New phase of aluminum trihydroxide and catalysts prepared therefrom

FIELD: structural chemistry and novel catalysts.

SUBSTANCE: invention provides composition including solid phase of aluminum trihydroxide, which has measurable bands in x-ray pattern between 2Θ=18.15° and 2Θ=18.50°, between 2Θ=36.1° and 2Θ=36.85°, between 2Θ=39.45° and 2Θ=40.30°, and between 2Θ=51.48° and 2Θ=52.59°, and has no measurable bands between 2Θ=20.15° and 2Θ=20.65°. Process of preparing catalyst precursor composition comprises moistening starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent in liquid carrier and a metal compound; ageing moistened starting material; drying aged starting material; and calcining dried material. Catalyst includes carrier prepared from catalyst composition or catalyst precursor and catalytically active amount of one or several metals, metal compounds, or combinations thereof. Catalyst preparation process comprises preparing catalyst carrier from starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent and catalytically active amount of one or several metals, metal compounds, or combinations thereof in liquid carrier, ageing starting material; drying and calcinations. Method of regenerating used material involves additional stage of removing material deposited on catalyst during preceding use, while other stages are carried out the same way as in catalyst preparation process. Catalyst is suitable for treating hydrocarbon feedstock.

EFFECT: improved activity and regeneration of catalyst.

41 cl, 3 dwg, 8 tbl, 10 ex

 

The technical field to which the invention relates.

The present invention relates to a newly discovered phase of trihydroxide aluminum. The present invention also relates to catalysts made from this new phase of trihydroxide aluminum, and the catalysts can be prepared in a special way to provide enhanced operational parameters for a large number of processing hydrocarbons. The present invention also relates to methods of obtaining mentioned a new phase of trihydroxide aluminum and derived from it the catalysts and to a method for improving the activity of the catalyst containing the medium silicon dioxide - aluminum oxide.

Prior art

The technical field relating to containing aluminum oxide media, the impregnation of such bearers of various catalytically active metals, compounds of metals and/or promoters and to various fields of use of such impregnated media as catalysts, widely and deeply developed. As a few of the many decisions that can be cited as examples in these areas, we can mention the following U.S. patents, which are all included in the present description as a reference for all purposes as are set forth: U.S. patent№№2838444; 2935463; 2973329; 3032514; 308907; 3124418; 3152865; 3232887; 3287280; 3297588; 3328122;3493493; 3623837; 3749664; 3778365; 3897365; 3909453; 3983197; 4090874; 4090982; 4154812; 4179408; 4255282; 4328130; 4357263; 4402865; 4444905; 4447556; 4460707; 4503911; 4588706; 4591429; 4595672; 4652545; 4673664; 4677085; 4732886; 4797196; 4861746; 5002919; 5186818; 5232888; 5246569; 5248412 and 6015485.

Although the prior art is characterized by a constant modification and improvement of such catalysts with improved catalytic activity, and in some cases actually achieved a very desirable level of activity, but still there is a growing need in the industry to an even higher activity of the catalysts provided by the present invention.

The main efforts in the development of catalysts of increased activity were aimed at the development of media that would be catalytic activity deposited on these metals. In the vast majority of applications selected for the carrier material is aluminum oxide, the most commonly - γ-aluminium oxide, but as the materials of the media used and are currently using the composites of silica - alumina, zeolites, and various other inorganic oxides and their composites.

In the case of aluminum oxide by various researchers developed methods for producing media having different specific surface area, the volume of pores and the distribution of the pore, R is smeru, so when applying the respective metals, they are particularly suitable to catalyze the desired reactions to specific raw materials, whether this response is related to hydrodesulfurization, hydrodemetallization, hydrocracking, reforming, isomerization, etc

In most cases the media based on γ-aluminium oxide produced by activated (usually by burning) of the source material on the basis of pseudoboehmite (AlOOH). In rare cases, the carrier is formed from one of the currently known of trihydroxide aluminum (Al(OH)3), gibbsite, bayerite or nordstrandite. When source material used bayerite or nordstrandite formed digidrirovanny the aluminum oxide has a different structure from the structure more typical γ-aluminium oxide, often called ηaluminum oxide; for gibbsite product of aluminum oxide can be χ-alumina. Each of these transition alumina has structural characteristics (porosity and specific surface area), which differs from more common γ-aluminium oxide. However, their typical drawback is a lower resistance than the γaluminum oxide; for specific processes of dehydrogenation and the ignition loss of specific surface area for the above-mentioned oxides of aluminum significantly b is the more what have undergone γ-alumina. U.S. patent 6015485 shows the way to improve the structure of the catalysts deposited on γ-aluminium oxide, synthesis of in-situ crystalline aluminum oxide on the carrier on the basis of γ-aluminium oxide. From this patent it is clear that formed the catalysts of increased activity.

As an example of a need for catalysts of increased activity, we can mention the need for a catalyst of increased activity for the first stage hydrocracking. In a typical process of hydrocracking of heavier hydrocarbons into more low molecular weight fractions in the presence of a hydrocracking catalyst, which is typically impregnated with a noble metal-silicon dioxide - aluminum oxide/zeolite. Currently known hydrocracking catalysts have a very high activity and capable of splitting a large amount passing through the plant material. However, such catalysts are very sensitive to the presence of contaminants such as sulfur, metals and nitrogen compounds, which, therefore, must be removed from the hydrocarbon stream prior to cracking. This is carried out in the first stage hydrocracking processes, such as gidromehanizaciya, hydrodesulfurization and hydrodemetallization. The catalysts of hydrobro ODI, used in these processes are typically soaked in a combination of metals of group VIB and group VIII of the substrate on the basis of aluminum oxide. However, existing catalysts hydrobromide insufficient to provide processing of high-volume passing through the installation of material that is recyclable catalysts for hydrocracking. As such, the first stage hydrocracking are a bottleneck in the overall process of hydrocracking, which must be compensated, for example, the size of the installation for hydrobromide relative to the hydrocracking unit.

Inventions

In accordance with the present invention in one of its aspects relates to a newly discovered phase of trihydroxide aluminum, which is formed as a result of thermal aging prepared and calcined carrier silica-alumina, obtained from a powder of amorphous alumina - enriched silicon dioxide aluminum oxide in an acidic aqueous medium. This newly discovered phase of trihydroxide aluminum, hereafter referred to as "Kamenitza", can be distinguished from the three previously known phases, gibbsite, bayerite and nordstrandite, the x-ray structure analysis. When drying and calcination Kamenitsa forming material, which structure is different from other nose is used. The catalysts obtained from this material are extremely high catalytic activity in many reactions of hydrobromide and reactions that are not related to hydrobromide. Indeed, with appropriate regulation of the conditions of aging used in the production kamenetska, the final structure of the catalyst can be adjusted to suit particular applications of the catalyst. There is evidence that the catalysts containing the same active metals and the same number of active metals behave differently with different oil feedstock, depending on the size and concentration of particles of crystalline aluminum oxide formed containing various Kamenitsa predecessors media.

Accordingly, the invention relates to compositions comprising the above-mentioned new solid phase trihydroxide aluminum, characterized by x-ray, described in more detail below.

More specifically, the invention relates to compositions comprising a solid phase of trihydroxide aluminum, and this phase has a measurable band x-rays between 2θ=18,15° 2θ=18,50°between 2θ=36,1° 2θ=eur36, 85°between 2θ=39,45° 2θ=40,30° and between 2θ=51,48° 2θ=52,59° and has no measurable bands of x-rays between 2θ=20,15�B0; and 2θ=20,65°.

The invention relates also to the above composition, in which the phase of trihydroxide aluminum additionally has a measurable band x-rays between 2θ=27,35° 2θ=27,90°between 2θ=34,75° 2θ=35,48° and between 2θ=62,40° 2θ=63,80°.

This invention relates to the above compositions, in which the phase of trihydroxide aluminum is additionally characterized by the fact that no measurable bands on the radiograph between 2θ=20,15° 2θ=20,65° and between 2θ=37,35° 2θ=37,75°and to the above described composition, in which the phase of trihydroxide aluminum has no measurable diffraction bands in the radiograph between 2θ=18,70° 2θ=18,90°between 2θ=20,30° 2θ=20,50° and between 2θ=40,30° 2θ=40,70°.

In addition, the present invention relates to precursors of catalysts comprising the above composition.

The present invention also relates to a method for obtaining these compositions Kamenetskii or including its predecessors catalysts of powder amorphous alumina - enriched silicon dioxide aluminum oxide. This method includes the process steps that are similar to those identified in the earlier patent (U.S. patent 6015485). Namely, the process involves the following stages:

(1) Simachev is the source material, comprising silica - alumina and amorphous alumina, chelat forming agent and a compound of the metal in liquid media;

(2) aging moistened thus the source material while it is wet;

(3) drying aged so the source material at temperatures and conditions which contribute significantly to the evaporation of a liquid medium; and

(4) calcining the dried thus the material.

However, in the present invention, the source material is different from that used in the patent '485, and the product of the process can be distinguished by the size and concentration of the formed particles of crystalline aluminum oxide and operating properties of the catalysts obtained from the prepared media.

In another aspect, the present invention relates to catalysts of high activity, including media based on Kamenetskii and impregnated with one or more corresponding catalytically active metal from group VIB and group VIII of the Periodic table.

In addition to the above catalyst, the present invention also relates to a method for producing such a catalyst on the basis of the above-described method of obtaining Kamenetskii adapted accordingly. So, the source material may first be form the van well-known specialists in the field of methods of obtaining catalyst carrier is desirable in a certain form. The obtained calcined carrier can then be moistened with liquid system chelate forming agent/carrier before the carrier impregnated corresponding catalytically active metals and/or simultaneously with such impregnation, and/or after the impregnation of the carrier catalytically active metals with subsequent implementation stages (2)to(4)as described above.

In addition, the present invention also relates to a method for increasing the activity of the catalytic composition containing crushed porous carrier containing silica - alumina and amorphous alumina and impregnated with one or more catalytically active metal, which includes stages:

(1') wetting the catalyst composition by contacting chelat forming agent in a liquid carrier;

(2') aging moistened thus the substrate while it is wet;

(3') drying the aged thus the substrate at a temperature and under conditions ensuring almost complete evaporation of the liquid carrier; and

(4') calcining the dried thus the substrate.

The method may be easily applied to existing catalysts, including crushed porous carrier containing silica - alumina and amorphous alumina, or may be used in the process p. the receipt of the catalyst simultaneously with the impregnation of the carrier and/or after such impregnation, containing silica - alumina and amorphous alumina, one or more catalytically active metal and/or its compounds. Furthermore, the method can be used to improve the activity of the spent catalyst in the regeneration process, and exhaust catalysts include crushed porous carrier containing silica - alumina and amorphous alumina, the spent catalyst moisten chelat forming agent in a liquid carrier, as in the above stage (1'), after removal of carbon deposits from subsequent stages (2'), (3') and (4').

The present invention relates also to a method for producing the catalyst, specially prepared for processing hydrocarbon material, and this method comprises: (a) determining the concentration of nitrogen-containing compounds in the hydrocarbon material; (b) selecting a source material comprising silica - alumina and amorphous alumina containing from about 4% of the mass. to about 8% of the mass. silicon dioxide and at least about 20% of the mass. the specified aluminum oxide is amorphous, with the specified aluminum oxide has a suitable concentration of silicon dioxide, such that being aged in a wet state at a temperature of aging in aznom condition, component, at least 20°during the period of time which shall be at least 1 day, it will form a catalyst precursor, with the specified catalyst precursor includes a sufficient concentration of the composition containing the phase trihydroxide aluminum with measurable strip in the radiograph between 2θ=18,15° 2θ=18,50°between 2θ=36,1° 2θ=eur36, 85°between 2θ=39,45° 2θ=40,30° and between 2θ=51,48° 2θ=52,59° and no measurable bands of x-rays between 2θ=20,15° 2θ=20,65°so that the catalyst derived from the specified catalyst precursor, will be effective for the treatment of specified hydrocarbon material, moreover, these concentrations of silicon dioxide, the temperature of aging in the wet state and time are chosen so that they were proportional to the concentrations of these nitrogen-containing compounds; (C) obtaining a catalyst carrier of a certain shape from a specified source material; and then wetting the obtained catalyst carrier chelat forming agent and a compound of the metal in the liquid medium, as in the above stage (1), followed by carrying out the above steps (2), (3) and (4).

Suppose (without intending to be bound by any theory)that the application of the UE is mentioned stages in this order there is an interaction between at least, silicon dioxide, aluminum oxide, amorphous aluminum oxide, chelat forming agent and aqueous acid, which under the influence of temperature and time conditions under aging leads to Kamenitsa. After drying and calcination product of this reaction forms a crystalline phase of aluminum oxide, which can be distinguished from that obtained in U.S. patent 6015485 size and concentration of particles of crystalline aluminum oxide. The size of the crystallites on the surface of the catalyst can be measured using known techniques including transmission electron microscopy.

Simultaneously with the appearance of this crystalline phase also achieved an increase in specific surface of the catalyst. In addition, in preferred embodiments of the invention, a structure is formed with porosity, reaching peak values in the first region of pore size 40Å or less, and more preferably in the range from 20Å to 40Å, the results of measurement of nitric parametria using the desorption isotherm.

The resulting catalysts of high activity find use in a number of areas that are examined in detail in many of the previously cited references. A particularly preferred field of use is the catalyst for the first stage g is dragracing if hydrogasification, hydrodesulfurization and hydrodemetallization.

Accordingly, the present invention relates also to a method of processing hydrocarbon material, comprising contacting the specified hydrocarbon material with the above-described catalysts.

These and other features and advantages of the present invention will be more readily understood by experts in this field when reading the following detailed description.

Brief description of drawings

Figure 1 shows the FTIR spectra of trihydroxide aluminum of the present invention, aged at 90°C for 1 day and 25 days, range and aged for 1 day material subtracted from the spectrum aged for 25 days material.

Figure 2 presents the FTIR spectrum of boehmite, bayerite, gibbsite and nordstrandite.

Figure 3 shows the x-ray when a 22-hour scan for the sample aged for 25 days at 90°C. Marked lanes refer to Kamenitsa. Several unmarked lines below the d-parameter 5Ådue to organic compounds, present in dried thermostat the sample. There is also a broad diffraction bands attributed to carrier-based γ-aluminium oxide and the active metal oxide.

Detailed description of the invention

A. New phase trigger is xida aluminum (Kamenitsa)

Source material

The preferred starting material for obtaining Kamenetskii powder is silica - alumina containing a significant amount of amorphous aluminum oxide. Measurable concentration Kamenetskii can be obtained from a powder, minimally containing only 4% of the mass. silicon dioxide, and the remainder is aluminum oxide, at least about 20% of the mass. which is amorphous aluminum oxide, and from a powder containing the maximum 8% of the mass. silicon dioxide, and the remainder is aluminum oxide, at least about 30% of the mass. which is amorphous aluminum oxide. Preferably, the source material contains from about 5% wt. to about 7% of the mass. silicon dioxide, and the remainder is aluminum oxide, and from about 20% wt. to about 50 wt%. aluminum oxide is amorphous.

The way to obtain

A new phase of aluminum hydroxide of the present invention can be obtained:

(1) wetting the source material by contacting with chelat forming agent in a liquid medium and the acid solution of the metal joining;

(2) the aging moistened thus the source material in the wet state in conditions (for example, a combination of temperature and duration of aging), which will lead to the formation of gelatin the nogo number kamenetska, preferably at temperatures higher than 50°C for from 1 to 10 days;

(3) drying aged so the source material at temperatures and conditions which contribute significantly to the evaporation of a liquid medium; and

(4) calcination of the dried thus the material.

Hepatoblastoma agents suitable for use in the present method include those which are known to form more stable complexes with transition metals and aluminum and, therefore, have high stability constants with respect to them. Especially preferred for use in the present invention is ethylenediaminetetraacetic acid (DTA) and its derivatives, including, for example, N-hydroxyethylnitrosamine acid, diammonium ethylenediaminetetraacetic acid. Also suitable are Tris(2-amino-ethyl)amine and Triethylenetetramine. Other candidates include diethylenetriaminepentaacetic acid, cyclohexanedimethanol acid, ethylene glycol-bis(beta-aminoacylase simple ether)-N,N'-tetraoxo acid, Tetraethylenepentamine etc. the Appropriateness of other chelat forming agents can easily estimate the specialists in this field by processing the sample source material according to the present invention, and then drying and use of the air traffic management sample determining, using transmission electron microscopy or x-ray analysis, there Kamenitsa with the appropriate size of the crystallites or not.

The number khelatoobrazuyushchimi agent is not a determining parameter for obtaining kamenetska, but affects the amount of product formed. Can be used number of khelatoobrazuyushchimi agent, changing in a wide range of values, depending on a number of factors, such as solubility in liquid media, the media type of the catalyst, and metals, which saturated the media, or they must be soaked. Normally, the source material should be moistened with liquid media containing chelate forming agent in a quantity lying in the range of 0.01 to 1.0 grams chelat forming agent per gram of starting material.

The material can be moistened by any conventional method such as dipping or spraying. To provide the necessary penetration chelat forming agent, it is preferable dipping, followed by a period of soaking. The preferred liquid carrier is water or a solution of water/ammonia.

The length of time required for aging soaked source material, is a function of the temperature in the aging process. At room temperature before occhialino age moistened substrate for at least 30 days, more preferably for at least 60 days. With increasing temperature the required aging time is reduced. At 80°preferably With age moistened material for at least two days, more preferably at least within three days. Preferably, aging is carried out at a temperature in the range from 20°to 90°C.

Then aged material is dried to substantially remove the carrier liquid. Preferably, the drying was first slowly and then rapidly at elevated temperatures in the range from 100°, 250°C. Preferably use a thermostat with forced air circulation to speed up the drying until the preferred duration of less than one hour.

The dried material is then calcined under conditions well known to specialists in this field. However, preferably the calcination takes place in two stages: first, more of the low-temperature stage in which the temperature high enough to evaporate or decomposed any remaining chelat forming agent, but which is not high enough to hepatoblastoma agents burned with the formation of carbon deposits. The temperature of this first stage will vary according to the specific t chelat forming agent, but it is usually sufficient temperature in the range from 250°With up to 350°C. as soon As any remaining chelate forming agent being removed, the catalyst may then be calcined under normal conditions of higher temperature, typically used for these purposes.

C. the Catalysts

The method of obtaining containing Kamenitsa catalysts

The method of obtaining Kamenetskii described above, may be adapted to obtain the final catalyst. The source material may first be formed as desired media known to experts in the field methods. The obtained calcined carrier can then be moistened with liquid system chelate forming agent/carrier before the carrier impregnated corresponding catalytically active metals and/or simultaneously with such impregnation, and/or after the impregnation of the carrier catalytically active metals with subsequent implementation stages (2)to(4)as described above. It is important to ensure that the stage of ageing flow conditions, when the impregnated carrier is moistened with a liquid carrier for chelat forming agent and an acidic solution of metal for impregnation.

The catalytically active metals

The present invention is applicable to catalysts impregnated with one or more of a wide range of catalytically Akti is different metals, well-known specialists in this field, which is confirmed by examples, for example, numerous referenced. In the context of the present invention "of catalytically active metals include themselves as metals and metal compounds. In addition to the catalytically active metal catalysts can also be impregnated with one or more well-known promoters, such as phosphorus, tin, silicon dioxide and titanium (including connections).

Typically, the catalytically active metals are transition metals selected from the group comprising metals of group VIB, group VIII and combinations thereof. The specific choice of metal(s), promoter(s) and their contents, of course, depend on the desired end use of the catalyst, and these variables can be easily adjusted by experts, based on end use. As specific examples may be mentioned the following (% mass. calculated on the total weight of the catalyst):

Operations hydrobromide

GidromehanizaciyaNi and/or Co, and preferably Ni, in an amount up to 7 wt. -%, designed for NiO and/or COO
Mo and/or W, preferably Mo, in an amount up to 35 wt. -%, designed for NGO3and/or WO3
optionally P, and preferably including P, in an amount up to 10 wt. -%, designed for P2O5
HydrodesulfurizationNi and/or Co, and preferably, in an amount up to 9 wt. -%, designed for NiO and/or COO
Mo or W, preferably Mo, in an amount up to 35 wt. -%, designed for NGO3and/or WO3
optionally P, and preferably including P, in an amount up to 10 wt. -%, designed for P2O5
Hydrodemetallizationoptional Ni and/or Co
preferably including Ni and/or Co in an amount up to 5 wt. -%, designed for NiO2and/or COO
Mo and/or W, preferably Mo, in an amount up to 20 wt. -%, designed for NGO3and/or WO3
optionally P, and preferably including P, in an amount up to 10 wt. -%, designed for P2O5
've got a hydro conversionNi and/or Co, and preferably Ni, in an amount up to 5 wt. -%, designed for NiO and/or COO,
Mo and/or W, preferably Mo, in an amount up to 20 wt. -%, designed for NGO3and/or WO3
optionally P, and preferably including P, in an amount up to 6 wt. -%, designed for P2O5
HydrocrackingNi and/or Co, and preferably Ni, in an amount up to 5 wt. -%, designed for NiO and/or COO,
Mo and/or W, preferably Mo, in an amount up to 20 wt. -%, designed for NGO3and/or WO3
optionally P, and preferably including P, in an amount up to 10 wt. -%, designed for P2About5
The hydrogenation/dehydrogenationnoble metal, preferably Pt or Pt in combination with Rh, in an amount up to 2 wt. -%, calculated
on
The reformernoble metal, preferably Pt or Pt in combination with other noble metal (such as Re
and/or Ir), and/or Sn in an amount up to 2 wt. -%, designed for

Operations not related to hydrobromide

Isomerizationnoble metal, preferably Pt or Pt in combination with other noble metal in quantity
up to 2 wt. -%, designed for
The process claw is and Ni and/or Co, and preferably Ni, in an amount up to 5 wt. -%, designed for NiO and/or COO,
Mo and/or W, preferably Mo, in an amount up to 20 wt. -%, designed for NGO3and/or WO3
optionally P, and preferably including P, in an amount up to 6 wt. -%, designed for P2O5

Such catalysts are impregnated media relevant components with the subsequent stages of drying, sulfatirovnie and/or annealing in accordance with the applicable end use. Such preparation of the catalyst is usually well known to specialists in this area, as evidenced by numerous examples, the above links, and additional details can include in this description reference or numerous other General reference works available on the subject.

Regeneration of the catalyst

As mentioned above, the method according to the present invention is applicable not only to the pre-formed catalyst, but can also be similarly applied for the regeneration of catalysts. In particular, after the removal of carbonaceous material from spent catalyst is well known methods such catalysts process then according to the SNO stages (1) through (4) similarly, as explained above.

Catalysts formed with the specific operations

By careful selection of the temperature and the duration of the aging stage, you can modify the blood levels and the size of the crystallites Kamenetskii together with the final pore structure.

Then the modified catalyst has a different effect, for example, hydrodesulfurization each of the pair of oils. One possibility of the formation of the catalyst of the present invention with a purpose discussed below in example 9. Example 9 is intended to illustrate the possibilities that exist when using the present invention and does not limit in any way the scope of the claims. Specialists in this field can determine other such features.

C. Characteristics Kamenetskii

X-ray diffraction analysis of the newly discovered phase of trihydroxide aluminum using Cuαirradiation of crystals confirms that the material is different from the three previously known phases of trihydroxide aluminum. As shown below in table 1, Kamenitsa gives a very strong peak at 2θ=18,33°the same angle as the main peak of gibbsite and relatively close to the main peaks of nordstrandite and bayerite. However, in the rest of the graph of the diffraction bands Kamenitsa provides a significant peaks at angles of diffraction, where the other phases do not have peaks or does not give peaks at angles where other phases have them. The position of the diffraction bands Kamenetskii shown here with a relative accuracy of 1% (confidence interval 95%), and relative intensities with a relative precision of 10% (confidence interval 95%).

Table 1
The relative intensity
Diffraction band 2θ, °Kamenitsa (1)gibbsite (2)nordstrandite (2)bayerite (2)
18,33100100--
18,50--100-
18,80---100
20,25-20,55-363070
27,633---
35,125---
36,4725---
37,55--30-
39,76--30-
39,8738---
40,50--100
52,0933---
63,126---
(1) Shows all the diffraction bands that grow with aging, indicating an increase in the concentration of a new phase.

(2) Shows only the main diffraction band for gibbsite, nordstrandite and bayerite.

As shown in table 2, the size of the crystallites Kamenetskii and integrated intensity of x-ray diffraction bands at 2θ=18,33° increase with temperature, aging and duration of aging.

Table 2
Aging temperature, °The duration of aging, daysThe size of the crystallites, AndThe integrated intensity of the band at 2θ=18,33°, ADU
901351972
2482354
3553086
5613510
7644039
10724438
801232165
753241246

Thermogravimetric analysis (TGA) and x-ray diffraction analysis containing Kamenitsa materials are heated to high temperatures, show the disappearance of the main peak at 2θ=18,33° at a temperature of approximately 250°C. Since we know that 250°represents the transition temperature trihydroxide aluminum transition oxides of aluminum, these data confirm that the new material represents a distinct new phase of trihydroxide aluminum.

In addition, the analysis by the method of IR-spectroscopy with Fourier transformation (FTIR) at 90°aged for 1 day and aged for 25 days products of low-temperature drying. The obtained spectra are shown in figure 1. It is clearly visible by the increased content of Kamenitsa in the material of the 25 days of aging, when the range of material 1-day aging subtracted from the spectrum of the material 25 days of aging, which is shown as spetr "difference" in the lower part of figure 1. The FTIR absorption bands at wave numbers 3512, 989 and 21 in the spectrum of "difference" confirm the presence of Al(OH) 3. For comparison, figure 2 shows FTIR spectra of boehmite, bayerite, gibbsite and nordstrandite.

Comparison with material obtained without silicon dioxide in the source material

The emergence of Kamenitsa in the material obtained by the method of the present invention is not so obvious when the source material contains less than about 4% of the mass. silicon dioxide. However, the correlation, which allows you to indirectly determine the number Kamenetskii contained in the product of the method of the present invention. This correlation relates the number kamenetska in the product with its structure, defined through its pore volume, measured by nitrogen adsorption. Extrapolating this correlation, we can conclude that a small amount Kamenetskii likely contained in the material obtained by using as a source material containing silicon dioxide and aluminum oxide. Data showing these extrapolated values for kamenetska in the materials obtained from such do not contain silicon dioxide and aluminum oxide, are presented in examples D and E.

Examples

The present invention, as described above, will be further explained by the following specific examples, which are presented only to illustrate and not limit the scope of claims of the invention.

Condition the conditions of the test

The test conditions used to compare the performance properties of the catalysts of the present invention and those described in U.S. patent 6015485, and the standard catalyst oil production, the following:

Test type a

Raw materials: direct distillation gas oil for the North American oil refinery

sulfur, % mass.1,25
total nitrogen, ppm65
density, g/CC0,848
aromatics, wt. -%8,63
diaromatics. wt. -%2,63

Distillation, °With:

initial114,5
50%286,7
95%368,9

Test conditions:

temperature, °343
pressure, kPa (psi)4,169 (590)
the gas flow rate, m3/m3(SCF/B)178,1 (1000)
hourly space velocity of fluids2
(LHSV), h-1

Test type

Raw material: mild Arab oil direct driving of the European refinery

sulfur, % mass.1,77
total nitrogen, ppm183
density, g/CC0,863
aromatics, wt. -%12,94
diaromatics. wt. -%4,46

Distillation, °With:

initial175
50%290,6
95%366,7

Test conditions:

temperature, °360
pressure, kPa(psi)4,155 (588)
the gas flow rate, m3/m3(SCF/B)178,1 (1000)
hourly space velocity of fluids1,2 and 3
(LHSV), h-1

Test types C1With2With3

Raw material: the mixture of oils

sulfur, % mass.1,637
total nitrogen, ppm401
density, g/CC0,887

Test conditions:

temperature, °C1=343; C2=57;
With3=371
pressure, kPa(psi)4,755 (675)
the gas flow rate, m3/m3(SCF/B)213,7 (1200)
hourly space velocity of fluids2,7
(LHSV), h-1

Test type D

raw material: a mixture of direct distillation gas oil/light circular

sulfur, % mass.0,8
total nitrogen, ppm196
density, g/CC0,889

Test conditions:

temperature, °349
pressure, kPa(psi)4,100 (580)
the gas flow rate, m3/m3(SCF/B)178,1 (1000)
hourly space velocity of fluids2,0
(LHSV), h-1

Test types E1E2

raw material: a mixture of direct distillation gas oil/light circular

Test conditions:

sulfur, % mass.0,508
total nitrogen, ppm760
density, g/CC0,859
temperature, °E1=343; F2=385
pressure, kPa(psi)4,928 (700)
the gas flow rate, m3/m3(SCF/B)178,1 (1000)
hourly space velocity of fluids2,4
(LHSV), h-1

Test type F

raw material: Arab oil direct distillation

sulfur, % mass.1,005
total nitrogen, ppm251
density, g/CC0,864

Test conditions:

temperature, °363
pressure, kPa(psi)4,100 (580)
the gas flow rate, m3/m3(SCF/B)178,1 (1000)
hourly space velocity of fluids3,0
(LHSV), h-1

Example 1

This example describes how to obtain samples of the catalysts of the present invention.

Powder comprising particles of aluminum oxide, coated with 6% of the mass. silicon dioxide, crushed to the crushing rollers, extruder is in the form of a rounded triangle, dried and calcined by conventional means. Details about powder 6% of the mass. silica - alumina described in the open literature (McMillan M, Brinen, J.S., Carruthers, D., Haller, G.L., "A29Si NMR Investigation of the Structure of Amorphous Silica-Alumina Supports", Colloids and Surfaces, 38(1989) 133-148). Used in this case, the powder meets the criterion of stability of porosity, as described in the above-cited publication.

is 95.6 g of the carrier silica - alumina impregnated to the initial humidity of 100 ml of solution "A". The solution indicated in the description as solution "A", consists of a mixture of two solutions: solution C obtained by the addition of 11.3 grams of ammonium hydroxide solution (28 wt. -%) it was 65.3 g of the solution tetraaminoanthraquinone acid (38% EDTA) from Dow Versene, and solution "D". Solution "D" is produced by adding 4,37 g of ammonium hydroxide solution (28 wt. -%) to 41,0 g of the solution "E". The solution outlined in this description as solution "E"is produced by adding 137 g of solid carbonate of cobalt to 500 g of the diluted solution of phosphoric acid (23,0 g H3PO4- 86,0% of the mass. and 475 g of deionized water, heating the mixture to 55°and then adding 300 g Climax of Moo3. The mixture is then heated to 98°C with stirring for 1.5 hours, after which was added 100 g of the solution of nitric acid (70% wt.) to fully dissolve the mixture placed. This solution is indicated in the description as solution "E", phosphoric acid containing compounds of cobalt and molybdenum, where the mass ratio of Co/Mo is 0,258, and the pH is approximately 0.6, cooled to room temperature and was 41.0 g of the solution used to obtain the solution mentioned in the present description solution "D".

Moistened granules leave to stand for 2 hours, and then dried in a thermostat thin layer at 230°C for 1 hour. 122,6 g of dried product then dip into a container of solution E and circulate 360 g of this solution to wet the pellets. Moistened granules are then separated from the excess solution by centrifugation and placed in a sealed flask in a thermostat at 75°C, and kept there at the same temperature for 3 days. The material is then rapidly dried at 230°C for 20 minutes to evaporate the liquid carrier to the level of the initial (LOI) at 30-32% of the mass. with subsequent calcination at 500°C for one hour in air to obtain a catalyst of the present invention, indicated in the present description as a catalyst C-2. Catalyst C-2 contains 5,97% of the mass. With, 19,7% of the mass. Mo and 0.77% of the mass. P, where % mass. calculated on the total weight of the catalyst, and has a specific surface area of 305 m2/g and the set intensity peaks kamenetska in 3344 reference.

The second 100 Gras is MoEHE portion of the carrier to moisten the initial moisture solution, comprising of 62.5 g of the solution demonoidregistration acid (40.0% of mass. EDTA) from Dow Versene and 77,59 g of the solution indicated in the present description as solution "F". The solution F is prepared by adding 329 g of Moo3, 100.0 g of Co(OH)2and 282,6 g monocrystalline citric acid to 695 g of deionized water and heated from room temperature to 80°C. Then the solution is boiled for approximately one hour until complete dissolution of all components, and then cooled to room temperature. Solution "F" contains compounds of cobalt and molybdenum, and the mass ratio of Co/Mo is 0,292 at pH approximately 0.6. Wet granules allow to soak for one hour and then dried in a thin layer in the dryer at 230°C for one hour.

After that, the dried granules are placed in 300 g of solution F and circulate the solution over the granules within one hour. Moistened granules separated from the solution by centrifugation and placed in a sealed flask in a thermostat set at 75°C, for 3 days. Then the material is subjected to rapid drying at 230°C for 1 hour to evaporate carrier liquid to LOI 30-32 wt. -%, and then calcined at 500°C for 1 hour to obtain a catalyst of the present invention, indicated in the present description as a catalyst D-2. Rolled the ATOR D-2 contains 4,11% of the mass. With and 16.3% of the mass. Mo has a specific surface area of 347 m2/g and the set intensity peaks kamenetska in 4320 times.

Third 100-gram portion of the carrier to moisten the initial moisture solution, including 64,7 g of the solution demonoidregistration acid (40.0% of mass. EDTA) from Dow Versene with 82.3 g of the solution indicated in the present description as solution "G". Solution "G" is prepared by adding 300 g of Moo3and 137,5 g Coco3to 575 g of deionized water followed by heating to 70-80°under stirring and then slowly adding 225,0 g monocrystalline citric acid. Then the solution is boiled until complete dissolution of all components within 30 minutes, and then leave it to cool. Solution G containing compounds of cobalt and molybdenum, in which the mass ratio of Co/Mo is 0,321 has a pH of approximately 2.0. Moistened granules leave to stand for 1 hour and then dried in a thin layer in thermostat installed on 230°within one hour.

After that, the dried granules are placed in 300 g of a solution "G" and circulate the solution over the granules within one hour. Moistened granules separated from the solution by centrifugation and placed in a sealed flask in a thermostat set at 75°C, for 3 days. Then the material is subjected to rapid drying Ave is 230° C for one hour to evaporate the carrier liquid to LOI 30-32 wt. -%, and then calcined at 500°C for an additional hour to obtain a catalyst of the present invention, indicated in the present description as the catalyst E-2. Catalyst E-2 contains a 4.53% of the mass. With and 14.6% of the mass. Mo has a specific surface area of 310 m2/g and the set intensity peaks Kamenetskii 1082 times.

Example 2 (Comparative)

This example describes how to obtain samples of the catalysts of U.S. patent 6025485.

The media is prepared by the same method as in example 1, except that the source material does not contain silicon dioxide.

Part of this media is treated in the same manner as for catalyst C-2, and get the catalyst C-1. Catalyst C-1 contains 4,67% of the mass. With, 18.1% of the mass. Mo and 0.61% of the mass. R has a specific surface area of 280 m2/g and the set intensity peaks Kamenetskii 195 times.

The second portion of the media is treated in the same manner as catalyst D-2 to obtain a catalyst D-1. Catalyst D-1 contains 4,08% of the mass. With and 14.7% of the mass. Mo has a specific surface area of 230 m2/g and the set intensity peaks Kamenetskii less than 100 times.

Example 3 (Comparative)

This example describes the generation of two catalysts obtained by the method of this image is to be placed, but insufficient for the formation of the catalyst of the present invention and with close to the minimum sufficient amount of silicon dioxide in the source material.

The media is prepared by the same method as in example 1, except that the starting material contains 2% of the mass. silicon dioxide. This carrier is treated by the same method as the catalyst E-2 and receive catalyst E-1. Catalyst E-1 contains 5,91% of the mass. With and 19.7% of the mass. Mo has a specific surface area of 215 m2/g and the set intensity peaks Kamenetskii 300 times.

The second medium is prepared by the same method as in example 1, except that the starting material contains 3.7% of the mass. silicon dioxide is less than the preferred number (6 wt. -%), but higher than 2 wt. -%, used for catalyst E-1. This media is treated in the same manner as catalyst D-2 and receive catalyst D-3. Catalyst D-3 contains 4,08% of the mass. With and 15.7% of the mass. Mo has a specific surface area of 245 m2/g and the set intensity peaks kamenetska in 1880 times.

Example 4

In this example, we compare the performance properties of the catalyst-2 in comparison with catalyst C-1 and the standard catalyst oil production ("Standard"), obtained by traditional means.

Each catalyst under the will eraut test type A. The results are presented in table 3.

Table 3
CatalystSproduct, mass. ppmRVA (1)
Standard330100
S-1175143
C-291202
(1) the Relative Volume Activity (RVA) is the relative volumetric activity represents the ratio of rate constants for catalysts that are defined by the concentration of sulfur in the product.

This test shows that catalyst C-2, i.e. the catalyst of the present invention, more effective at removing sulfur than any of the other two catalysts.

Example 5

In this example, we compare the performance properties of the catalyst D-2, catalyst D-1 and the standard catalyst oil production ("Standard"), obtained by traditional means.

Each catalyst was tested type C. the Results are presented in table 4.

Table 4
CatalystSproduct, mass. ppmRVA (1)
Standard350 100
D-1350117
D-2350143
(1) the Relative Volume Activity (RVA) is the relative volumetric activity represents the ratio LHSV necessary to achieve the sulfur content in the product of 350 masses. h/million

This test shows that to achieve the desired sulfur content in the product requires a smaller amount of catalyst D-2 of the present invention than any of the other two catalysts.

Example 6

This example compares the performance properties of the catalyst E-2, catalyst E-1 and the standard catalyst oil production ("Standard"), obtained by traditional means.

Each catalyst was tested type C. the Results are presented in table 5.

Table 5
CatalystSproduct, mass. ppmRVA (1)
Standard350100
E-1350102
E-2350124
(1) the Relative Volume Activity (RVA) is the relative volumetric activity represents the ratio LHSV necessary to achieve the content of the project of sulfur in the product of 350 masses. h/million

This test shows that to achieve the desired sulfur content in the product requires a smaller amount of catalyst E-2 of the present invention than any of the other two catalysts. The test also shows that the use of the source material containing the shortage of silicon dioxide with respect to the method of preparation of the catalyst according to the present invention leads to the production of the catalyst, i.e. the catalyst E-1, which is not more effective than the standard catalyst of the refinery.

Example 7

This example describes how to obtain samples of the catalysts of the present invention, in which both Ni and Co are included in the final catalyst, and the products get subjected to significantly different conditions of aging.

100 g of the carrier silica - alumina described in example 1, to impregnate the initial moisture 152,4 g of the solution "To". The solution indicated in the present description as a solution "To", consists of a mixture of two solutions: 68,0 g of the solution L, the resulting addition of 6.66 g of solid Nickel acetate (23,58% of the mass. metal Ni) to 99,54 g of the solution demonoidregistration acid Dow Versene (40% of the mass. EDTA), and 84.4 g of the solution "F"described above in example 1.

Moistened granules leave to stand for 2 hours, as in p is adidasi cases, and then dried in a thermostat thin layer at 230°C for 1 hour. 143,8 g of dried product then dip into a container of solution F and circulate 317 g of this solution to wash the pellet. Then the moistened granules are separated from the excess solution by centrifugation and pomest in a closed flask in a thermostat set at 75°and hold at the same temperature for 3 days. The material is then rapidly dried at 230°C for 20 minutes to evaporate carrier liquid to LOI 30-32 wt. -%, with subsequent calcination at 500°C for one hour in air to obtain a catalyst of the present invention, designated as catalyst A. Catalyst a contains 4,3% of the mass. With, of 17.0% of the mass. Mo and 0.68% of the mass. Ni has a specific surface area of 347 m2/g and the set intensity peaks kamenetska in 2670 times.

A second process of obtaining carried out on identical to the catalyst And the scheme, but the aging is carried out at 90°C for 7 days instead of 3 days at 75°C. This catalyst is denoted in the present description as catalyst B. Catalyst b contains 4,24% of the mass. With, 16,8% of the mass. Mo and 0.68% of the mass. Ni has a specific surface area of 340 m2/g and the set intensity peaks kamenetska in 6,138 for samples.

Example 8

This example shows that the catalyst of the present invention in oceesa compared to the standard activity of the catalyst oil production while stimulating working conditions.

The catalyst a and the standard catalyst oil production ("Standard"), obtained by traditional means, is subjected to the test types C1C2and C3that are identical, except that the operating temperature is increased from C1to C3. The test results presented in table 6.

Table 6
CatalystTest type
C1With2With3
RVA-HDS (1)SproductRVA-HDS (1)SproductRVA-HDS (1)Sproduct
Standard100797100420100209
And132584144261159112
(1) the Relative Volume Activity (RVA) is the relative volumetric activity represents the ratio of rate constants for catalysts that are defined by the concentration of sulfur in the product.

You should pay attention to increase the relative volumetric activity increased and operating temperature of 343° With up to 357°and to 371°C. the data Presented show that the performance characteristics of the catalyst of the present invention in comparison with a standard catalyst oil production increase with the intensification of working conditions.

Example 9

This example illustrates the ability to form the catalysts of the present invention taking into account the expected operating conditions.

Catalyst A, the catalyst and the standard catalyst oil production ("Standard"), obtained by traditional means, each subjected to testing types D, E1and E2. Raw materials for the type test D contains a moderate concentration of nitrogen (196 mass. h/m), while raw materials for testing types of E1and E2has a high content of nitrogen (760 masses. h/m).

In this example, the operational parameters of the catalyst according to the invention compared with the operating parameters of the catalyst obtained with a significantly higher concentration kamenetska in his material-the predecessor. This increase Kamenitsa is achieved by increasing both the temperature and the duration of the aging stage. With this intensified aging increase concentration and crystallite size Kamenitsa. Along with changes in Kamenitsa pret is chevet a significant change in the pore structure of the final catalyst. In the modified catalyst gives a completely different response to the temperature increase in the process of hydrodesulfurization it is one particular of gasoil. This can be seen in the following test results are presented in table 7.

Table 7
CatalystTest type
C1With2With3
RVA-HDS (1)SproductRVA-HDS (1)SproductRVA-HDS (1)Sproduct
Standard10022410031310051
And12315912123410055
In13014312821313134
(1) the Relative Volume Activity (RVA) is the relative volumetric activity represents the ratio of rate constants for catalysts that are defined by the concentration of sulfur in the product.

This table lists three catalyst, namely minimalist guest is enom the description of the standard industrial catalyst comparison, catalyst A, i.e. the catalyst according to the invention obtained so that it shows moderate concentration kamenetska in material precursor, and the catalyst, i.e. a catalyst having a high concentration Kamenetskii material predecessor. Then, each catalyst was tested along with the other at a constant temperature and pressure using two mixtures of direct distillation gas oil/light circular, as described in the test methods types D and E, G1 and G2.

When the test type D both catalyst of the present invention are more active than the standard, and a catalyst with a higher concentration Kamenetskii slightly better than the other (130 123 against RVA). Similar results are obtained for type test E1. However, you should note that when the processing conditions are changed for the three catalysts in the test type, F2option with a higher content Kamenetskii retains its operational benefits, and one that contains fewer Kamenetskii inferior to him.

Not meaning to be bound by any theory, the authors believe that the catalysts obtained from materials with a high content of Kamenitsa have a large number of active sites per unit volume of catalyst than traditionally received utilizatori. In the example above, the two catalyst of the present invention have different effects when the temperature increase during the test, the type of E2. Raw materials for the type test E differs from gasoil for tests of type D in the first place, the concentration of nitrogen-containing molecules.

At low pressure and low speed handling hydrogen in these tests, the removal of nitrogen-containing molecules is far from complete. In addition, non-nitrogen-containing molecules become gidrirovanie (basic) nitrogen-containing molecules in the process of partial (incomplete) hydrogeochemical gasoil. It is known that these molecules reduce the activity of the catalyst desulfurization by adsorption on its more acidic centers. Therefore, we can reasonably assume that the catalyst reaching a more complete removal of nitrogen-containing molecules (catalyst) and having more accessible centres hydrodesulfurization, will reduce the effect of dynamic poisoning" other nitrogen-containing molecules and maintain, thus, higher activity of hydrodesulfurization in the catalyst. Therefore, the presented results show that the catalysts of the present invention can be formulated according to the optimal operating properties, depending on the hypoxia concentrations of nitrogen-containing molecules in raw materials.

Example 10

In this example, we compare the performance characteristics of the catalyst obtained "sufficient" level of silica in the media docid silica - alumina, and the catalyst obtained with the "close to the minimally sufficient" silicon dioxide content in the carrier is silica - alumina. Catalyst D-2 compare with catalyst D-3 and the standard catalyst oil production ("Standard"), obtained by traditional means, standard test type F.

Table 8
CatalystSproduct, mass. ppmRVA (1)
Standard212100
D-2117140
D-3161117
(1) the Relative Volume Activity (RVA) is the relative volumetric activity represents the ratio of rate constants for catalysts that are defined by the concentration of sulfur in the product.

This test shows that the use of the source material, containing close to a minimally sufficient amount of silicon dioxide in the process of preparation of the catalyst of the present invention, results in the catalysis of the ora, i.e. catalyst D-3, which is more effective than the standard catalyst oil production, but not as active as the catalyst with a sufficient amount of silicon dioxide in the carrier of silica - alumina catalyst D-2.

1. Composition comprising a solid phase of trihydroxide aluminum, and this phase has a measurable band x-rays between 2θ=18,15° 2θ=18,50°between 2θ=36,1° 2θ=eur36, 85°between 2θ=39,45° 2θ=40,30° and between 2θ=51,48° 2θ=52,59°and has no measurable bands of x-rays between 2θ=20,15° 2θ=20,65°.

2. The composition according to claim 1, further characterized in that the phase of trihydroxide aluminum has a measurable band x-rays between 2θ=27,35° 2θ=27,90°between 2θ=34,75° 2θ=35,48°and between 2θ=62,40° 2θ=63,80°.

3. The composition according to claim 1 or 2, further characterized in that the phase of trihydroxide aluminum has no measurable bands on the radiograph between 2θ=20,15° 2θ=20,65° and between 2θ=37,35° 2θ=37,75°.

4. Composition according to any one of claims 1 to 3, further characterized in that the phase of trihydroxide aluminum has no measurable diffraction bands in the radiograph between 2θ=18,70° 2θ=18,90°between 2θ=20,30° 2θ=20,50° and between 2θ=40,30° and 2θ=40,70°.

5. The catalyst precursor comprising a composition according to claims 1, 2, 3, or 4.

6. A method of obtaining a composition according to claims 1, 2, 3, or 4, or catalyst precursor according to claim 5, including

(a) wetting the source material comprising silica-alumina and amorphous alumina containing from 4 to 8 wt.% silicon dioxide, and at least 20 wt.% the specified aluminum oxide is amorphous, by contact with a certain number of chelat forming agent in the range from 0.1 to 1.0 g per 1 g of starting material in a liquid carrier and a compound of the metal;

(b) aging moistened thus the source material while it is wet;

(c) drying aged so the source material at a temperature of from 100 to 230°; and

(d) calcining the dried thus the material.

7. The method according to claim 6, in which the original material comprises less than 8 wt.% silicon dioxide and at least 30 wt.% aluminum oxide is amorphous.

8. The method according to claim 6, in which the source material includes from about 5 to 7 wt.% silicon dioxide and from 20 to 50 wt.% aluminum oxide is amorphous.

9. The method according to any of p, 7 or 8, in which the chelate forming agent is selected from ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylamine is acetic acid, demonoidregistration acid, Tris(2-amino-ethyl)-amine, Triethylenetetramine, diethylenetriaminepentaacetic acid, cyclohexanedicarboxylic acid, ethylene glycol-bis(beta-aminoacylase simple ether)-N,N'-tetraoxane acid or Tetraethylenepentamine.

10. The method according to any of p, 7, 8 or 9, in which the aging moistened thus the source material in the wet state, is carried out at room temperature for at least about 30 days.

11. The method according to any of p, 7, 8 or 9, in which the aging moistened thus the source material in the wet state, is carried out at a temperature of at least 80°C for at least about two days.

12. The catalyst including the carrier obtained from the composition according to claims 1, 2, 3, or 4, or catalyst precursor according to claim 5, and a catalytically active amount of one or more metals, metal compounds or combinations thereof.

13. The catalyst according to item 12, in which one or more metals, metal compounds or combinations thereof selected from the catalytically active transition metals of group VIB and group VIII of the Periodic table and their compounds and combinations of such metals and compounds.

14. The catalyst according to item 12 or 13, in which the catalyst additionally includes the t promoter.

15. The catalyst 14, in which the promoter is selected from phosphorus, phosphorus compounds, and combinations thereof.

16. The catalyst according to any one of p, 13, 14 or 15, in which one or more metals, metal compounds or combinations thereof selected from Nickel, cobalt, molybdenum and tungsten, their compounds, and combinations of these metals and compounds.

17. The catalyst according to item 16, in which one or more metals, metal compounds or combinations thereof include molybdenum or molybdenum compounds in an amount up to 35 wt.% based on Moo3, cobalt or compounds of cobalt in an amount up to 9 wt.% in the calculation of the Soo, and optionally phosphorus, phosphorus compounds, and combinations thereof in an amount up to 10 wt.% in the calculation of the P2O5moreover , wt.% calculated on the total weight of the catalyst.

18. The catalyst according to item 16, in which one or more metals, metal compounds, or combinations thereof include molybdenum or molybdenum compounds in an amount up to 35 wt.% based on Moo3and Nickel or compounds of Nickel in an amount up to 7 wt.% in the calculation of NiO, and optionally phosphorus, phosphorus compounds, and combinations thereof in an amount up to 10 wt.% in the calculation of the P2About5moreover , wt.% calculated on the total weight of the catalyst.

19. The catalyst according to item 16, in which one or more metals, metal compounds, or combinations thereof include molybde is or compounds of molybdenum in an amount up to 20 wt.% based on Moo 3and Nickel and/or cobalt and their compounds in an amount up to 5 wt.% in the calculation of NiO and/or COO, and optionally phosphorus, phosphorus compounds, and combinations thereof in an amount up to 10 wt.% in the calculation of the P2O5moreover , wt.% calculated on the total weight of the catalyst.

20. The catalyst according to item 16, in which one or more metals, metal compounds, or combinations thereof include molybdenum or molybdenum compounds in an amount up to 20 wt.% based on Moo3and Nickel and/or cobalt and their compounds in an amount up to 5 wt.% in the calculation of NiO and/or COO, and optionally phosphorus, phosphorus compounds, and combinations thereof in an amount up to 6 wt.% in the calculation of the P2O5moreover , wt.% calculated on the total weight of the catalyst.

21. The catalyst according to item 13, in which one or more metals represent one or more noble metals in an amount up to 2 wt.% calculated on the total weight of the catalyst.

22. The catalyst according to item 21, in which the noble metal is Pt or a combination of Pt and Rh.

23. A method of processing hydrocarbon material, comprising contacting the specified hydrocarbon material with the catalyst according to item 12.

24. The method according to item 23, where this method is way catalytic hydrodesulfurization hydrocarbon feedstock comprising contacting the feedstock under conditions of hydrodesulfurization with cat what lyst by 17.

25. The method according to item 23, where this method is way catalytic hydrogasification hydrocarbon feedstock comprising contacting the feedstock under conditions of hydrogeochemical with catalyst p.

26. The method according to item 23, where the method is a method of catalytic hydrodemetallation hydrocarbon feedstock comprising contacting the feedstock under conditions of hydrodemetallation with the catalyst according to claim 19.

27. The method according to item 23, where this method represents a method for the catalytic hydrocracking of hydrocarbonaceous feedstock comprising contacting the feedstock in a hydrocracking conditions with a catalyst according to claim 19.

28. The method according to item 23, where this method is way catalytic hydroconversion hydrocarbon feedstock comprising contacting the feedstock under conditions of hydroconversion with the catalyst according to claim 20.

29. The method according to item 23, where this method represents a method for the catalytic reforming of hydrocarbon feedstock comprising contacting the feedstock at reforming conditions with a catalyst according to item 21.

30. The method according to item 23, where the method is a method of catalytic hydrogenation-dehydrogenation of hydrocarbon feedstock comprising contacting the feedstock under conditions of hydrogenation-dehydrogenation catalyst at p.22.

31. The way p is item 23, where this method represents a method for the catalytic isomerization of hydrocarbon feedstock comprising contacting the feedstock at isomerization conditions with a catalyst according to item 21.

32. The method of producing catalyst according to item 12, including

(a) obtaining a catalyst carrier of a particular form from the source material comprising silica - alumina and amorphous alumina containing from about 4 to about 8 wt.% silicon dioxide and at least about 20 wt.% the specified aluminum oxide is amorphous;

(b) wetting the source material by contacting with chelat forming agent and a catalytically active amount of one or more metals, metal compounds or combinations thereof in a liquid medium;

(c) aging moistened thus the source material while it is wet;

(d) drying the aged thus the source material at a temperature of from 100 to 230°; and

(e) calcining the dried thus the material.

33. The method according to p, in which the source material includes less than about 8 wt.% silicon dioxide, and at least 30 wt.% aluminum oxide is amorphous.

34. The method according to p, in which the source material includes from about 5 to about 7 wt.% silicon dioxide, and the t of about 20 to about 50 wt.% aluminum oxide is amorphous.

35. The method according to PP, 33 or 34, in which the chelate forming agent is selected from ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylnitrosamine acid, demonoidregistration acid, Tris(2-amino-ethyl)amine, Triethylenetetramine, diethylenetriaminepentaacetic acid, cyclohexanedicarboxylic acid, ethylene glycol-bis(beta-aminoacylase simple ether)-N,N'-tetraoxane acid or Tetraethylenepentamine.

36. The method according to PP, 33, 34 or 35, in which the number chelat forming agent has a value of from about 0.1 g to about 1.0 g per g of starting material.

37. The method according to PP, 33, 34, 35 or 36, in which the aging moistened thus the source material in the wet state, is carried out at room temperature for at least about 30 days.

38. The method according to PP, 33, 34, 35 or 36, in which the aging moistened thus the source material in the wet state, is carried out at a temperature of at least 80°C for at least about two days.

39. Method for improving the catalytic activity of the catalyst on a carrier of silica-alumina containing from about 4 to about 8 wt.% silicon dioxide and at least about 20 wt.% the specified aluminum oxide is amorphous, and meta is l or compound of the metal, including

(a) wetting the specified catalyst by contacting with chelat forming agent in a liquid carrier;

(b) aging moistened thus the catalyst while it is in the wet state;

(c) drying the aged in such a way catalyst at a temperature of from 100 to 230°and in conditions providing essentially complete volatilization of a liquid medium; and

(d) calcining the dried thus the catalyst.

40. Method of regeneration of the used catalyst on a carrier of silica-alumina containing from about 4 to about 8 wt.% silicon dioxide and at least about 20 wt.% the specified aluminum oxide is amorphous, and the metal or metal joints, including

(a) removing material deposited on the specified catalyst in the process prior to use;

(b) wetting the specified catalyst by contacting with chelat forming agent in a liquid carrier;

(c) aging moistened thus the catalyst while it is in the wet state;

(d) drying the aged in such a way catalyst at a temperature of from 100 to 230°and in conditions providing essentially complete volatilization of a liquid medium; and

(e) calcining the dried thus the time of the catalyst.

41. The method of preparation of the catalyst, specially prepared for processing hydrocarbon material, including

(a) determining the concentration of nitrogen-containing compounds in the hydrocarbon material;

(b) selecting a source material comprising silica-alumina and amorphous alumina containing from about 4 to about 8 wt.% silicon dioxide and at least about 20 wt.% the specified aluminum oxide is amorphous, with the specified aluminum oxide has a suitable concentration of silicon dioxide, such that being aged in a wet state at a temperature of aging in the wet state, component, at least 20°during the period of time which shall be at least 1 day, it will form a catalyst precursor, with the specified catalyst precursor includes a sufficient concentration of the composition containing the phase trihydroxide aluminum with measurable strip in the radiograph between 2θ=18,15° and 2θ=18,50°between 2θ=36,1° 2θ=eur36, 85°between 2θ=39,45° 2θ=40,30° and between 2θ=51,48° 2θ=52,59°and no measurable bands of x-rays between 2θ=20,15° 2θ=20,65°so that the catalyst derived from the specified catalyst precursor, to be effective DL is processing the specified hydrocarbon material, where indicated concentration of silicon dioxide, aging temperature in the wet state and time are chosen so that they were proportional to the concentrations of these nitrogen-containing compounds;

(c) receiving the catalyst carrier of a certain shape from a specified source material;

(d) wetting the specified source material by contacting with chelat forming agent and a compound of the metal in liquid media;

(e) aging moistened thus the source material while it is in the wet state at a temperature selected in stage (b) during the period of time selected in stage (b);

(f) drying aged so the source material at a temperature of from 100 to 230°; and

(g) calcining the dried thus the material.



 

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3 tbl

FIELD: catalyst carrier preparation methods.

SUBSTANCE: invention has for object development of catalyst carrier based on oxygen-containing aluminum compound having specific chemical analysis, morphologic and texture properties, elevated ability of interacting with catalyst components, and also specified particle size, which catalyst allows preparation of high-strength, active, and stable catalysts. Problem is solved by means of microspherical shape of catalyst carrier including aluminum compounds of formula Al2O3·nH2O having X-ray amorphous structure and prepared via fast partial dehydration of hydroargillite. Carrier represents spheroid particles consisted of hexagonal rods with system of planar parallel pores corresponding to cleavage along face (001). Carrier contains water in amount corresponding to n=0.5-1.0, has particle size 20-250 μm, specific surface 80-250 m2/g, and pore volume 0.1-0.3 cm3/g. Carrier serves for preparation of fluidized bed catalysts used in paraffin hydrocarbon dehydrogenation, oxychlorination, cracking, and other processes. Carrier may also be used as precursor for various hydroxide modifications, including pseudobauhmite, bayerite, various alumina modifications, adsorbents, fillers, fore-retardants and the like.

EFFECT: increased strength, activity, and stability of catalysts.

9 cl, 3 dwg, 2 tbl, 5 ex

FIELD: composite materials.

SUBSTANCE: invention relates to catalyst carriers and methods for preparation thereof. Novel porous composite material particles are proposed comprising alumina component and swelled clay component finely dispersed in alumina component in amount effective to raise hydrothermal stability, pore volume, and/or pore mode in the mesopore region in composite material particles as compared to swelled clay-free material. Also proposed are composite material particles and agglomerate particles obtained therefrom as well as a method for hydroprocessing of petroleum feedstock using agglomerates as hydroprocessing catalyst carrier.

EFFECT: increased hydrothermal stability and pore volume.

44 cl, 24 dwg, 19 tbl, 28 ex

FIELD: hydrometallurgy; production of aluminum oxide.

SUBSTANCE: the invention is pertaining to the field of hydrometallurgy of aluminum compounds and bauxites and may be used for production of aluminum oxide at processing of the bauxites containing alumina. The method of production of aluminum oxide provides for a settling of aluminum hydroxide from a solution of sodium aluminate, its drying and calcination. At that sodium aluminate is produced from aluminum-containing raw material in the capacity of which use a by-product of etching of an aluminum band in production of aluminum constructions. Aluminum-containing raw material is treated at the temperature of 70°C with 3-7 % solution of a sodium hydroxide in amount of 100, 125 or 150 cm3 within 3-5 hours. Produced sediment is filtered out and fed to retreatment with sodium hydroxide, and the filtrate containing sodium aluminate is mixed with about 1-2 M solution of sulfuric acid till obtaining pH = 6.4-7.4, the produced sediment of aluminum hydroxide is filtered out and flushed by water to remove sodium ions, then the produced aluminum hydroxide is heated up in a drying cabinet up to the temperature of 200°C at the rate of heating of 10-20°C /hour and annealed in the muffle furnace within 9 hours up to the temperature of 650°C at the speed of heating of 50°C /hour. The offered method of production of aluminum oxide allows: to reduce the net cost of aluminum hydroxide, to utilize a by-product of etching of an aluminum band in production of aluminum constructions.

EFFECT: the invention allows to reduce the net cost of aluminum hydroxide, to utilize a by-product of etching of an aluminum band in production of aluminum constructions.

1 tbl, 15 ex

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

FIELD: inorganic compounds technologies.

SUBSTANCE: invention relates to production of activated alumina appropriate as catalyst carrier for petrochemical and organic synthesis, in particular as reforming catalyst carrier. Process comprises continuous precipitation of aluminum hydroxide with pseudoboehmit structure from basic aluminum sulfate solution by neutralization with alkali reagent, filtration, autoclave treatment of resulting aluminum hydroxide precipitate in aqueous ammonia solution at pH 10.0-11.0 of reaction mixture, 135-145°C, and agitation time 1.0-2.0 h, washing of precipitate with chemically desalted water, drying, and final heat treatment.

EFFECT: improved quality of activated alumina and reduced consumption of water in washing of final product.

2 cl, 1 tbl

FIELD: industrial inorganic synthesis.

SUBSTANCE: invention relates to manufacture of ceramic powders, namely to production of optical purity-grade α-alumina. Process comprises autoclave heating of water and aluminum oxide or hydroxide, taken at weight ratio 1:(0.7-1.2), respectively, to synthesis temperature 250-400°C at elevated pressure followed by aging for 20 h at the same temperature and pressure 300-600 atm. After aging, heat treatment is carried out either by way of cooling the mixture to ambient temperature for 24 h at the same pressure or by reducing pressure with rate 20-50 atm/h to atmospheric value at synthesis temperature followed by stopping heating in autoclave.

EFFECT: enabled formation of high-purity microcrystalline alumina.

3 cl, 1 tbl, 2 ex

The invention relates to the field of chemical technology and can be used in the production of oxides and hydroxides of aluminum, various modifications, aluminum salts, etc

The invention relates to chemical technology and can be used in the production of aluminum hydroxide with the structure bayerite and this is of aluminum oxide on its basis, used in the manufacture of catalysts, carriers, etc

FIELD: oxidation catalysts.

SUBSTANCE: invention relates to sorption engineering and can be used for regeneration of different kinds of hopcalite lost catalytic activity during long-time storage. Regenerated sorbents can be used un respiratory masks and in processes or removing carbon monoxide from industrial emissions. Invention provides a method for activating carbon monoxide oxidation catalyst involving heat treatment thereof and characterized by that activation is conducted by heating catalyst bed 2-3 cm thick to 180-380°C at temperature rise velocity 10-20°C/min while constantly carrying away reactivation products.

EFFECT: enabled restoration of catalytic activity.

3 ex

FIELD: catalyst preparation.

SUBSTANCE: invention relates to supported catalysts and provides a method for preparing catalyst-containing solid product comprising step, wherein ceramic carrier is applied onto metallic surface, and depositing catalytically active material onto ceramic carrier, which was preliminarily coated with supporting porous metallic material, ceramic carrier being applied onto and/or into supporting porous metallic material. Invention also describes device used in preparation of catalyst-containing solid product for applying supporting porous material onto inside or outside metallic surfaces of the hollow body.

EFFECT: increased stability of catalyst.

7 cl, 2 dwg

FIELD: production of carbon carrier for catalysts.

SUBSTANCE: proposed method includes heating of moving layer of granulated furnace black used as backing, delivery of gaseous or vaporous hydrocarbons into soot layer followed by their thermal decomposition on soot surface forming layer of pyrocarbon at forming of layer of pyrocarbon and activation of material compacted by pyrocarbon at temperature of 800-900°C and unloading of finished product. Granulated furnace black at specific surface of 10-30 m2/g and adsorption rate of 95-115 ml/100 g is used as backing for compacting with pyrocarbon. Then, product is subjected to activation for obtaining total volume of pores of 0.2-1.7 cm3/g. Black is compacted by pyrocarbon at two stages: at first stage, granulated black is compacted to bulk density of 0.5-0.7 g/cm3, after which material is cooled down and screened at separation of fraction of granules of 1.6-3.5 mm; at second stage, this fraction is subjected to repeated pyrolytic compacting to bulk density of granules of 0.9-1.1 g/cm3.

EFFECT: enhanced economical efficiency; increased productivity of process.

3 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods of preparing catalysts based on sulfurized styrene/divinylbenzene copolymer and thermoplastic polymer material, which are used in processes for preparing alkyl tert-alkyl ethers, hydration of olefins, dehydration of alcohols, preparation of esters, and the like. Invention provides molded ionite catalyst consisted of sulfurized styrene/divinylbenzene copolymer in the form of mixture of powdered copolymers with macroporous and gel structure and, as thermoplastic material, propylene polymers and propylene/ethylene copolymers. Preparation of catalyst is accomplished by extrusion at temperature of heating extruder cylinder 140-200°C and temperature of forming head equal to temperature of the last heated zone of heating cylinder.

EFFECT: increased catalytic activity.

10 cl, 3 tbl, 15 ex

FIELD: alternative fuel production and catalysts.

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

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

6 cl, 2 tbl, 16 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: catalyst constitutes cements formed during heat treatment and depicted by general formula MeO·nAl2O3, where Me is at least one group IIA element and n is number from 1.0 to 6.0, containing modifying component selected from at least one oxide of magnesium, strontium, copper, zinc, indium, chromium, manganese, and strengthening additive: boron and/or phosphorus oxide. The following proportions of components are used, wt %: MeO 10.0-40.0, modifying component 1.0-5.0, boron and/or phosphorus oxide 0.5-5.0, and alumina - the balance. Catalyst is prepared by dry mixing of one group IIA element compounds, aluminum compounds, and strengthening additive followed by mechanochemical treatment on vibromill, molding of catalyst paste, drying, and calcination at 600-1200°C. Modifying additive is incorporated into catalyst by impregnation and succeeding calcination. Method of pyrolysis of hydrocarbon feedstock producing C2-C4-olefins is also described.

EFFECT: increased yield of lower olefins.

3 cl, 2 tbl, 18 ex

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

FIELD: petroleum processing catalysts.

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

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 3 ex

FIELD: hydrocarbon conversion catalysts.

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

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

4 cl, 1 tbl, 8 ex

The invention relates to the field of technical chemistry, namely, carriers for catalysts that can be used in various heterogeneous catalytic processes in the chemical industry

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods for preparing catalyst precursors and group VIII metal-based catalysts on carrier, and to a process of producing hydrocarbons from synthesis gas using catalyst of invention. Preparation of precursor of group VIII metal-based catalyst comprises: (i) imposing mechanical energy to mixture containing refractory oxide, combining catalyst precursor with water to form paste comprising at least 60 wt % of solids, wherein ratio of size of particles present in system in the end of stage (i) to that in the beginning of stage (i) ranges from 0.02 to 0.5; (ii) mixing above prepared paste with water to form suspension containing no more than 55% solids; (iii) formation and drying of suspension from stage (ii); and (iv) calcination. Described are also method of preparing group VIII metal-based catalyst using catalyst precursor involving reduction reaction and process for production of hydrocarbons by bringing carbon monoxide into contact with hydrogen are elevated temperature and pressure in presence of above-prepared catalyst.

EFFECT: increased catalytic activity and selectivity.

12 cl, 1 tbl, 3 ex

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