filtering. Preferably the removal of the fluid carried out by heating the suspension to facilitate evaporation. More preferably, heating is carried out in an oven with forced air circulation at a temperature of about 50-200°With (preferably about 100-150°). Such heating can be performed on a periodic basis or on a continuous basis. Stage of liquid removal, as a rule, removes a significant portion of the liquid medium of the suspension. However, in the resulting product may still be a small part of a liquid medium. The slurry can be dried by other methods, such as spray drying or spray drying under vacuum. In addition, the suspension can be used without drying.

The dried particles of the composite can be further processed by washing to remove or reduce the amount of salts, such as Na2O, annealing, glomerulone and/or application. During annealing removes essentially all volatile substances, and the phase of boehmite will be converted into other phases of alumina. At normal temperature annealing for measuring surface area and pore volume (2 hours at 538° (C) the aluminum oxide is in the form of gamma phase.

During annealing, as a rule, the material is heated to a temperature typically from about 400 to 1000, predpochtitelnei from 400 to 800, and most preferably from about 500 to 750° C and maintained at this temperature until the free water is removed and preferably at least about 90 wt.% related volatile components. The annealing can be performed before or after agglomerating and/or impregnating, described below, or both before and after agglomerating and/or impregnation. Typically the clay will dehydrosilybin at temperatures of annealing 650-750°C.

The composite product can be sorted according to size by any conventional method (e.g., crushing or screening). Stage crushing can be performed in any suitable way, including by crushing in a hammer mill, grinding in a roller crusher or grinding in a ball mill. You can use any method of grinding the dried material precursor. The term "segmentation" is used to include all such methods.

Composite product obtained in the state typically will include (a) component aluminum oxide containing at least 70, preferably at least 85, and most preferably at least 90 wt.% crystalline boehmite having a range of sizes of crystallites, described in more detail hereinafter, and the content of crystalline boehmite component of aluminum oxide may typically be in the range of about the 70 to 100, preferably from about 85 to 95, and most preferably from about 90 to 95 wt.% relative to the weight component of aluminum oxide, and (b) the remainder of the additional component, representing a growth inhibitor size crystals homogeneously dispersed in the component of aluminum oxide; and an additional component is included or embedded in the boehmite crystallites in the process of their education. More specifically, IRRC, for example, cations of alkaline earth metals, particularly the alkali metal cations can result in a decrease of the pore volume and surface area of composite product by calcination, if they are present above certain threshold amounts. This may be a drawback for many applications. The reduction of pore volume and surface area typically appears when the content of cations of alkali or alkaline earth metal in the composite is greater than about 0.5 wt.% relative to the weight of the composite. Thus, it may be desirable to exchange such cations for other cations, which do not have any adverse effect on the morphological properties of the composite, or at least affected to a much lesser extent. The material used, leading to this result, called here the ion exchange salt.

Typical examples of cations suitable DL is used in ion-exchange salt, include ammonium, cations derived from salts, dilute acids, such as sulphuric, nitric and HCl, transition metals such as Nickel, cobalt, molybdenum or tungsten, and salts of rare earth metals derived from rare earth elements, such as elements of the cerium subgroup of the Periodic table.

The preferred cations for the implementation of the cation-exchange capacity cations are ammonium. Accordingly, it is preferable to wash initially obtained boehmite composite with an aqueous solution of water-soluble ion-exchange salt.

Typical examples of anions suitable for ion exchange salts include sulfates, chlorides and nitrates.

Typical examples of suitable ion exchange salts include ammonium sulfate, ammonium carbonate, ammonium nitrate, ammonium chloride, Nickel chloride, cobalt sulfate, cobalt nitrate and similar.

Rinsing solution ion-exchange salt typically will not displace a significant amount of anions inhibitor of the growth of the crystals, as they tend to cling more strongly than the cations, although the degree of anion exchange is not critical. Actually anions inhibitor of the growth of crystals can show their own positive impact on the prepared of these catalysts. For example, the phosphate can help atomized Ni, With whom, Mo or W on impregnowana catalyst, and silicate can increase the activity of the media and its thermal/hydrothermal stability.

Cation leaching can hold suspendirovanie one or more times boehmite composite in an aqueous solution, typically containing from about 0.1 to 10, preferably from about 0.2 to 8 and most preferably from about 0.4 to 5 wt.% suitable for the exchange of salt. The content of boehmite suspension typically is about 10 to 15 wt.% relative to the weight of the suspension.

Typically the boehmite is suspended in a dilute solution of ion-exchange salt for about 5 to 30 minutes at 65°With moderate stirring. the pH can be lowered to approximately range from 4.5 to 5.7 acid to help remove Na2O, if present. The suspension is typically filtered and washed with water to remove salts. If the level of sulfate is high, the material can be re-suspended at pH 8 or above, using ammonium hydroxide or ammonium carbonate to strengthen the currency.

As you can see from the above, the final composition of the composite boehmite regarding additional component, representing a growth inhibitor of crystal sizes, more accurately described as a composition derived from a specific inhibitor of crystal growth used in modified the Ohm, if this is the case, in the stage of leaching with a cationic exchange, if it applies. Accordingly, for convenience, the final component of the inhibitor of the growth of crystals that reflect such modification, called here a remnant of an additional component, representing a growth inhibitor of crystal sizes.

In the absence of a stage of washing with a cationic exchange amount and nature of the balance of the additional component, representing a growth inhibitor of crystal sizes, Beketova the composite will reflect and essentially be the same as its original amount and composition used in the suspension, which hydrothermal process. After the stage of washing with a cationic exchange amount of the initial cation(s) an additional component, representing a growth inhibitor of the size of the crystals remaining in the composite, typically is from about 0 to 100, preferably from about 0 to 10 and most preferably from about 0 to 5 wt.% the number of cation(s)initially present before leaching. Similarly, after the stage of leaching, the amount of the initial anion inhibitor of the growth of the crystals remaining in the composite, typically is from about 50 to 100, preferably from 75 to 100 and most preferably is from about 95 to 100 wt.% from initially present before leaching the number.

Thus, any reduction in the initial content of the cation or anion inhibitor of the growth of crystals in the composite will be accompanied by appropriate substitution of cations and anions exchange salt.

Accordingly, it is possible to characterize the remainder of the additional component, representing a growth inhibitor of the size of the crystals, the composite comprising any of the above-described initial growth inhibitors of the size of the crystals together with any swap salt, so that the total balance will typically be from about 0.5 to 10, preferably from about 0.5 to 5, most preferably from about 0.5 to 3 wt.% relative to the weight of the joint component of aluminum oxide and the remainder of the additional component.

Amitava part of the resulting component of aluminum oxide in the composite will have a crystalline form, typically described as conventional boehmite, for example, in U.S. patent No. 4716029 in column 1, lines 19 and following, but may also include non-traditional forms. At high levels of the inhibitor of the growth of the boehmite crystals will be presented as pseudoboehmite, i.e. it can have a very small crystallites. Given the high levels normally get the crystallite size from 30 to 60 angstroms.

The crystallite size in the crystal b is the mit component of aluminum oxide is typically equal to about 20 to 200 (for example, from 100 to 200), preferably from about 30 to 150 (e.g., 120-150) and most preferably from about 35 to 100 angstroms.

The crystallite size of boehmite, you can define the following procedure. The sample is ground manually using a mortar and pestle. Smooth layer of the sample is placed 3.5 g of PVA (polyvinyl alcohol) and pressed in for 10 seconds at 3000 psi (˜20684 kPa or ˜204 ATM)to obtain a tablet. Then the tablet is scanned by a radiation Cuα(alpha) and get x-rays between 22 and 33 degrees 2 theta. The peak at 28 degrees 2 theta is used to calculate the crystallite size using the equation of Scherer (Scherer, +Equation 1 below) and the measured width of the peak at half height. Correction of the instrumental broadening of the peak determined by applying the same procedure fit the profile for scanning NIST SRM 660 (provides the calibration of the profile line of laboratory hexaborate lanthanum) and then using the peak width as a standard in the form b in the following equation:

where B = width of the peak sample;

b = width of the peak standard.

Discussed above, the scan angle 22-33 degrees corresponds to samples that do not contain other crystal form of aluminum oxide in addition to boehmite, sufficient to mask the characteristic peaks of boehmite (in the example, gibbsite). If such masking occurs, you can access other unmasked characteristic peaks for crystallite size determination, for example at 14, 28, 38 and 48° 2θ.

The amount of crystalline boehmite in the aluminum oxide containing different from boehmite form, can be defined, as described in further for agglomerates.

Samples dried in a drying Cabinet at 142°during the night before a quantitative assessment of the content of crystalline boehmite.

The resulting composite particles can be separated, thermally activated under the same conditions as described for agglomerates in the future, or be used directly for applying to a catalyst.

Preferably the particles of the composite is separated and dried and optionally sorted by size. Suitable particle size can typically be in the range of about 1 to 150 (for example, from 1 to about 100, preferably from about 2 to 60, and most preferably from about 2 to 50 microns.

The separation is performed by filtration, evaporation, centrifugation, and similar ways. The suspension can also be subjected to spray drying for effective separation.

The resulting composite particles have a surface area by nitrogen adsorption typically, ENISA least about 80, preferably at least about 150 and most preferably at least about 200 m2/g and a surface area typically can be in the range of from about 80 to 500, preferably from about 150 to 450, and most preferably from about 200 to 400 m2/year

The average pore diameter of the particles of the composite in nitrogen at a partial pressure of nitrogen R/R00,995 will typically be in the range of from about 60 to 1000, preferably from about 80 to 500 and most preferably from about 90 to 350 angstroms.

Total pore volume, determined by the desorption of nitrogen particles of the composite at the same partial pressure of nitrogen can vary from about 0.2 to 2.5, preferably from about 0.5 to 2.4 and most preferably from about 1.0 to 2.3 cm3/year

The advantage of the present invention is that the combined use of activated alumina and inhibitor of the growth of the size of the crystals increases the average pore diameter of the nitrogen and total pore volume, at the same time increasing the surface area. Thus, by variation of the synthesis conditions can be monitored and modified pore volume and average pore diameter, in order to achieve increased catalytic activity without loss of surface area. The catalyst with a high average pore diameter of which you can make application metals to calcination at a high temperature, reducing the need for pre-treatment steam to increase the average diameter of the pores.

The content of macropores (i.e.% of the pores within the total volume of pores desorption of nitrogen, which fall within the scope macropores) of the composite particles will typically be no more than about 90, preferably about 75, and most preferably no more than about 60% of the total pore volume, and the content of macropores will typically be in the range of from about 0 to 90, preferably from about 5 to 75 and most preferably from about 5 to 60% of the total pore volume.

The content of mesopores by desorption of nitrogen will typically be in the range of from about 10 to 100, preferably from about 15 to 90, and most preferably from about 30 to 80% of the total pore volume. Moreover, typically, at least 20, preferably at least 40, and most preferably at least 60% of the pores within the area of mesopores will have pore diameters typically approximately from 100 to 400, preferably from about 100 to 300 and most preferably from about 100 to 250 angstroms.

It is also desirable that the content of mesopores on the nitrogen in the composite particles as they are received, they had a fashion then, preferably only one fashion then (modal), typically equal to about 60 to 400, preferably from about 70 to 300 naibolee preferably from about 80 to 250 angstroms.

The content of micropores on the nitrogen in the composite particles will typically be not more than about 80, preferably not more than about 60, and most preferably not more than about 50% of the total pore volume, and the content of micropores typically may be in the range of from about 0 to 80, preferably from about 5 to 60, and most preferably about 10 to 50% of the total pore volume.

In addition, the agglomerates can be mixed with other conventional oxides of aluminum, to receive media having a distribution of pore sizes with two or more modes in the area of mesopores. Each aluminum oxide contributes in Vogue mesopores in its unique characteristic position. Also considered a mixture of two or more of aluminum oxide, prepared from can swell clays having different fashion then.

While the composite particles of aluminum oxide can be used directly as carriers, more convenient and more frequent is the agglomerating particles for such use.

Such agglomerates or agglomerated particles of aluminum oxide can be used as catalysts or carriers for catalysts in any reactions that require special structure then, together with good mechanical, thermal and hydrothermal properties. The agglomerates is of emita the present invention thus may find particular application as carriers for catalysts for the treatment of exhaust gases, created in internal combustion engines, and for processing hydrogen petroleum products, such as hydrodesulfurization, hydrodemetallization and gidrogenizirovanii. They can also be used as carriers for catalysts in the reactions of removal of sulfur (Claus catalysis), dehydrogenation, reforming, steam reforming, dehydrohalogenation, hydrocracking, hydrogenation, dehydrogenization and dehydrocyclization hydrocarbons or other organic compounds, as well as in the reactions of oxidation and reduction.

In addition, they can be used as catalysts themselves in reactions that typically catalyze the oxides of aluminum, such as hydrocracking and isomerization reactions.

Thus, favorable properties, consisting in increased volume of pores with a high (large) surface area, good mechanical strength and hydrothermal stability of the composite particles, are transferred to the agglomerates.

More specifically, once the properties of the pores of the agglomerate are thermally stable and are essentially not affected by heat treatment at moderate temperatures equal to 500-700°With, before or after impregnating the carriers of the catalytic metal.

The term "agglomerate" refers in this description to the product, which is combine particles, which are held together by various physico-chemical forces.

More specifically, each agglomerate consists of a set of contiguous components (composite) primary particles, the size of which is determined, as described above, preferably the United and connected at their points of contact.

Thus, the agglomerates of the present invention can show a higher content of macropores than their constituent primary particles due to the presence of voids between the components of the composite particles of aluminum oxide.

However, agglomerated particles still retain a high volume of pores in the area of mesopores.

Accordingly, the agglomerates of the present invention are characterized by the fact that they have the following properties after annealing for conversion into gamma phase:

(1) surface area equal to at least about 100, preferably at least about 150 and most preferably at least about 200 m2/g, and surface area can be in the range typically from about 100 to 450, preferably from about 125 to 425 and most preferably from about 150 to 400 m2/g;

(2) the average pore diameter of typically from about 50 to 500, preferably from about 60 to 400, and most preferably from about 70 to 300 angstroms;

(3) total is the total volume of pores on mercury is equal to, from 0.2 to 2.5, preferably from about 0.5 to 2.4 and most preferably from about 1.0 to 2.3 cm3/g;

(4) the content of macropores (i.e. the pores inside the total volume of the pores fall within the scope of the macropores) is typically not more than about 90, preferably not more than about 80, and most preferably not more than 50% of the total pore volume, and the content of macropores will typically be in the range of from about 0 to 90, preferably from about 5 to 80 and most preferably from about 5 to 50% of the total pore volume;

(5) the content of mesopores is typically about 10 to 100, preferably from about 15 to 90, and most preferably from about 30 to 80% of the total pore volume. More typically, at least about 20, preferably at least about 40, and most preferably at least about 60% of the pores within the area of mesopores will have diameters typically from about 100 to 400, preferably from about 100 to 300 and most preferably from about 100 to 250 angstroms.

It is also desirable that the content of mesopores in the agglomerated particles as they are formed, they had a fashion then in the field meopar typically from about 60 to 400, preferably from about 70 to 300 and most preferably from about 80 to 250 angstroms.

The average diameter of the agglomerated shall ASTIC typically approximately from 0.5 to 5, preferably from about 0.6 to 2, and most preferably from about 0.8 to 1.5 mm

In addition, the agglomerates can be mixed with other conventional oxides of aluminum, to receive media having a distribution of pore sizes with two or more modes in the area of mesopores. Each aluminum oxide contributes fashion in the area of mesopores in its unique characteristic position. Mixtures of these oxides of aluminum can also be prepared in the form of agglomerates with a bimodal distribution of pore sizes. Mixture and the resulting fashion then it is possible to make so that to match the size of the molecular masses of the reacting substances.

The agglomerating composite oxide of aluminum is performed by methods well known in the art and, in particular, by methods such as granulation, extrusion, molding granules in a rotating drum, and similar. You can also use the technique of sintering, where the composite particles having a diameter of approximately less than 0.1 mm, aglomerated into particles with a diameter of at least about 1 mm by a granulating liquid.

As is well known to specialists in this field, sintering can be carried out when necessary, in the presence of additional amorphous or crystalline binders, and to the mixture, which must be glomerulopathy, you can add the ing a pore-forming reagents. Traditional binders include other forms of alumina, silica, silica-alumina, clay, Zirconia, silica-Zirconia, magnesia and silica-boron oxide. Traditional pore-forming reagents that can be used, in particular, include wood flour, charcoal, cellulose, starches, naphthalene, and in General all organic compounds that are able to be removed by annealing. However, adding a pore-forming reagents is not necessary or desirable.

If you want, you can then perform aging, drying and/or calcining the agglomerates.

The agglomerates, as soon as they are received, then typically subjected to a thermal activation treatment (annealing) at a temperature in the range typically from about 300 to 900, preferably from about 400 to 800, and most preferably from about 450 to 750°C for time periods of typically from about 0.1 to 4, preferably from about 0.2 to about 3 and most preferably from about 0.5 to 2 hours. The atmosphere activate typically represents the air, but may include inert gases such as nitrogen. Powder of aluminum oxide, of which the agglomerate, typically not calcined prior to agglomerating, because it may be difficult to link h is Stacy together to obtain a sinter.

The activation processing can be done in several stages, if this is desirable, or it may be part of processing of the agglomerate. Depending on the particular activation temperature and the applied time agglomerates of alumina mainly exhibit characteristics of the crystal structure of boehmite and gamma-alumina, or mixtures thereof.

More specifically, when the annealing temperatures and times, increasingly greater than about 300°and one hour, boehmite will increasingly turn into gamma alumina. However, gamma-aluminum oxide will have properties then boehmite, from which he received. Moreover, in the preferred annealing temperatures and times essentially the entire crystalline boehmite turns into gamma alumina. Therefore, the amount of crystalline boehmite (wt.%), discussed above, plus the presence of gamma-alumina obtained by calcination of boehmite, typically will not exceed the original content of boehmite. This conclusion is equally applicable to particles of the composite, which can activate and use directly in the form of composite particles without agglomerating.

Percentage γ-Al2O3(gamma-alumina) in the sample of the alumina is determined as follows:

(1) 100% ; -Al2O3defined as the integrated intensity (area under the peak) (440) peak standard γ-Al2O3.

(2) the intensity of the (101) peak of the quartz plate is used as a monitor of the x-ray intensity.

(3) data Collection is performed on an automatic diffractometer Philips® 3720, equipped with a graphite monochromator diffraction beam and sealed Cu x-ray tube. The x-ray generator operates at 45 kV and 40 mA.

(4) the Full width at half maximum (FWHM) and integrated intensity (area under the peak) (440) peak γ-Al2O3get fit empirical curve. When one peak does not give a good fit fitting parameters for peak use two peaks. When using two peaks to fit the empirical curve, get two crystallite size using equation 3. Percentage γ-Al2O3two sizes of crystallites is obtained using equation 2.

(5) the Percentage of γ-Al2O3in the sample is determined from the following equation:

where Isample= The integral intensity of the (440) peak of the sample;

Iquartz.c= Intensity of the (101) peak of quartz, measured in time, when measured by standard γ-Al2O3;

Istandart2O3; and

Iquartz.s= Intensity of the (101) peak of quartz measured when measuring the sample.

The crystallite size γ-Al2O3(L) is determined by the following procedure. The sample is ground manually using a mortar and pestle. Smooth layer of the sample is placed 3.5 g of PVA (polyvinyl alcohol) and pressed in for 10 seconds at 3000 psi, (˜204 ATM)to obtain a tablet. Then the tablet scan using radiation To Cuαand get x-rays between 63 and 73 degrees (2θ). To calculate the crystallite size using equation 4 using peak at 66,8 C (2θ) and measured the width of the peak at half height.

L(size in Angstrom)=82,98/FWHM(2θ°)cos(θ°) (Equation 4)

where FWHM = Full width at half maximum; and

θ = the diffraction Angle between the flux of x-rays and a planar surface on which the sample.

The percentage of boehmite present in the sample of aluminum oxide, with respect to crystalline boehmite is determined as follows:

(1) 100% of boehmite is defined as the integrated intensity (area under the peak) (020) peak alumina Capatal.

(2) the intensity of the (101) peak of the quartz plate is used as a monitor of the x-ray intensity.

(3) data Collection is performed on auto the systematic diffractometer Philips® 3720, equipped with a graphite monochromator diffraction beam and sealed Cu x-ray tube. The x-ray generator operates at 45 kV and 40 mA.

(4) the Full width at half maximum (FWHM) and integrated intensity (area under the peak) (020) peak boehmite obtained by fitting the empirical curve. When one peak does not give a good fit fitting parameters for peak use two peaks. When using two peaks to fit the empirical curve, get two crystallite size using equation 6. The percentage of boehmite two sizes of crystallites is obtained using equation 5.

(5) the Percentage of boehmite in the sample determined by the following equation:

%of boehmite=(Isample·Iquartz.c)/(Icapatal·Iquartz.s) (Equation 5)

where Isample= The integral intensity of the (020) peak of the sample;

Iquartz.c= Intensity of the (101) peak of quartz measured when measured alumina Capatal;

Icapatal= The integral intensity of the (020) peak alumina Capatal; and

Iquartz.s= Intensity of the (101) peak of quartz measured when measuring the sample.

The crystallite size of boehmite (L) is determined by the following procedure. The sample is ground manually using a mortar and pestle. Smooth layer of the sample is placed 3.5 g of PVA (polyvin Lowy alcohol) and pressed for 10 seconds at 3000 lbs/sq. inch (˜204 ATM)to obtain a tablet. Then the tablet scan using radiation To Cuαand get x-rays between 22 and 33 degrees (2θ). To calculate the crystallite size using equation 6 using peak at 28 degrees (2θ) and measured the width of the peak at half height.

L(size in Angstrom)=82,98/FWHM(2θ°)cos(θ°) (Equation 6)

where FWHM = Full width at half maximum; and

θ = the diffraction Angle between the flux of x-rays and a planar surface on which the sample.

Particles of a composite oxide of aluminum is particularly adapted for use as a carrier for various catalytic systems that use heavy metals as the catalytic component. Therefore, the metal components of such catalysts should be added and entered in the composite oxide of aluminum.

This addition can be accomplished by mixing the catalytic materials with aluminum oxide before or after hydrothermal treatment for the preparation of agglomerates, such as extrudates or pellets and the like, causing the agglomerates of alumina, such as extrudates or pellets, the catalytic material by immersion in a solution containing catalytic material, etc. Method of "dry" impregnation is a friend is a suitable alternative, where the composite particles or agglomerates are contacted with a certain amount of impregnating liquid, the volume of which corresponds to the pore volume of the carrier. Other and additional methods for modification of aluminum oxide may be desirable for professionals in this field.

Porous composites of aluminum oxide according to the present invention are particularly useful when used as carriers for catalytically active hydrogenation components, such as metals of group VIB and group VIII. These catalytically active materials can be appropriately used in the operations of hydroperiod.

More specifically, when used herein, the term "hydroperiod" means methods of refining response of feedstock (complex mixtures of hydrocarbons present in the oil, which is a liquid at standard conditions of temperature and pressure with hydrogen under pressure in the presence of a catalyst to reduce: (a) the concentration of at least one of the substances selected from sulfur impurities of metals, nitrogen and Conradson carbon and are present in the specified raw materials processed, and (b) at least one of the properties, including viscosity, pour point and the density of the processed material. Hydroperiod includes the% is si hydrocracking, isomerization/dewaxing, refining and hydrotreatment, which differ in the number of reactive hydrogen and the nature of the processed crude oil.

Typically understand that the refining includes hydroperiod liquid petroleum products, mainly containing (by weight) hydrocarbon compounds in the boiling range of lubricating oil ("feedstock"), where the feedstock is in contact with a solid caused by the catalyst under conditions of elevated pressure and temperature to saturation of aromatic and olefinic compounds and removal present in the feedstock compounds of nitrogen, sulfur and oxygen, and to improve color, odor, thermal properties, oxidation stability, UV stability of raw materials.

Typically understand that the hydrocracking includes hydroperiod predominantly hydrocarbon compounds containing at least five (5) carbon atoms per molecule ("feedstock"), which is carried out: (a) at a partial hydrogen pressure above atmospheric; (b) at temperatures typically below 593,3°With (1100°F); (C) in full leaf chemical consumption of hydrogen; (a) in the presence of applied solid catalyst containing at least one (1) hydrogenating component; and (e), where the specified raw materials processed typically provides output is more than about one hundred and thirty (130) to the moles of hydrocarbon, containing at least about three (3) carbon atoms per molecule, for every one hundred (100) of moles of the processed material containing at least five (5) carbon atoms in the molecule.

Typically understand that the Hydrotreating includes hydroperiod predominantly hydrocarbon compounds containing at least five carbon atoms per molecule ("feedstock") for desulfurization and/or denitrification of the specified recyclable raw materials, where the process is carried out by: (a) at a partial hydrogen pressure above atmospheric; (b) at temperatures typically below 593,3°With (1100°F); (C) in full leaf chemical consumption of hydrogen; (d) in the presence of applied solid catalyst containing, at least one hydrogenating component; and (e), where (i) the feedstock typically provides an output of approximately one hundred to one hundred and thirty of moles of hydrocarbons (inclusive)containing at least three carbon atoms per molecule, for every 100 moles of the source of raw materials processed; or (ii) the feedstock comprises at least 50 volume percent of the liquid mediafilter.org residue, typically boiling at about 565,6°With (1050°F), as defined by ASTM D-1160 Distillation, and where the primary function of hydroperiod is desulphurization specified source of raw materials;or (iii) the feedstock is a product of the operation of the production of synthetic oil.

Typically understand that the isomerization/dewaxing involves hydroperiod predominantly hydrocarbon oil with a viscosity index (VI) and a boiling range corresponding to lubricating oil ("feedstock"), where the specified feedstock in contact with a solid catalyst, which contains as active component microporous crystalline molecular sieve under conditions of high pressure and temperature and in the presence of hydrogen to obtain a product whose fluidity at cold temperatures is significantly improved relative to the specified feedstock and whose boiling range is essentially located in the boiling range of the feedstock.

More specifically well-known components of the catalyst for hydroperiod typically include at least one metal component selected from the group consisting of VIII group metals, including platinum group metals of group VIII, in particular platinum and palladium, metals of the iron group of group VIII, in particular cobalt and Nickel, the metals of group VI, in particular molybdenum and tungsten and their mixtures. If the feedstock has a sufficiently low sulfur content, for example less than about 1 wt.% and preferably less than about 0.5 wt.%, as the hydrogenating component can be used metals of the platinum group VII group. In this embodiment, the platinum group metals of group VIII are preferably present in amounts in the range of from about 0.01 wt.% up to 5 wt.% of the total weight of catalyst, based on elemental platinum group metal. When the processed feedstock contains more than about 1.0 wt.% sulfur, preferably hydrogenating component is a combination of at least one metal of the iron group of group VIII and at least one metal of group VIB. Hydrogenating components of the base metals are preferably present in the final catalyst composition as oxides or sulphides, preferably in the form of sulphides. Preferred full catalytic compositions contain at least about 2, preferably about 5 to 40 wt.% metal of group VIB, preferably molybdenum and/or tungsten, and typically at least 0.5 and preferably about 1 to 15 wt.% metal of group VIII of the Periodic system of elements, preferably Nickel and/or cobalt determined as the corresponding oxides. Sulfide form of these metals are preferred because of higher activity, selectivity and conservation activity.

Catalytic components, such as catalytic components for hydropower ODI, can be entered in full catalytic composition using any of the many of the procedures described.

Although the components of the base metals can be combined in the catalyst in the form of sulfides, it is not preferable. Such components are usually combined in the form of a metal salt, which can be thermally converted to the corresponding oxide in an oxidizing atmosphere or to recover hydrogen or other regenerating agent. Then the composition can be sulphydrate reaction with the sulfur compound, such as di-disulfide, hydrogen sulfide, thiols hydrocarbons, elemental sulfur, and similar.

The catalytic components can be introduced into the composite of aluminum oxide at any stage of the preparation of the catalyst. For example, metal compounds such as sulfides, oxides or water-soluble salts such as heptamolybdate ammonium, ammonium tungstate, Nickel nitrate, cobalt sulphate and similar, you can add a joint grinding, application or precipitation (crystallization) after degidratatsii, but before the final composite agglomerated. Alternative data components can be added to the composite after agglomerating application in water, alcohol or hydrocarbon solution of soluble compounds or precursors. Impregnation is preferred is entrusted method.

Another variant of implementation of the present invention is directed to a method of Hydrotreating a hydrocarbon feedstock, at least one reaction zone with pseudocyesis layer. More specifically, the hydrocarbon feedstock is in contact with hydrogen in one or a series of reaction zones with pseudocyesis layer in the presence of a catalyst to hydroperiod comprising hydrogenating component of the catalytic metals and derivatives, as described above, precipitated described here the agglomerates of a composite oxide of aluminum.

As is well known, this feedstock contains Nickel, vanadium and asphaltenes, for example, from about 40 ppm to more than 1000 ppm combined total amount of Nickel and vanadium, and up to about 25 wt.% asphaltenes. Further, for economic reasons this process it is desirable to produce lighter products and a fully demetilirovanny residual by-product, which can be used to obtain coke anode quality. This method is especially useful when cleaning feedstock with significant quantities of metals containing 150 ppm or more of Nickel and vanadium and having a sulfur content in the range of from about 1 to 10 wt.%. Typical raw materials which can be satisfactorily cleaned by the method according to the present invention, will gain a significant number of components, which boil substantially above 537,8° (1000°F). Examples of typical feedstocks are crude oil, topped crude oil, oil residues, residues as atmospheric and vacuum distillation, the oil obtained from bituminous sand, residues, obtained from oil of bituminous sand, and hydrocarbon fractions derived from coal. Such hydrocarbon fractions contain ORGANOMETALLIC impurities that create harmful effects in different processes of oil refining, which use catalysts for the conversion of specific recyclable hydrocarbon fraction. Metal contaminants that are found in such raw materials include, but are not limited to, iron, vanadium and Nickel.

While metal impurities, such as vanadium, Nickel and iron are often present in various hydrocarbon fractions, other metals are also often present in a particular hydrocarbon fraction. Such metals exist in the form of oxides or sulfides of the metal, or in the form of a soluble salt of the metal, or in the form of high molecular weight ORGANOMETALLIC compounds, including naphthenate metals and metal porphyrins and their derivatives.

Another characteristic phenomenon hydrotreatment of heavy hydrocarbons is the deposition of insoluble the x carbonaceous substances from asfaltenovyh fraction of the feedstock, which cause production problems. The number of such formed insoluble substances increases with the amount of material boiling above 537,8° (1000° (F)that convert, or with increase of the applied reaction temperature. Data insoluble substances, also known as solid hot filtration Shell, create technological difficulties to install hydroconversion and thereby limit temperature and raw materials, which can work setting. In other words, the resultant solids limits the conversion of this raw material. Technological difficulties, as described above, can begin to manifest themselves at solids levels as low as 0.1 wt.%. Levels below 0.5 wt.%, as a rule, are recommended to prevent contamination of the processing equipment. Description of the test Shell hot filtration available in the work A.J.J., Journal of Inst. of Petroleum (1951) 37, pp. 596-604 Van Kerkvoort, W.J. and Nieuwstad, A.J.J., which is incorporated herein by reference.

An assumption was made that such insoluble carbonaceous substances are obtained when heavy hydrocarbons are converted into installing hydroconversion by providing them with more bad solvent for the unconverted asfaltenovyh fraction and, consequently, create the traveler insoluble carbonaceous substances. The formation of such insoluble substances can be reduced by having the highest surface area of the catalyst for hydroconversion available through a very large pores, so that the greatest part of the catalyst surface would be available to a large asfaltovym molecules. In addition, large pores facilitate the deposition of Nickel and vanadium in the catalyst for Hydrotreating. Thus, it may be desirable to increase the content of macropores in the agglomerates of the present invention using methods well known in the prior art for use in Hydrotreating.

It was found that the use of IRC offers the developer a means for regulating the distribution of pore size in the region from 400 to 80 angstroms, in order to adapt to changes in the molecular mass of the processed raw material for controlling the diffusion process.

The composites of the present invention is particularly adapted for use in Hydrotreating.

The operation of the hydrogenation is typically carried out in one or a series of reactors with pseudocyesis layer. As previously explained, pseudocyesis layer is a layer in which particles of the solid catalyst maintained at random (chaotic) motion upward flow of liquid or gas. Pseudocyesis layer typically has a large amount of that PR is over, at least from 10% to 70% volume of solids in the besieged state. The desired boiling catalyst particles supported by the introduction of liquid raw materials, including recycling, if available, into the reaction zone at a linear velocity in the range from about 0.02 to 0.4 feet per second (˜0,61-12 cm/s) and preferably about from 0.05 to 0.20 feet per second (˜1.5-6 cm/s).

Operating conditions for the Hydrotreating of heavy hydrocarbon fractions, such as petroleum hydrocarbon residues and similar well known in the art and include a pressure in the range of from about 1000 psi abs. (68 ATM) up to 3000 lbs/sq. in. abs. (204 ATM), the average temperature of the catalyst layer in the range of from about 700°F (371° (C) to 850°F (454°C), clock volumetric liquid velocity (LHSV) in the range from about 0.1 volume of hydrocarbon per hour per volume of catalyst to 5 volumes of hydrocarbon per hour per volume of catalyst and the rate of recirculation of the hydrogen or the speed of adding hydrogen in the range of from about 2000 standard cubic feet per barrel (SCFB) (356 m3/m3) to 15,000 SCFB (2671 m3/m3). Preferred operating conditions include a total pressure in the range of from about 1200 psi abs. up to 2000 lbs/sq. in. abs. (81-136 ATM); the average temperature of the catalyst layer in the range of the zone from approximately 730° F (387° (C) to 820°F (437°C), LHSV in the range from about 0.1 to 4.0 and the rate of recirculation of the hydrogen or the speed of adding hydrogen in the range of from about 5000 SCFB (890 m3/m3) to about 10,000 SCFB (1781 m3/m3). Typically, the process temperature and flow rate are chosen so that at least about 30. % submitted fraction, boiling above 1000°F, were converted to product boiling below 1000°F and more preferably to at least about 70. % recyclable fractions were converted to product boiling below 1000°F.

For the treatment of hydrocarbon distillates working conditions typically include the partial pressure of hydrogen in the range of from about 200 lbs/sq. in. abs. (13 ATM) up to 3000 lbs/sq. in. abs. (204 ATM), the average temperature of the catalyst layer in the range of from about 600°F (315° (C) to 800°F (426°C), LHSV in the range of from about 0.4 volume of hydrocarbon per hour per volume of catalyst to 6 volumes of hydrocarbons and the rate of recycling or the speed of adding hydrogen in the range of from about 1000 SCFB (178 m3/m3) to about 10,000 SCFB (1381 m3/m3). Preferred operating conditions for the Hydrotreating of hydrocarbon distillates include the partial pressure of hydrogen in the range of from about 200 lbs/sq. in. abs. (13 ATM) up to 1200 lbs/sq. in. abs. (81 ATM); average temperature of the Loya catalyst in the range of from about 600° F (315° (C) up to 750°F (398°C); LHSV in the range of from about 0.5 volume of hydrocarbon per hour per volume of catalyst to 4 volumes of hydrocarbon per hour per volume of catalyst; and the rate of recirculation of the hydrogen or the speed of adding hydrogen within the range of from about 1000 SCFB (178 m3/m3) 6000 SCFB (1068 m3/m3).

However, the most desirable conditions for the conversion of specific raw materials in predefined product can best be obtained by converting raw materials at several different temperatures, pressures, space velocities and speeds of added hydrogen, with correlation of the influence of each of these variables and choosing the best compromise between full conversion and selectivity.

All made here refer to elements or metals belonging to a particular group, refer to the Periodic table of elements and Hawley's Condensed Chemical Dictionary, 12thEdition. In addition, any references to the group or groups should be references to the group or groups as reflected in this Periodic table of the elements, using the CAS system for numbering groups.

The following examples are given as specific illustrations of the invention. However, it should be understood that the invention is not limited to the specific details set out in the examples. Everything Asti and percentages in the examples, as well as in the remainder of this description are the mass, unless otherwise agreed. If this is not specified here otherwise, all measurements or transfer surface area and properties of pores in the description and the claims should be construed as made on samples that were calcined at 537,8° (1000°F) for 2 hours at atmospheric pressure in air.

As for tables 1A and 1B, we used inhibitors of the growth of the size of the crystals was a silicate in the form of sodium silicate, alkali as NaOH, sodium phosphate (Piro) chetyrehkolenny (TSPP, i.e. Na4P2O7), sodium sulfate (Na2SO4and Laponite™. The weight used Laponite™ reported on dry basis and correct for the total content of volatile components (total volatiles, TV), as measured 954,4° (1750°F). Source NaOH is sodium silicate (3,2 SiO2/Na2O), and NaOH. TSPP was added in the form of a hydrate with 10 molecules of water, but water is not included in the reported added mass, i.e. used Na4P2O7. It was determined that TV gibbsite is 34,65%, measured at 954,4° (1750°F). When cooked shredded suspension gibbsite, % solids was determined by first drying a weighed portion of the suspension when 137,8° (280°F) and then Prokaeva for 1 hour at 954,4° (1750°F). TV calcined priming of aluminum oxide was determined by calcination at 954,4° (1750°F) and measuring the mass loss.

Moreover % solids, reported in column 1 of table 1A, represents the total wt.% solids in suspension, which is kept in the autoclave. Columns 7 and 9 of table 1A represent the % solids of the column 1, which consist of priming aluminium oxide (column 7), IRC (column 9), respectively. Column 8 of table 1A represents the % solids of the column 9, which correspond to the individual components that make up the total number of IRRC from the column 9.

Next, it is assumed that any range of numbers in the description or the claims, such as that representing a particular set of properties, conditions, physical States or percentages, is definitely includes any number falling within such range, including any subset of numbers within any range listed thus.

Comparative example 1

This comparative example describes a typical beketovy product derived from gibbsite. Used gibbsite available commercially under the trademarks SUPERFINE, HYDRAL.710 and FRF85 supplied by ALCAN, ALCOA and ALCAN, respectively. The average particle size (NAC) for each sample gibbsite in microns for series 1-3 was 11, 7 and 4, respectively. The information the Oia about the NAC for gibbsite, used in episodes 4-5, available there. Accordingly, the suspension data gibbsite with small particle size is prepared by adding each sample in water up to about 15% solids. The suspension is kept in an autoclave for 1 hour at 200°under stirring and then dried over night at 138°C. This gives a large boehmite crystallites with low pore volume for nitrogen, which is also reported in table 1, series 1-5.

Comparative example 2

This example illustrates the effect of changing the number of the seed of boehmite on the morphological properties of boehmite derived from hydrothermally treated gibbsite. Suspensions of gibbsite, milled in a sand mill and supplied by ALCOA under the trademark C-30D, type in the suspension of water and different amounts of nucleating boehmite having a crystallite size of 130 angstroms. The final solids content is about 20 wt.%. Each suspension is kept in the autoclave with stirring at 200°and then dried in an oven overnight at 138°C. the Results are summarized in table 1, a series of 6-9. Table 1 shows that the increase of the seed has only a relatively small effect on the reduction of the crystallite size and the increase of pore volume resulting from belitovogo product.

Example 1

This example of illustri is the duty to regulate the effect of the inhibitor of the growth of crystals and content of the seed of aluminum oxide on the crystallite size of boehmite and properties of the pores. The suspensions of gibbsite (which are characterized by columns 2, 3 and 4 of table 1A)sold by ALCOA under the trademark C-30D, the particle size of which is reduced by grinding the suspension at a speed of 1500 ml/minute, and second passage at 800 ml/minute to an average particle size of about 3 microns, add a slurry of activated alumina sold by ALCOA under the trademark CR-3, and a solution of sodium silicate and sodium hydroxide (which in some cases, i.e. for the series 12 is subjected to aging for 18 hours, and for series 13 for 1 hour) in different amounts, so that the contents of the resulting suspensions that can withstand autoclave, is summarized in table 1A series. 10-13.

The suspension is then aged in an autoclave at 200°within 1 or 2 hours, as reported in table 1A. Product characteristics are summarized in table 1B, series 10-13. Table 1B illustrates that under these reaction conditions 30% loading of the seed of the series 12 and 13 give a much higher volume of pores and surface area than the 20% loading of the seed of series 10 and 12.

Example 2

This example illustrates the effect of milled gibbsite on the pore volume, the resulting boehmite. To milled gibbsite suspensions obtained from Reynolds Aluminum company. under the trademark RH30 add or CF-3 (aktivirovannyj alumina with NAC 3 micron), or AR-15 (activated alumina with NAC 8 microns) together with 2% sodium silicate with a molar ratio of Na2O:SiO2equal to 1.0. The final solids content for both suspensions equal to about 15 wt.%. Individual number, expressed as a percentage of the solids are summarized in columns 4, 7 and 9 of table 1A. After exposure in an autoclave for 2 hours at 200°the suspension is dried over night at 138°C. the Results of analysis of the product are summarized in table 1B, series 14 and 15. It is seen that the seed of aluminum oxide with a smaller particle size gives the boehmite with a higher pore volume than the seed of aluminum oxide with a large particle size.

Example 3

This example illustrates the influence of the used metasilicate as a growth inhibitor of crystal sizes. To double-milled in a sand mill suspensions of gibbsite C-30D with NAC about 100 microns, add water, metasilicate sodium and CF-3 seed, which represents an activated alumina having a NAC about 30 microns. The content of solids in the resulting slurry is approximately 15 wt.% and the content of the active ingredients as the percentage of solids is equal to 68 wt.% gibbsite, 30 wt.% CF-3 and 2 wt.% metasilicate. After exposure in an autoclave for 2 hours at 200°the suspension is dried in the tip is the night when 138° C. the resulting product is analyzed and the results are summarized in table 1, series 16. You can see that to produce aluminium oxide with a high volume of pores with an average pore diameter of greater than 200 angstroms.

Example 4

This example illustrates the influence of the joint grinding of all active ingredients on the morphological properties of the product. To 11446,1 grams N2O add 360,0 grams (12.5 wt.%) sodium silicate (3,2 mol of SiO2/NaO2) and 83.9 grams of 50 wt.% the sodium hydroxide solution. Then to the resulting solution add 2410,1 grams N-30 gibbsite and 700 grams AR-15 activated aluminum oxide, sold by the company Porocel. The suspension is double-shredded 4 l sand mill until the NAC gibbsite and activated alumina will not be equal to approximately 3.0 microns, aged in an autoclave for 2 hours at 200°With, then dried in an oven overnight at 138°C. the Total solids content in the suspension is 15.3 wt.%, and the content of active ingredients in the form of a percentage of such solids is 68,18 wt.% gibbsite, to 29.27 wt.% AR-15, 1,95 wt.% SiO2and 2.64 wt.% NaOH. The product was identified rentgenograficheski as boehmite with crystallite size 95 angstroms. This example and morphological properties are described in table 1B, series 17.

Example 5

This example is illustrious the separate grinding gibbsite without other active ingredients on joint grinding of all active ingredients. Thus, for series 18 a suspension of 25 wt.% gibbsite type of ALCOA C-30 double-shredded 4 l sand mill until the NAC does not become equal to 3.0 microns. Of gibbsite, obtained by grinding in a sand mill, make the suspension in the water together with the seed representing the alumina type CF-3 with NAC 3.0 microns, and sodium metasilicate in the quantities reported in table 1A, series 18. For series 19 the same source material gibbsite, as used for series 18, mixed with the same aluminum oxide and sodium metasilicate in the same proportions as in the series 18, except that the content of metasilicate is only about 1 wt.% compared to about 2 wt.% for series 18, and crushed together until, until you get the same NAC.

Both suspensions are subjected to microwave treatment for 20 minutes at 200°in a tightly closed reactor, cooled and dried over night at 138°C. the Content of suspensions and analysis products are summarized in table 1A and b, series 18 and 19. In both cases there is about 90% conversion of gibbsite to boehmite only for 20 minutes at 200°C. Despite the rest of gibbsite, total pore volume for nitrogen is much greater than 1 cm3/year / This example also illustrates that microwave heating can give boehmite with a high pore volume of crushed suspension.

p> Example 6

This example illustrates the influence of the used combinations of inhibitors of the growth of crystals on the crystallite size of the aluminum oxide and pore volume. Prepare three suspensions containing gibbsite H-30 and the seed that represents the active alumina AR-15. The nature of the inhibitor of growth of the size of the crystals varies among sodium metasilicate, sodium sulfate and sodium phosphate (Piro) chetyrehjadernogo (TSPP), as reported in table 1 And series 20-22. Each suspension is milled together using two passes in 4 l sand mill. Each suspension is kept in an autoclave for 2 hours at 200°With stirring at 600 rpm, cooled and dried in a drying Cabinet overnight at 138°C. This example and morphological properties of the resulting products are summarized in tables 1A and 1B, series 20-22. You may notice that the crystallite size decreases significantly when adding TSPP, surface area and total pore volume for nitrogen increases significantly when adding TSPP, and adding sodium sulfate does not give a significant effect on the crystallite size, but increases the total pore volume for nitrogen.

Example 7

This example illustrates that the boehmite with a very high average diameter of pores can be obtained by aging in an autoclave together powdered mixture of gibbsite and intense activity is consistent alumina with 6% silica in the form of sodium metasilicate.

Accordingly, the suspension gibbsite (H-30), activated alumina (AR-15), silicon dioxide in the form of sodium metasilicate and sodium phosphate (Piro) chetyrehjadernogo (TSPP) is prepared at about 15 wt.% the total content of solids. This suspension is prepared by dissolving TSPP (Na4P2O7·10H2O) in deionized water, adding an aqueous solution of sodium silicate with a molar ratio of SiO2/Na2O, equal to 3.2, the solution of sodium hydroxide, activated alumina AR-15 and gibbsite N-30. The composition of the resulting suspension, which is kept in the autoclave, is summarized in table 1A, series 23. Any additions do when mixing using a mixing device type Cowles. The slurry is then milled in a 4 liter DRAIS mill with the first passage at about 1.5 l/min and the second passage at about 500 ml/min, Then the suspension is kept in an autoclave for 2 hours at 200°With stirring at 580 rpm After cooling, the suspension is dried overnight at about 140°C. Conduct ion exchange sample to lower the sodium content, re-suspendirovanie with a solution of ammonium sulfate (A/S), using 1 g A/S/g sample for 15 minutes, filtered, washed with water and dried in a drying Cabinet. Then the samples calcined for 2 hours at 538,7°d the I dimension of the surface area. Morphological properties of the product are summarized in table 1B, series 23. This material is very stable hydrothermal, as evidenced by the surface area of 154 m2/g or save 83% of the surface area after treatment at 800°C for 4 hours in an atmosphere of 20% steam.

Example 8

This example illustrates the effect of using sodium hydroxide as a growth inhibitor of crystal sizes. Suspension with 15% solids is prepared from N-30 (gibbsite), AR-15 (activated alumina) and NaOH receiving the suspension, the characteristics of which are given in table 1A, series 24. The suspension is prepared by adding 162,2 g of 50 wt.% aqueous solution of NaOH to a 7158 g of water. Then to the resulting solution with vigorous stirring 1258 g (without additional processing) H-30 (gibbsite) and 619,9 g (without additional processing) AR-15 (activated alumina). The suspension is double-crushed together in 4 l DRAIS mill with the first passage at 1.5 l/min and with a second passage at 500 ml/min, resulting in a solids content falls to about 15 wt.% to 11.5 wt.%. Then the suspension is kept in an autoclave for 2 hours at 200°C. Morphological properties are summarized in table 1B, series 24.

Example 9

Repeat example 8, except that the level of activated oxide of aluminum solid substance with lower 38,18 to 23.6 wt. %. After crushing and aging in an autoclave as in example 8 was measured morphological properties, which are shown in table 1B, series 25. As can be seen from the series 24 and 25, the increase in crystallite size decreases the surface area and reduces the pore volume and the NAC.

Example 10

This example illustrates the effect of high levels of seed and 3-component IRRC, i.e. sodium metasilicate, NaOH and TSPP, surface area and pore volume. A suspension of N-30 (gibbsite), AR-15 (activated alumina), silica, added in the form of sodium metasilicate, and 0,0065 moles TSPP/mol of aluminum oxide is prepared by adding of 37.7 g TZR·10H2About to 6848,1 g of water, followed by Association with rapid stirring of 441.6 g of 12.5 wt.% sodium metasilicate (the molar ratio of SiO2/Na2O 3,2), to 102.9 g of 50 wt.% aqueous solution of NaOH, 1224,8 g H-30 and 582,7 g AR-15. A suspension having a solids content of, as reported in table 1A, series 26, crushed a double pass to example 8. The suspension is divided and one part is kept in an autoclave for 2 hours at 200°With, while another part is kept in an autoclave for 1 hour at 200°C. Both of the product is dried overnight at 140°C. Morphological properties of the two products are summarized in table 1B, series 26 and 27, respectively.

Example 11

This example illustrates the use of the Finance silicate and TSPP as IRRC without alkali. Prepared and designated as series 28 and 29 of the two suspensions containing N-30 (gibbsite), AR-15 (activated alumina), silica and TSPP. The content of each suspension is summarized in table 1A. However, for series 28 the molar ratio of TSPP:the total number of aluminum oxide is 0,0065, and for a series of 29 it is 0,00325. Both suspension double-shredded 4 l DRAIS mill with the first passage at 1500 ml/min and with a second passage at 500 ml/min Both suspensions incubated in an autoclave for 2 hours at 200°C, cooled and then dried overnight at 140°C. the Results of the morphological analysis are summarized in table 1B, series 28-29. Sample of a series of 28 experience on hydrothermal stability, heating the sample for 4 hours at 800°C in an atmosphere of 20% steam, the surface area of the test and discover that it is equal to 249 m2/g, which is 71% of the original.

Example 12

This example illustrates the use and impact of TSPP and NaOH as IRRC. This material also has a pretty sharp distribution of pore size with an average pore diameter of between 150-200 angstroms. A suspension is prepared from N-30 (gibbsite), AR-15 (activated alumina) and sodium hydroxide, getting to 5.35 wt.% NaOH and 0.02 mole of TSPP/mol total alumina. The suspension is prepared by dissolving of 120.7 g of sodium phosphate (Piro) chetyrehjadernogo (TSPP) in 7034,7 g of water, adding 164,2 is 50 wt.% an aqueous solution of sodium hydroxide, 613,3 g AR-15 and 1267 N-30. Add all substances carried out under stirring device Cowles. A suspension of crushed together in a DRAIS mill with the first passage at 1500 ml/min and with a second passage at 500 ml/min, Then the suspension is kept in an autoclave for 2 hours at 200°C, cooled and then dried overnight at 140°C. the Results of the morphological analysis are summarized in table 1A, series 30.

Example 13

This example illustrates the effect of adding NaOH and Laponite™, synthetic hectorite manufactured by Laporte Industries as IRRC. Two suspensions (series 31 and 32), milled in a sand mill to example 8, prepared from C30D gibbsite, ALCOA CP-3 activated alumina and SiO2from the molar ratio 3,22 SiO2/Na2O with the addition of alkali to the molar ratio of Na2O/SiO2equal to 2.0. Separate fully dispersed clay Laponite within 1/2 hour in water before adding to it crushed suspension for series 32. After exposure of both suspensions in an autoclave for two hours at 200°With products dried over night at 138°C. the Content of the suspension, which is kept in the autoclave, is summarized in table 1A, and the results of the morphological analysis are given in table 1B, series 31 and 32. It is seen that Laponite™ reduces the size of the crystallites increases the area of the surface the displacement and significantly increases the total pore volume for nitrogen.

Example 14

This example compares the same suspension, sustained in an autoclave with/without Laponite RDS™. Note that Laponite RDS contains phosphate additive (so that the molar ratio R2About5/Al2About3in the final suspension is 0,018), so it can be atomized in water at higher concentrations. The first chopped in two passes in a sand mill suspensions of gibbsite add water, activated alumina CF-3 in diluted sodium silicate and sodium hydroxide having a molar ratio of SiO2/Na2O, equal to 3.2, and the resulting suspension is designated as the series 33. The series 33 is repeated and the resulting suspension is designated as the series 34, except that the suspension of the series 34 add well dispergirovannoyj suspension of Laponite RDS™ (physical mixture of Laponite RD™ and TSPP, having the composition of 6.7 wt.% Na2O; for 26.7 wt.% MgO; 1.9 wt.% SO4; 4.5 wt.% P2O5; 0,76 wt.% LiO2; 59 wt.% SiO2and ATV 13,77 wt.%) so that the final suspension contained 5 wt.% Laponite RDS™ relative to the weight of solids. Both suspensions incubated in an autoclave for 2 hours at 200°With stirring at 600 rpm compositions of the suspensions to aging in an autoclave are summarized in table 1A, series 33 and 34. After cooling, the suspension is dried in a drying Cabinet during the night when 138° C. Their morphological properties are summarized in table 1B, series 33 and 34. It is seen that the addition of Laponite RDSTMgives boehmite with a higher pore volume for nitrogen, a smaller crystallite size, higher surface area and significantly increased the total pore volume.

Example 15

This example illustrates the effect of adding small amounts of sodium phosphate (Piro) chetyrehjadernogo (TSPP) on the crystallite size and pore volume of the product from aluminum oxide, aged in an autoclave made of Laponite™. Prepare two identical suspension and denote them as lots 35 and 36, respectively, except that one (series 36) add 0,00234 moles TSPP/mol of aluminum oxide. Suspensions are prepared by dispersing 3.0 g Laponite RD™ (able to swell clay, characterized in that it contains 59-60 wt.% SiO2, 27-29 wt.% MgO, 0.7 to 0.9 wt.% LiO and 2.2 to 3.5 wt.% Na2O) in 596,6 g H2O. Then TSPP added to suspensions of Laponite™ from the series 36 and do not add to the suspension of the series 35. Then, for each suspension of Laponite™ add to 14.4 g of sodium silicate solution (12.5 wt.% SiO2, the molar ratio of SiO2/Na2O = 3,2) and 8.1 g of 50 wt.% aqueous solution of NaOH. Then, for each suspension type 522,8 g chopped in two passes in a sand mill gibbsite (H-30 from Kaiser, the total content of volatile components (TV)=75,9 wt.%) instead of the e from 55.1 g of activated alumina CF-3 (TV=10.0 wt.%). Both suspensions incubated in an autoclave for 2 hours at 200°and the product of the alumina is dried over night at 138°C. the composition of the suspension, which is kept in the autoclave, is summarized in table 1A, and the results of the morphological analysis are given in table 1, series 35 and 36. It is seen that the addition of small amounts of phosphate salt significantly reduces the size of the crystallites and increases pore volume.

Example 16

This example illustrates the influence of the joint grinding of all original material, instead of grinding only gibbsite on the properties stored in the autoclave boehmite in the system containing Laponite™. Prepare two suspensions, denoted by the series 37 and 38, containing about 68 wt.% gibbsite, about 27 wt.% AR-15 (activated alumina), about 2 wt.% SiO2(the molar ratio of Na2O/SiO21.0) and about 3 wt.% Laponite™as shown in table 1A. For series 37 only gibbsite was milled in a sand mill in suspension, while for series 38 all suspension, a member of the autoclave was crushed together. Both suspensions to grind a double transmission with moderate first passage and a strong second. Morphological analysis is given in table 1B, series 37 and 38. It is seen that the co-grinding reduces the crystallite size of boehmite and increases the volume of pores in AZ is that.

As in all cases, determination of surface area and properties of the pores, such properties as reported in the series 37 and 38, obtained after calcination at 537,8°C for 2 hours. However, part of the ' green ' sample series 38 has probalily for 4 hours at 800°C in an atmosphere of 15 wt.% pair, then determine the morphological properties and they are reported as a series of 39 in table 1B. Among the noteworthy features of the distribution of pore size product series 38 and 39, you can specify a very small pore volume in pores <100 angstroms, the fashion then in the area of the mesopores at about 250 angstroms and excellent hydrothermal stability preserving 95% of the surface area after steam treatment.

Example 17

This example illustrates the influence of Laponite™ on two different crushed together suspensions prepared with 0 and 5 wt.% Laponite™ and designated as series 40 and 41, respectively. The input data and the analysis of the products after exposure in an autoclave for 2 hours at 200°and then drying during the night are summarized in table 1A. Thus, the joint procedure of grinding the same as used for example 16, and the compositions of the suspensions are summarized in table 1A, series 40 and 41. Adding 5 wt.% Laponite™ provides aluminum oxide with a smaller crystallite size, higher surface area and much higher is the volume of the pores, than in the sample aged in an autoclave without Laponite™. The distribution of pore sizes in nitrogen for boehmite with 5% added Laponite™ (series 41) confirms a high proportion of pores with a diameter between 300 and 1000 angstroms with fashion then in the area of macropores at 780 angstroms.

Example 18

This example illustrates the effect of grinding on for very high volumes of pores. Thus, a series of 41 repeat twice (and designated as series 42 and 43), except that the co-grinding of change by controlling the number of passes through a sand mill. Also change the particle size of the original gibbsite. More specifically, in the series from 42 to 43 using 1 and 0 passes through a sand mill, respectively. The particle size of the original gibbsite to joint grinding equal to 8 microns for lots 42 and 43 relative to 100 microns for series 41. The particle size of 8 microns, get pre-grinding of gibbsite. All milled suspension is ground with everyone present ingredients. The input levels and the results are summarized in tables 1A and b, series 42 and 43. From the comparison series 41-43 shows that the pore volume is increased, and the crystallite size decreases with increasing fineness. The distribution of pore size on nitrogen confirms the increase of pore volume with increasing degree of grinding.

Example 19

This is the example illustrates the effects of using TSPP as IRRC in various quantities. Thus, prepare three identical suspension (denoted by the series 44-46)containing gibbsite, a seed crystal of aluminum oxide (AR-15), sodium silicate, sodium hydroxide and Laponite™ in the quantities reported in table 1A, series 44-46. Also suspensions add sodium phosphate (Piro) chetyrehkolenny (TSPP) in quantities 0,0; 0,00256 or 0,00511 mol TSPP on mol Al2O3, respectively, for series 44-46. All suspensions are crushed, twice passing through a sand mill after added all the ingredients, and then aged in an autoclave for 2 hours at 200°With stirring at 600 rpm, Each product is then dried in a drying Cabinet overnight at 138°C. the Results of the morphological analysis are summarized in table 1B, series 44-46. It is seen that the addition of TSPP reduces the size of the crystallites and increases the pore volume of the alumina in the form of boehmite. However, it will be observed that if the number of TSPP is too high, as in a series of 46, it will inhibit the conversion of gibbsite to boehmite. Accordingly, the series 46 is regarded as comparative example 3. High levels of TSPP can be used without inhibiting the conversion of gibbsite by changing the reaction conditions, for example, by reducing the level of silicate or increasing the level of depositing the seed of aluminum oxide.

Example 20

This example Illus who operates the effect of the use of natural clay Polargel® T (a mixture of about 10 wt.% natural hectorite and about 90 wt.% montmorillonite clays) from American Colloid Co. as IRRC. You can characterize that Polargel™ contains of 2.35 wt.% Na2O, 14,43 wt.% Al2O3, 75,35 wt.% SiO2, 3,11 wt.% MgO, 1,78 wt.% CaO, 0.84 wt.% To2O 0,067 wt.% Li2O and TV at 954°With equal 11,68 wt.%. Two suspensions, denoted as series 47 and 48, cooked with 1627,4 g gibbsite N-30, 469,2 g of activated alumina AR-15, 250,2 g (12.5% SiO2) sodium silicate (molar ratio SiO2/Na2O=3,2), 58,3 g 50% NaOH solution and 6741 g H2O. Suspension from the series 47 contains 1 g of Laponite™ RD (TV=13,26 wt.%), and suspension for series contains 48 of 54.1 g Polargel™ T (TV=11,68 wt.%). Each suspension is prepared by dispersing the respective clay in water for 1/2 hour with rapid stirring. To each suspension were then added to the silicate and alkali, and then activated alumina and gibbsite. Both suspensions are crushed dual passage 4 l sand mill, stand in an autoclave for 2 hours at 200°C, cooled and then dried in an oven overnight at 138°C. the Results of the morphological analysis are given in table 1B, series 47 and 48. It is seen that the oxides of aluminum with a close high pore volume are obtained from synthetic hectorite or mixed with natural clay.

Example 21

This example Illus what induces the action unground gibbsite in the system, containing TSPP/Laponite™ and a variable number of TSPP. Prepare three suspensions, designated as series 49-51, using 190,1 g gibbsite ('green ' AR-15 from Porocel), 50.0 g of activated alumina AR-15, 14,4 g (12.5%) of sodium silicate (3,2 SiO2/Na2O), 3.4 g of 50% sodium hydroxide, 10.4 g Laponite RD™ and 0,00256, and to 0.0039 moles TSPP/mol of aluminum oxide for lots 49-51, respectively. All the suspension is stirred, incubated in an autoclave for 2 hours at 200°and dried in an oven overnight at 138°C. Morphological analytical results are reported in table 1B, series 49-51. It is seen that without TSPP and without grinding, you can get the aluminum oxide with a moderately high pore volume, and adding TSPP reduces the size of the crystallites and additionally increases the pore volume.

Example 22

This example illustrates the effect of carrying out hydrothermal treatment with microwave radiation. To 54,9 g H2O added 0.87 g Laponite RD™ and stirred for 1/2 hour for dispersing the clay. Then the dispersion is added 1.2 g of a 12.5% solution of SiO2(SiO2/Na2O molar ratio=3,2), together with 0,28G 50% sodium hydroxide solution. Then add to 4.2 g of activated alumina CF-3 and 42.8 g of crushed double passage through a sand mill gibbsite N-30 prepared when the solids content primerno%, and the suspension is treated with microwave radiation in a tightly closed container for 20 minutes at 200°C. After cooling, the suspension is dried over night at 138°C. Morphological analytical results are summarized in table 1B, the series 52. It is seen that although the conversion of boehmite less than 100%, the total pore volume for nitrogen above 1 cm3/year

The principles, preferred embodiments of and modes of operation of the present invention have been described in the foregoing description. However, the invention intend here to protect, should not be construed as limited to the specific described forms, as they should be viewed as illustrative than restrictive. Specialists in this field can make variations and modifications without deviating from the spirit of the invention.

1. Porous particles of the composite containing the component of aluminum oxide and the remainder at least one additional component of the inhibitor of growth crystal is s, dispersed within the component of aluminum oxide, and these composite particles have

(A) specific surface area of at least 80 m2/g;

(B) an average pore diameter of nitrogen from 60 to 1000 Å;

(C) total pore volume for nitrogen from 0.2 to 2.5 cm3/g; and

(D) average particle diameter of 1 to 15 μm, and in these composite particles

(i) component aluminum oxide contains at least 70 wt.% (a) crystalline boehmite having an average crystallite size from 20 to 200 Å; (b) gamma alumina derived from the specified crystalline boehmite; or (C) mixtures thereof;

(ii) the remainder of the additional component derived from at least one ionic compound having a cation and an anion, where the cation is selected from the group consisting of ammonium, cation of an alkali metal, cation of the alkali earth metal and mixtures thereof, and the anion is selected from the group consisting of hydroxyl, silicate, phosphate, sulfate and mixtures thereof and is present in the composite particles in an amount of from 0.5 to 10 wt.% on the combined weight of the component of aluminum oxide and the remainder of the additional component.

2. The porous composite particles according to claim 1, characterized in that the aluminum oxide obtained from a mixture of gibbsite and activated alumina.

3. The porous composite particles according to claim 1, Otley is ausina fact, the remainder of the additional component obtained from a mixture of at least one silicate and at least one hydroxide.

4. The porous composite particles according to claim 2, characterized in that the balance of the additional component obtained from a mixture of at least one silicate and at least one phosphate.

5. The porous composite particles according to claim 3, characterized in that the pore volume for nitrogen is characterized as follows:

(i) the content of macropores no more than 75% of the total pore volume;

(ii) the content of mesopores from 15 to 90% of the total pore volume for nitrogen, and where at least 20% of the pores in the area of the mesopores have a diameter of from 100 to 400Å; and

(iii) the content of micropores less than 80% of the total pore volume for nitrogen.

6. The porous composite particles according to claim 2, characterized in that the balance of the additional component obtained from a mixture of at least one silicate, at least one phosphate and at least one is able to swell clay.

7. The porous composite particles according to any one of claim 2 to 6, characterized in that the balance of the additional component is present in an amount of from 0.5 to 5 wt.% relative to the weight component of aluminum oxide and the remainder of the additional component in the composite particles.

8. The porous composite particles according to claim 2, characterized in that the average size of the crystallites present in nabomita equal to from 30 to 150Å .

9. The porous composite particles of claim 8, characterized in that the surface area is from 150 to 450 m2/g, total pore volume for nitrogen ranges from 0.5 to 2.4 cm3/g and the average pore size is from 80 to 500Å.

10. The porous composite particles according to claim 2, characterized in that the balance of the additional component comprises at least one member received from the group consisting of ammonium sulfate, ammonium phosphate, alkali metal silicate, dvuhkamernyi the alkali metal silicate, Tetra-substituted silicate of an alkali metal, dvuhkamernyi phosphate of an alkali metal, an alkali metal polyphosphate and alkali metal sulfate.

11. The method of obtaining porous composite particles having a surface area of at least 80 m2/g, total pore volume for nitrogen from 0.2 to 2.5 cm3/g and an average pore diameter of nitrogen from 60 to 1000Åincluding the stage at which

(A) mixing (i) alumina trihydrate, (ii) a liquid medium capable of dissolving at least part of the three-hydrate of aluminum oxide under the conditions of the hydrothermal treatment stage (B), (iii) at least one component of the seed of activated alumina, and (iv) at least one additional component selected from the group (a) at least one hydroxide, silicate, phosphate or sulfate or alkaline saloons the land metal or ammonium, (b) is able to swell clay and (C) mixtures thereof, in such manner and under such conditions sufficient for dispersion of three-hydrate of aluminum oxide component and priming of aluminum oxide in the form of particles in a liquid medium, and the alumina trihydrate component and a dose of activated alumina together and/or individually have an average particle size of from 0.1 to 15 microns;

(B) carry out the hydrothermal treatment of the dispersion obtained in stage A, at a temperature and for a time sufficient for the conversion of the activated alumina and the three-hydrate of alumina in the crystalline boehmite having an average crystallite size from 20 to 200Åand to obtain composite particles containing the remainder of the specified additional component, dispersed in the specified crystalline boehmite, which is suspended in a liquid medium;

(C) separating the liquid medium from the composite particles obtained in stage C.

12. The method according to claim 11, characterized in that the alumina trihydrate is a gibbsite.

13. The method according to item 12, wherein the gibbsite additionally separately pulverized to an average particle size of from 5 to 20 μm before contact with activated alumina and an additional component.

14. The method according to item 12, wherein the gibbsite, activated acidline and additional component together crushed before hydrothermal treatment to obtain a gibbsite and activated aluminum oxide with an average particle size of from 0.1 to 15 microns.

15. The method according to item 12, wherein the resulting composite particles optionally washed with a solution of ammonium sulfate.

16. The method according to item 12, wherein the additional component comprises a mixture of at least one silicate and at least one hydroxide.

17. The method according to item 12, wherein the additional component comprises a mixture of at least one silicate and at least one phosphate.

18. The method according to item 12, wherein the additional component comprises a mixture of at least one silicate and at least one is able to swell clay.

19. The method according to item 12, wherein the additional component comprises a mixture of at least one silicate, at least one phosphate and at least one is able to swell clay.

20. The method according to claim 19, characterized in that it is able to swell the clay is selected from the group consisting of montmorillonite, hectorite and saponite.

21. The method according to claim 19, wherein the additional component comprises at least one member selected from the group consisting of ammonium sulfate, ammonium phosphate, alkali metal silicate, dvuhkamernyi the alkali metal silicate, Tetra-substituted silicate of an alkali metal, dvuhkamernyi phosphate of an alkali metal, an alkali metal polyphosphate, sulfate saloon the first metal, montmorillonite, hectorite and aponitolau clay.

22. Porous agglomerated particles containing porous particle composite according to claim 1 or 36, and the size of the agglomerated particles is from 0.5 to 5 mm

23. Porous agglomerated particles according to item 22, wherein the agglomerated particles as a carrier of the catalyst after calcination for conversion into gamma phase have

(i) the specific surface area of at least 100 m2/g;

(ii) an average pore diameter of from 50 to 500Å; and

(iii) the total pore volume by mercury from 0.2 to 2.5 cm3/year

24. Porous agglomerated particles according to item 22, wherein the component of aluminum oxide obtained from a mixture of gibbsite and activated alumina.

25. Porous agglomerated particles according to item 22, wherein the remainder of the additional component obtained from a mixture of at least one silicate and at least one hydroxide.

26. Porous agglomerated particles according to item 22, wherein the remainder of the additional component obtained from a mixture of at least one silicate and at least one phosphate.

27. Porous agglomerated particles according to item 22, wherein the remainder of the additional component obtained from a mixture of at least one silicate, at least one FOS is ATA and at least one hydroxide.

28. Porous agglomerated particles according to item 22, wherein the remainder of the additional component obtained from a mixture of at least one silicate, at least one phosphate and at least one is able to swell clay.

29. Porous agglomerated particles according to item 22, wherein the remainder of the additional component comprises at least one member selected from the group consisting of ammonium sulfate, ammonium phosphate, alkali metal silicate, dogsleding of alkali metal silicate, Tetra-substituted silicate of an alkali metal, dogsleding phosphate of an alkali metal, an alkali metal polyphosphate, alkali metal sulfate, montmorillonite, hectorite and aponitolau clay.

30. Porous agglomerated particles according to item 22, wherein the remainder of the additional component is present in an amount of from 0.5 to 5 wt.% on the combined weight of aluminum oxide and the remainder of the additional component.

31. Porous agglomerated particles according to any one of p-30, characterized in that they impregnated a number of at least one catalytic component effective for hydroperiod of crude oil.

32. Porous agglomerated particles according to any one of p-30, characterized in that they are impregnated at periodnum hydrogenating component, representing the metals having hydrogenating activity selected from the group consisting of metals of group VIII and group VIB of the Periodic table.

33. Porous agglomerated particles according to item 22, wherein said they were calcined at a temperature of from 300 to 900°during the period of time from 0.1 to 4 hours

34. How hydroperiod of crude oil, according to which the specified raw materials in contact with hydrogen under pressure in the presence of the applied catalyst for hydrogenation, characterized in that as the carrier for the deposited catalyst used porous agglomerated particles on p.22.

35. The method according to clause 34, wherein the agglomerated particles as a carrier of the catalyst after calcination for conversion into gamma phase have

(i) the specific surface area of at least 100 m2/g;

(ii) an average pore diameter of from 50 to 500Å; and

(iii) the total pore volume by mercury from 0.2 to 2.5 cm3/year

36. Porous particles of the composite containing the component of aluminum oxide and the remainder of the additional component, dispersed in the component of aluminum oxide, and having

(i) specific surface area of at least 80 m2/g;

(ii) an average pore diameter of nitrogen from 60 to 1000Å; and (iii) total pore volume for nitrogen from 0.2 to 2.5 cm2/is; and obtained by the method, which includes

(A) mixing (i) three-hydrate of alumina, (ii) a liquid medium capable of dissolving at least part of the three-hydrate of aluminum oxide under the conditions of the hydrothermal treatment, (iii) at least one component of the seed of activated alumina, and (iv) at least one additional component selected from the group consisting of (a) hydroxide, silicate, phosphate or sulfate of an alkaline or alkaline earth metal and (b) is able to swell the clay in this way and under conditions sufficient to disperse the three-hydrate of aluminum oxide component and priming of aluminum oxide in the form of particles having an average particle size of from 1 to 15 μm, in a liquid medium;

(B) hydrothermal treatment of the dispersion obtained in stage A, at a temperature and for a time sufficient for the conversion of the activated alumina and the three-hydrate of alumina in the crystalline boehmite having an average crystallite size from 20 to 200 Åand to obtain composite particles containing the remainder of the specified additional component, dispersed in the specified crystalline boehmite, which is suspended in a liquid medium;

(C) separating the liquid medium from the composite particles obtained in stage C.



 

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