Catalytic system for catalytic hydrodesulfurization, hydrodenitrogenation, reforming, hydrogenation-dehydrogenation and isomerization of hydrocarbons, its preparation, activation, regeneration and use of

 

(57) Abstract:

Describes a catalytic system for catalytic hydrodesulfurization, hydrodenitrogenation, hydroconversion, hydrodemetallization, hydrocracking, reforming, hydrogenation-dehydrogenation and isomerization of carbon-containing raw material containing the powdery porous carrier comprising gamma-alumina having a surface area at least 100 m2as measured by nitrogen adsorption, and a pore volume of at least 0.25 cm2/g as measured by mercury porosimetry, and impregnated with one or more of the catalytically active metal, wherein the catalyst further comprises partially nanocrystalline phase of alumina crystallite size of 8 to 25 as measured by the method of transmission electron microscopy, and the nanocrystalline phase of alumina in the surface layer of the catalyst in combination with the gamma alumina which has a crystallite size in the surface layer of the catalyst of greater than 30 as measured by electron microscopy, and the catalyst has at least a bimodal mesoporous structure. Describes its method of production, activation, regeneration

The present invention relates to highly active catalysts, which are based on gamma-alumina containing substrates impregnated with one or more catalytically active metals, to methods for their preparation and use in this invention. More specifically, the present invention relates to a method of increasing the activity of such catalysts; catalysts with increased activity, thus obtained; and a variety of specific catalysts and their use.

The technique related to the powdery porous gamma-alumina containing media, the impregnation of such bearers of various catalytically active metals, metal compounds and/or catalytic "promoters" (activators) and various applications such impregnated media as catalysts, widely and relatively well developed.

As the many examples of descriptions relating to these areas, we can mention several U.S. patents, all of which are incorporated herein by reference in full for all purposes set here- 2935463, 3032514, 3124418, 3152865, 3232887, 3287280, 3297588, 3493493, 3749664, 3778365, 3897265, 3909453, 3983197, 4090874, 4090982, 4154812, 4179408, 4255282, 4328130, 4357263, 4402865, 4444905, 4447556, 4460707, 4530911, 4588706, 4591429, 4595672, �has a continuous modification and testing of such catalysts to improve their catalytic activity, and while in some cases really managed to achieve relatively high activity, in industry there is a continuing need for catalysts with higher activity, which is provided by the present invention.

As an example, such a need may be the need for more high activity of the catalyst in the first stage hydrocracking. In the usual process for hydrocracking hydrocarbons with higher molecular weight divided into fractions with lower molecular weight in the presence of a catalyst, which is usually the zeolite (aluminosilicate, acid aluminum containing water) mixed with a noble metal. Suitable hydrocracking catalysts have a very high activity and capable of high noise ability amount, subject to cracking. Such catalysts, however, are highly sensitive to contaminating impurities, such as sulfur, a mixture of metals and nitrogen, which, therefore, must be removed from the hydrocarbon stream prior to cracking. This is done in the first stage hydrocracking, such as hydrogencitrate (removal of nitrogen), hydrodesulfurization (obeserved carriers of alumina, impregnated with additives from a combination of metals of Group VIB and Group VIII. Suitable hydroabrasive catalysts, however, are not active enough to make it possible to process with the same high volumetric throughput, as you can do this by hydrocracking catalysts. As such, the processes in the first stage hydrocracking represent a bottleneck in the overall process of hydrocracking, which must be compensated, for example, the ratio of units of hydrobromide to the hydrocracking unit.

In accordance with the present invention presents a highly active catalyst system containing a powdery porous carrier containing gamma-alumina having a surface area at least 100 m2(measured by nitrogen adsorption) and a pore volume of at least 0.25 cm3/g (as measured mercury "Porosimeter" - a device for determining porosity), and impregnated with one or more catalytically active metals, owing to which the catalyst is then contains part of the nanocrystalline phase of alumina crystallite size at the surface to

In addition, the present invention relates to a highly active catalyst, sauna least 100 m2(measured by nitrogen adsorption) and a pore volume of at least 0.25 cm3/g (as measured mercury "Porosimeter" - a device for determining porosity), and impregnated with one or more catalytically active metals, and the catalyst shows the relative volumetric activity (abbreviated RVA) not less than 115, preferably 120, and in special cases, at least 125, at the first stage hydrocracking, as was measured by the method described by the authors Carruthers and DiCamillo in the article "Pilot Plant Testing of the Hydrotreating Catalysts", Applied Catalysts, 43(1988) 253-276 that as the standard use of the catalyst, commercially available under the trademark HC-H (as of may 1994) from the company Unocal Corporation, Brea, CA.

In addition to the above catalyst of the present invention also relates to a method for increasing the activity of a catalytic system containing a porous carrier containing gamma-alumina and amorphous alumina having a surface area at least 100 m2(measured by nitrogen adsorption) and a pore volume of at least 0.25 cm3/g (measured mercury "Porosimeter"), and impregnated with one or more catalytically active metal, in the following way:

(1) the CMA shall indicate the aging moistened thus the substrate, until it gets wet;

(3) dried subjected to aging of the substrate at a temperature and under conditions that the liquid medium is substantially evaporated; and

(4) burn dried thus the substrate.

This method can be very easily applied to existing catalysts containing powdery porous carrier containing gamma-alumina and amorphous alumina, or may be used in the manufacturing process of the catalyst either before or at the same time, or after impregnation of the carrier containing gamma-alumina and amorphous alumina, one or more catalytically active metals and/or mixtures thereof. In addition, this method can be used to increase the activity of the catalyst during regeneration (recovery), when used catalysts contain powdery porous carrier containing gamma-alumina and amorphous alumina, and in which the spent catalyst is wetted in the same way as in the above stage (1) with the subsequent removal therefrom of precipitation containing carbon, the following stages (2), (3) and (4).

Following these steps in the specified order, you can be sure (having no desire to deal with any particular theory) that has mostactive components, the resulting nanocrystalline phase of alumina crystallite size (grain, pellets) on the catalyst surface to 25, preferably between 8 and 25 in combination with the gamma alumina which has a crystallite size at the surface of the catalyst is greater than 30 , and typically in the range from 30 to crystallite Size in the surface layer of the catalyst can be measured by well known techniques including transmission electron microscopy.

Simultaneously with the emergence of this nanocrystalline phase, also achieved an increase in surface area of the catalyst. In addition, in preferred embodiments, appears, at least bimodal mesoporous structure, along with the emergence of peaks porosity first region of pore size and less, more preferably in the range from 20 to and the second region of pore size or more, and more preferably in the range from 50 to that measured nitrogen porosimetry using desorption isotherms.

The resulting highly active catalysts are widely used in various fields, which are described in detail in many of the previously United the links. Especially preferred demetallization.

These and other features and advantages of the present invention will become more clear to the specialists from reading the following detailed description.

Substrates

As shown above, the substrates are suitable for preparing catalysts of the present invention are powdered porous substrates that contain at least part of the gamma-alumina and amorphous alumina, preferably at least 5% amorphous alumina based on the weight of the substrate. As specific examples may be mentioned substrates based on alumina and composite substrates, in which the alumina acts at least partially as a carrier for other substances, such as aluminosilicates and zeolites. Such substrates and methods for their production in General is well known in the art, as shown in the example previously United links.

The catalytically active metals.

The present invention is applicable to catalysts impregnated with one or more of a large variety of catalytically active metals is well known in the art, as shown by the example of numerous previously United links. In the framework of the present invention, Catalytica the metal catalysts may also be impregnated with one or more of the known promoters (promoters), such as phosphorus, tin, silica, and titanium, (including their connections).

Usually are catalytically active transition metals selected from the group comprising Group VIB metals, Group VIII metals and combinations thereof. The specific choice of metal (minerals), activator (ditch) and fillers, of course, depends on the desired end use of the catalyst, and these options can be easily selected by specialists for their specific purposes. As specific examples of this include the following (the weight. % are based on total weight of catalyst):

Operations hydrobromide

Hydrogencitrate (removal of nitrogen)

Ni (Nickel) and/or Co (cobalt), and preferably Ni, in an amount up to 7 wt.%, calculated as NiO (Nickel oxide) and/or CoO (cobalt oxide)

Mo (molybdenum) and/or W (tungsten), preferably Mo, in an amount up to 35 wt.%, calculated as MoO3(molybdenum trioxide) and/or WO3(tungsten trioxide)

if necessary, P (phosphorus), and preferably P in an amount up to 10 wt.%, calculated as P2O5(phosphorus oxide)

The desulfurization

Ni and/or Co, and preferably Co in an amount up to 9 wt.%, calculated as NiO and/or CoO

Mo and/or W, preferably Mo, in quantities/BR> P in an amount up to 10 wt.%, calculated as P2O5< / BR>
Gidromechanizaciya (demetallisation)

if necessary, Ni and/or Co, and preferably including Ni and/or Co in an amount up to 5 wt.%, calculated as NiO and/or CoO

Mo and/or W, preferably Mo, in an amount up to 20 wt.%, calculated as MoO3and/or WO3< / BR>
optionally P, and preferably P in an amount up to 10 wt.%, calculated as P2O5< / BR>
've got a hydro conversion

Ni and/or Co, and preferably Ni, in an amount up to 5 wt.%, calculated as NiO and/or CoO

Mo and/or W, preferably Mo, in an amount up to 20 wt.%, calculated as MoO3and/or WO3< / BR>
optionally P, and preferably P in an amount up to 6 wt.%, calculated as P2O5< / BR>
Hydrocracking

Ni and/or Co, and preferably Ni, in an amount up to 5 wt.%, calculated as NiO and/or CoO

Mo and/or W, preferably Mo, in an amount up to 20 wt.%, calculated as MoO3and/or WO3< / BR>
optionally P, and preferably P in an amount up to 10 wt.%, calculated as P2O5< / BR>
The hydrogenation/Dehydrogenation

noble metal, and preferably Pt (platinum) or Pt in combination with Rh (rhodium) in an amount up to 2 wt.%, calculated another noble metal, such as Re (rhenium) and/or Ir (iridium), and/or Sn in an amount up to 2 wt.%, calculated on the basis of

Operations not included in hydrobromide

Isomerization

noble metal, and preferably Pt or Pt in combination with other noble metal, such as Re (rhenium) and/or Ir (iridium), and/or Sn in an amount up to 2 wt.%, calculated on the basis of

The Claus process

Ni and/or Co, and preferably Ni, in an amount up to 5 wt.%, calculated as NiO and/or CoO

Mo and/or W, preferably Mo, in an amount up to 20 wt.%, calculated as MoO3and/or WO3< / BR>
optionally P, and preferably P in an amount up to 10 wt.%, calculated as P2O5< / BR>
Such catalysts are prepared by impregnation of substrates suitable components with different stages: drying, solifidianism and/or burning, depending on your desired end goal. Such preparation of the catalyst is generally well known in the art, as shown by the example of numerous previously merged references and further details you can refer to them, or others, appropriate to the subject matter of the invention numerous sources.

As shown above, the activity of catalytic is openly offered to the invention in the following way:

(1) moisten the catalytic system by contact with chelat forming" an agent in the liquid carrier;

(2) subject to aging moistened thus the substrate until it gets wet;

(3) dried subjected to aging of the substrate under such temperature conditions, so that the carrier liquid is substantially evaporated; and

(4) burn dried thus the substrate.

Suitable for use in this way hepatoblastoma agents include known that they form more stable complexes with transition metals and aluminum and, therefore, have a higher stability parameters. Especially preferred for use in the present invention is ethylenediaminetetraacetic acid (EDTA) and its derivatives, including, for example, N-acetylenedicarboxylic acid, diammonium ethylenediaminetetraacetic acid. Also suitable are three(2-ethylamine)Amin, Triethylenetetramine. In addition, they include diethylenetriaminepentaacetic acid, cyclohexanedimethanol acid, etilenglikoli-(beta-aminoacylase ether)-N,N'-tetraoxane acid, Tetraethylenepentamine and the like. The suitability of other chelat forming agentem, using transmission electron microscopy, checking, formed or not the nanocrystalline structure of the alumina with a suitable size of the crystallite.

The number chelat forming agent is not critical to achieve the effect, but has influence on the strength of the effect. Varying within wide limits the number of chelat forming agent can be used, depending on a number of factors such as the solubility in the liquid carrier, the type of the catalyst carrier and the metal which is impregnated with or you want to impregnate them. Basically catalytic system should be moistened with liquid media containing chelate forming agent in amounts from 0.01 - 1.0 g chelat forming agent per gram of catalyst system.

The catalytic system can be soaked in any conventional manner as, for example, by immersion or by spraying. To ensure sufficient absorption chelat forming agent, the dip is preferable to conduct periodic soaking (cycle vymachivanie). The preferred liquid carrier is water or an aqueous solution of ammonia (ammonia water).

The aging of the substrate is a function of the very least, days 10 and better still 14 days. With increasing temperature, the desired aging time is reduced. At 333K (60oC) it is preferable to expose the moistened substrate ageing, at least 1 day, and even better - 3 days. Aging may be accelerated only up to one hour, by heating the moistened sample in a microwave oven. Mostly aging is performed at a temperature of 20oC to 90oC.

Then the catalyst was subjected to aging, dried to substantial evaporation of the liquid carrier. Preferably, this drying took place rapidly at elevated temperatures in the range from 100oC to 250oC. Usually, to accelerate the drying up of the optimal time, less than one hour, use a heater with a fan.

Dried thus the catalyst was then calcined under conditions well known in the art. It is desirable that the firing took place in 2 stages: first, the low-temperature phase, in which the temperature is high enough to display or to decompose any remaining chelate forming agent, but not high enough to hepatoblastoma agents were burnt to soot (carbon deposits). At this first stage the temperature is variovacoC to 350oC. as soon As any remaining chelate forming agent is sufficiently removed, the catalyst can burn at high temperatures normally used.

As shown above, the process in accordance with the present invention is applicable not only to the original catalysts, but also to the catalysts regenerated (reduced) by any means. More precisely, following the removal of carbonaceous material from the spent catalyst by well-known procedures, it should be treated according to the stages (1) to (4), similar to the above.

This method can also be adapted to obtain a new catalyst. More specifically, the substrate can be wetted chelat forming agent/liquid media or to, or simultaneously with, or after impregnation of the carrier suitable catalytically active metals, following the stages (2) to (4) as described above. Only it is important to ensure that there is a stage of aging, when the impregnated carrier is wetted with liquid media chelat forming agent and/or metal impregnation.

The present invention, as described above, is further demonstrated by the specific examples which are given for illustration only and not for avandiagenericpy acid

MEA - monoethanolamine

SA(N2- the surface area measured by nitrogen adsorption

SA/g Al2O3- surface area per gram of alumina

RVA relative volume activity on the 1-St stage hydrocracking measured by the method described by the authors Carruthers and DiCamillo in the article "Pilot Plant Testing of Hydrotreating Catalysts", Applied Catalysts, 43 (1988) 253-276. The relative volumetric activity was determined using as a standard catalyst, commercially available under the trademark HC-H (as of may 1994) from the company Unocal Corporation, Brea, CA

RWA is the relative weight activity, which was determined in accordance with the above article.

Example 1

266 g of catalyst carrier based on alumina, commercially available from the firm Criterion Catalyst Company (Houston, Texas), is prepared from alumina powder containing some of amorphous alumina in the form of a hydrate (aqueous), and with a pore volume of 0.62 cm3/g (as measured by the mercury porosimetry), and with a maximum pore size of about 78 (as measured by nitric porosimetry using the desorption isotherm), placed in a stainless vessel and immersed in 1800 ml of impregnating an aqueous solution. Propitious in a dilute solution of phosphoric acid (263 g of a 85% solution in 1509 g of distilled water). To the solution was added 226 g of solid EDTA. Then the solution recycle through an alumina carrier within one hour. Then wet impregnated carrier is removed from the vessel and centrifuged.

Wet media are divided into 4 batches and subjected to aging in a sealed vessel at room temperature for 2 hours, 3 days, 14 days and 22 days. Following this, each batch is dried using either the standard procedure of drying (250oF (121oC) within one hour), or the quick drying (300oF (149oC) for 20 minutes with a powerful air flow). Each sample is then placed in a muffle furnace and calcined at 850oF (454oC) within one hour. The resulting catalyst is designated as E1, E2, E3, E4 and E5 in table 1.

The second series of catalysts prepared in a similar manner, with the only difference that instead of EDTA added to 94.3 g of MEA. The wet impregnated carrier is divided into two parts and subjected to aging at room temperature for 2 hours and 15 days. The catalyst is dried by the method of Rapid Drying and calcined as described above. The obtained catalysts indicated in table 1 as M1 and M2, respectively.

The third series of catalysts prepared similarly, with the only difference that instead of at room temperature for 2 hours and 18 days. The catalyst is dried by the method of Rapid Drying and calcined as described above. The obtained catalysts indicated in table 1 as S1 and S2, respectively.

The fourth series of catalysts prepared similarly, with the only difference that instead of EDTA add 216 g of citric acid. The wet impregnated carrier is divided into three parts and subjected to aging at room temperature for 2 hours, 2 days and 9 days. The catalyst is dried by the method of Rapid Drying and calcined as described above. The obtained catalysts indicated in table 1 as C1, C2, C3, respectively.

Finally, a control series of catalysts prepared as above, with the only difference that instead of EDTA don't add anything. The wet impregnated carrier is divided into two parts and subjected to aging at room temperature for 2 hours and 12 days. The catalyst is dried by the method of Rapid Drying and calcined as described above. The obtained catalysts indicated in table 1 below as A1 and A2.

Although some increase in surface area is measured for each of the samples subjected to aging for more than 10 days, only one chelate forming agent of this series, EDTA, shows a significant increase in catalytic AK is Onen microscopy (AEM) clearly showed "nanocrystalline phase of alumina present in the samples treated with EDTA and subjected to aging, but not in the other alumina samples processed by other agents, or in the alumina raw samples A1 and A2.

Example 2

188 g of the alumina carrier described in example 1, process 1300 ml of solution "A" in the same manner as in example 1, except that instead of EDTA was added 100 g of solid diammonium-EDTA.

The wet impregnated carrier is divided into two portions and one portion is subjected to aging at room temperature 68oF (20oC) within 2 hours, while the second portion is placed in a sealed vessel and subjected to aging at 140oF (60oC) for 17 hours. These 2 servings dried at 450oF (232oC) for 20 min before final finishing and kiln fired at 800oF (427oC). The samples listed in table 2 as DE1 and DE2, respectively.

The sample is subjected to aging for 17 hours at 140oF (60oC) and quickly dried, exhibits high catalytic activity, similar to that obtained using EDTA acid in the previous example 1.

Example 3

100 g of the alumina carrier, described the Institute of economy and management of 46.7 g of the solution "C", containing to 36.8 wt.% trioxide of molybdenum, 6.5 wt.% Nickel oxide and 10 wt.% phosphorus pentoxide to 30 g of 44.7% (by weight) solution of diammonium EDTA and 23 ml of concentrated (29%) of ammonia. The material is then subjected to aging for 2 hours and dried in two stages, first at 250oF (121oC) for 2 hours and then at 500oF (260oC) a further 2 hours.

The dried catalyst is then subjected to a second saturation of the pore solution "D", which consisted of 46.7 g of solution C, diluted with 23 ml of water. The wet impregnated carrier is then subjected to aging in a sealed vessel at 158oF (70oC) for 18 hours in an oven. The catalyst is quickly dried and calcined described above by. The catalyst indicated in table 3 as "F1".

Example 4

750 g of the catalyst carrier based on alumina, commercially available firm Criterion Catalyst Company (Houston, Texas), prepared from alumina powder containing some of amorphous alumina hydrate (aqueous), and pore volume 0,78 cm3/g and with a pore size of about 82 placed in a stainless steel basket and immersed in 5300 ml solution E containing 32 weight. % of molybdenum trioxide, 7.2 wt.% Nickel oxide and 10.7 weight. % phosphoric acid. Then the solution recircul refugium.

The wet impregnated carrier is subjected to aging for 2 hours at room temperature and then dried at 250oF (121oC) and calcined at 800oF (427oC) within 1 hour.

Then the cavity then seven 100 g samples of the finished catalyst is subjected to saturation using eight different aqueous solutions chelat forming agents:

(1) of 7.6 g Ethylenediamine-N,N-luxusni acid in 47 ml of solution.

(2) of 8.25 g Nitryltriacetic acid in 37 ml of solution.

(3) of 12.7 g of Tri-(2-ethylamine)amine in 37 ml of solution.

(4) 8.0 g of ethylene diamine in 38 ml of solution.

(5) 8.0 g of ethylene Glycol in 37 ml of solution.

(6) 11.5g of Triethylenetetramine in 37 ml of solution.

(7) to 31.5 g of 44.7%-aqueous solution of diammonium-EDTA acid in 40 ml of solution.

Each sample is then subjected to aging at 167oF (75oC) in a sealed vessel for 3 days, cooled, and then quickly dried at 450oF (232oC) for 20 min before a final firing at 850oF (454oC). Each catalyst was then analyze and test its activity for nitrogen removal at the 1st speed stage hydrocracking catalytic test (table. 4).

The Primacy Of Texas), which is prepared from alumina powder containing some amorphous hydrate of alumina with a pore volume of 0.71 cm3/g and pore size 78 is subjected to saturation of the pore solution F containing 240 g of diammonium EDTA in 1 l of an aqueous solution. The second 150 g sample of the medium is then saturated with a solution in a ratio of 66:33, respectively, F: water mixture. Third 150 g sample is prepared by saturating a solution F:water mixture in the ratio of 50:50.

Each of the wet impregnated carriers leave for 2 hours, followed by drying in an air oven at 450oF (232oC). Each of the dried material is then placed in a stainless steel basket and immersed in 1200 ml of solution E (example 4). The solution is then recycled, dried over alumina carrier containing the diammonium-EDTA, within one hour after the pellets were centrifuged and subjected to aging for 64 hours at 140oF (60oC). The wet catalyst was then quickly dried at 450oF (232oC) for 20 min in air and calcined at 800oF (427oC) within one hour.

The treated catalysts were characterized by surface area, designed for "grams of catalyst" as well as "grams of alumina". Activity catalysate and thus a decrease of the concentration of diammonium EDTA before soaking (table 5).

Example 6

150 g of the carrier based on alumina described in example 4, is subjected to the saturation of the pore solution "G" containing 48 g of diammonium-EDTA, 9 g of 29% ammonium hydroxide and 12.7 g of uranyl nitrate Nickel in 114 ml of an aqueous solution. Wet material is left for 2 hours before drying it at 250oF (121oC) for one hour in an air oven, followed by drying at 375oF (191oC) for 1 hour. The dried material is then placed in a stainless steel basket and immersed in a solution H containing a 35.6 wt.% trioxide of molybdenum, 9.1 wt.% phosphoric acid and 7.3 wt.% oxide of Nickel. Then recycle through the dried alumina carrier solution containing diammonium-EDTA, within one hour after the pellets were centrifuged.

The resulting material is divided into 2 parts, and one part is subjected to aging at room temperature for three weeks (sample 6A), while the other part is placed in a sealed vessel and subjected to aging for 72 hours at 167oF (75oC) (sample 6B). Both parts are then quickly dried at 450oF (232oC) for 20 minutes and fired in 2 stages: at 575oF (302oC) for 30 min and subsequently at 850oFe activity in the test of hydrogencitrate (table 6).

Example 7

200 g of the carrier based on alumina described in example 4, is subjected to the saturation of the pore solution "J" containing 48 g of diammonium-EDTA, and 15.3 grams of 29 wt.% the ammonium hydroxide and 62 g of the solution "K", containing 32,8% wt. trioxide of molybdenum, 5.9 weight. % oxide and 9.0 wt.% phosphoric acid. The wet impregnated carrier then leave for 2 hours and dried at 250oF (121oC) for 1 hour and then at 450oF (232oC) for 1 hour. The dried material is then placed in a stainless steel basket and immersed in 1400 ml "H". The solution containing the diammonium-EDTA, then recycle through the dried alumina media for one hour, after which the granules are centrifuged, the resulting material is then subjected to aging in a sealed vessel for 3 days at 167oF (75oC) (sample 7A), then quickly dried at 450oF (232oC) for 20 minutes and fired in 2 stages, as in example 6. The increase in surface area and activity of the catalyst in the experience of hydrogencitrate were both highly significant. The results are also shown in table 6.

Example 8

200 g of the carrier based on alumina described in example 4, is subjected to the saturation of the pore solution containing 80 g of diammonium-EDTA, 25,2 g achala at 250oF (121oC) for 1 hour and then at 450oF (232oC) for a further 1 hour. The dried material is then placed in a stainless steel basket and immersed in 1900 ml "H". The solution containing the diammonium-EDTA, then recycle through the dried alumina media for one hour, then centrifuged pellets. The resulting material is divided into two portions, one portion is subjected to aging for 16 hours at 167oF (75oC), another part is subjected to aging for 1 hour in a sealed vessel in a microwave oven to check the temperature of the catalyst at 167oF (75oC) (sample 9B). The samples are then dried in a short time and calcined as before. The increase in surface area and activity of both catalysts was good (table 7).

Example 9

310 g of regenerated industrially used sample Criterion C-424 (Company Criterion Catalyst, Houston, Texas), is subjected to saturation with a solution containing 54.6 g of diammonium-EDTA. The sample is then subjected to aging at 140oF (60oC) in a sealed vessel for 4 days, followed quickly dried and calcined as before (example 10A). Both commercially regenerated education is the quality improvement of catalysts in Catalytic Hydrotest raw materials (blanks) before Fluid Catalytic Cracking (CFH-test). The results of the test and the test conditions shown in table 8. You can see that the regenerated catalyst is treated with EDTA, was significantly improved as compared with the catalysts regenerated by the methods HDS (hydrodesulfurization) and HDN**(hydrogencitrate).

1. Catalytic system for catalytic hydrodesulfurization, hydrodenitrogenation, hydroconversion, hydrodemetallization, hydrocracking, reforming, hydrogenation-dehydrogenation and isomerization of hydrocarbon raw material containing the powdery porous carrier comprising gamma-alumina having a surface area at least 100 m2as measured by nitrogen adsorption, and a pore volume of at least 0.25 cm2/g as measured by mercury porosimetry, and impregnated with one or more of the catalytically active metal, wherein the catalyst further comprises partially nanocrystalline phase of alumina crystallite size of 8 to 25 as measured by the method of transmission electron microscopy, and the nanocrystalline phase of alumina in the surface layer of the catalyst in combination with the gamma alumina which has a crystallite size at the surface of the em at least bimodal mesoporous structure.

2. The catalytic system under item 1, characterized in that the catalyst has a bimodal mesoporous structure with peaks of porosity in the first range of pore sizes from 40 or less, and in the second range of pore sizes from 50 or more, as measured by nitric porosimetry using desorption isotherms.

3. The catalytic system under item 2, characterized in that the catalyst has a bimodal mesoporous structure with peaks of porosity in the first range of pore sizes 20 to 40 second range of pore sizes of 50 to 150 , as measured by nitric porosimetry using desorption isotherms.

4. The catalytic system under item 1, characterized in that the carrier is impregnated with one or more catalytically active metal selected from the group of metals of group VIB and VII of the group.

5. The catalytic system under item 4, characterized in that the carrier is then impregnated with an activator.

6. The catalytic system under item 5, characterized in that the activator is phosphorus.

7. The catalytic system under item 4, characterized in that the carrier is impregnated with one or more of the following metals: Nickel, cobalt, molybdenum and tungsten.

8. The catalytic system according to p. 7, different Teitel impregnated with molybdenum in an amount up to 35 wt.%, calculated as of Moo3and cobalt in an amount up to 9 wt.%, calculated as COO, and the weight percent of the charge, based on the total weight of the catalyst.

10. The catalytic system under item 8, characterized in that the carrier is impregnated with molybdenum in an amount up to 35 wt.%, calculated as of Moo3, cobalt in an amount up to 9 wt.%, calculated as COO and the phosphorus in the amount of up to 10 weight. % calculated as R2ABOUT5and the weight percent of the charge, based on the total weight of the catalyst.

11. The catalytic system under item 7, characterized in that the carrier is impregnated with molybdenum in an amount up to 35 wt.%, calculated as of Moo3and Nickel in an amount up to 7 wt.%, calculated as NiO, with the weight percent of the charge, based on the total weight of the catalyst.

12. The catalytic system under item 8, characterized in that the carrier is impregnated with molybdenum in an amount up to 35 wt.%, calculated as of Moo3, Nickel in an amount up to 7 wt.%, calculated as NiO, and phosphorus in the amount of up to 10 weight. % calculated as R2ABOUT5and the weight percent of the charge, based on the total weight of the catalyst.

13. The catalytic system under item 7, characterized in that the carrier is impregnated with molybdenum in calichera.

14. The catalytic system according to p. 13, characterized in that the medium is additionally impregnated with cobalt and/or Nickel in an amount up to 5 wt.%, calculated as COO and/or NiO, and the weight percent of the charge, based on the total weight of the catalyst.

15. The catalytic system under item 14, characterized in that the carrier is then impregnated with phosphorus in an amount up to 10 wt.%, calculated as R2ABOUT5and the weight percent of the charge, based on the total weight of the catalyst.

16. The catalytic system under item 4, characterized in that the carrier is impregnated with a noble metal in an amount of 2 wt.%, taken on the basis of the total weight of the catalyst.

17. The catalytic system under item 16, characterized in that the noble metal is platinum.

18. Method for the catalytic desulfurization of hydrocarbon raw materials, including the state of contact of the raw materials in the conditions of the desulfurization catalyst described in any of paragraphs.1 - 17.

19. Way catalytic hydrogencitrate hydrocarbon raw materials, including the state of contact of the raw material in terms of hydrogencitrate with a catalyst according to any one of paragraphs.1 - 17.

20. Way catalytic hydroconversion hydrocarbon si

21. Way catalytic hydrodemetallization hydrocarbon raw materials, including the state of contact of the raw material in terms of hydrodemetallization with a catalyst according to any one of paragraphs.1 - 17.

22. Method for catalytic hydrocracking of hydrocarbon feedstocks, including the state of contact of the raw material in the hydrocracking conditions with a catalyst as set in any of paragraphs.1 - 17.

23. Way catalytic reforming of hydrocarbon raw materials, including the state of contact of the raw material in the reforming conditions with a catalyst according to any one of paragraphs.1 - 17.

24. Method of catalytic hydrogenation-dehydrogenation of hydrocarbon raw materials, including the state of contact of the raw materials in the conditions of the hydrogenation-dehydrogenation catalyst according to any one of paragraphs.1 - 17.

25. Way catalytic isomerization of hydrocarbon raw materials, including the state of contact of the feedstock in the isomerization conditions with a catalyst according to any one of paragraphs.1 - 17.

26. Method of increasing the activity of the catalytic system under item 1 for catalytic hydrodesulfurization, hydrodenitrogenation, hydroconversion, hydrodemetallization, hydrocracking, reforming, hydrogenation-dehydrogenation and isomerization of hydrocarbons of the earth, having a surface area at least 100 m2as measured by nitrogen adsorption, and a pore volume of at least 0.25 cm2/g as measured by mercury porosimetry, and impregnated with one or more catalytically active metal by:

(1) wetting the catalytic composition by contact with chelat forming agent in a liquid carrier;

(2) aging moistened thus the substrate until it gets wet;

(3) drying the thus subjected to the aging of the substrate under such temperature and conditions under which the carrier liquid is substantially vaporized;

(4) firing the dried substrate so.

27. The method for the catalytic system under item 1, which consists in the fact that it comprises the following stages:

(1) soaking the powdered porous support containing gamma-alumina and amorphous alumina, one or more catalytically active metals;

(2) before, simultaneously or after stage 1, the wetting of the carrier by contact with chelat forming agent in a liquid carrier;

(3) aging moistened thus impregnated carrier until it gets wet;

(4) drying thus subjected to ageing media when such temperature and conditions, to 28. Method of regenerating the spent catalytic system under item 1 for catalytic hydrodesulfurization, hydrodenitrogenation, hydroconversion, hydrodemetallization, hydrocracking, reforming, hydrogenation-dehydrogenation and isomerization of hydrocarbon raw material containing powdered media, including gamma-alumina and amorphous alumina, impregnated with one or more catalytically active metal, which consists in the fact that it comprises the following stages:

(1) processing spent catalyst to remove hydrocarbon deposits;

(2) wetting the thus treated carrier by contact with chelat forming agent in a liquid carrier;

(3) aging moistened so the media until it gets wet;

(4) drying thus subjected to ageing media when such temperature and conditions under which the carrier liquid is substantially vaporized;

(5) firing the dried thus media.

29. The method according to PP.26, 27 or 28, which consists in the fact that the chelate forming agent has a high-stability parameters in respect to the catalytically active metals of the catalyst.

30. The method according to PP.26, 27 or 28, in which thomposon on PP.26, 27 or 28, which consists in the fact that the chelate forming agent selected from the group consisting of ethylenediaminetetraacetic acid, three(2-ethylamine)amine and Triethylenetetramine, diammonium ethylenediaminetetraacetic acid.

32. The method according to PP.26, 27 or 28, which consists in the fact that the substrate is subjected to aging, is dried at a temperature in the range 100 - 250oC.

33. The method according to PP.26, 27 or 28, which consists in the fact that the substrate is subjected to aging, dried using a heater with air jet (fan).

34. The method according to PP.26, 27 or 28, which consists in the fact that the dried substrate is fired first at the first stage at a temperature which is sufficiently high to output or to decompose any remaining chelate forming agent, but not high enough to hepatoblastoma agents were burnt to soot (carbon deposits), and then in the second stage ambient temperature firing.

 

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