Method of producing hydrotreatment catalyst through saturation with phosphorus-containing compound

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a hydrotreatment catalyst. Described is a method of producing a hydrotreatment catalyst which involves the following steps: a) at least one step for saturating a dried and/or annealed catalyst precursor containing at least one group VIII element and/or at least one group VIB element and an amorphous support using an impregnating solution consisting of at least one phosphorus-containing compound dissolved in at least one polar solvent with relative permittivity higher than 20; b) a step for maturation of said saturated catalyst precursor obtained at step a); wherein said maturation step is carried out at atmospheric pressure, at temperature ranging from ambient temperature to 60°C for maturation period of 12 to 340 hours; c) a step for drying without a subsequent step for annealing said catalyst precursor obtained at step b), wherein the drying step c) is carried out in a drying oven at atmospheric or low pressure and at temperature 50-200°C. Described is use of the catalyst obtained using the described method to carry out hydrofining and hydroconversion of hydrocarbon material.

EFFECT: high catalyst activity.

14 cl, 8 tbl, 17 ex

 

The invention relates to the field of Hydrobromic.

It relates mainly to a method for producing the catalyst used in the methods of hydrobromide, in particular in the way hydrodesulfurised, gidrogenizirovanii, hydrodemetallization, hydrogenation and hydroconversion oil fractions.

Typically, the catalyst hydrobromide hydrocarbon fractions is used to remove sulfur-containing or nitrogen-containing compounds present in these fractions, so that the oil product was consistent with, for example, requirements specifications (sulfur content, aromatic content, and so on) to use for a given purpose (motor fuel, gasoline or diesel fuel, heating oil, jet fuel). This can be also pre-processing of the raw materials to remove impurities before to send raw materials to various refining processes to modify its physico-chemical properties, such as, for example, the processes of reforming, hydrocracking of vacuum distillates, hydroconversion residues of atmospheric or vacuum distillation. The composition and application of catalysts hydrobromide described, in particular, article B.S Clausen, H.T.Topsoe et F.E.Massoth document Catalysis Science and Technology, volume 11 (1996), Springer-Verlag. After sulfonation on the surface of the carrier form is I some substances, not having satisfactory characteristics for carrying out the desired reactions. These substances are described, in particular, in the publication Topsoe and others, published in 26 journal Catalisis Review Science and Engineering 1984, pp. 395-420.

The tightening of the European community requirements for pollution car exhaust (Journal Officiel de l'union européene, L76, 22 mars 2003, Directive 2003/70/EC, .L76/10-L76/19) forcing refineries to significantly reduce the sulfur content in diesel fuel and gasoline (up to 10 parts per million (ppm) by weight of sulfur, from 1 January 2009, compared to 50 ppm from 1 January 2005). These requirements dictate the need for new treatment facilities or a significant increase in activity when equal volumes of the catalysts hydrobromide.

Therefore, to improve the catalyst activity it is necessary to optimize each stage of their receipt in order to receive the maximum amount of surface substances having a high activity at hydrobromide. In particular, it is necessary to control the interaction between the carrier and the precursor of the active phase, which lead to the formation of refractory compounds, resistant to sulfonation (e.g., Al2(MoO4)3, CoAl2O4or NiAl2O4not useful for the catalytic process and providing unwanted eff the CT on the catalytic activity. These interactions between aluminium-containing media and dissolved salts precursors are well known to the specialist: ions Al3+retrieved from aluminium-containing matrix can form heteropolyanions patterns of Anderson's formula [Al(OH)6Mo6O18]3-detected Carrier and others (Journal of the American Chemical Society 1997, 119(42), 10137-10146). The formation of heteropolyanions patterns Anderson identified using Raman spectrometry on the surface of the aluminium-containing media. However, when it comes to significant concentrations of molybdenum, the refractory phase, resistant to sulfonation may be formed as a result of sintering on the surface of the catalyst, such as phase CoMoO4or Co3O4(B.S.Clausen, H.T.Topsøe et F.E.Massoth document Catalysis Science and Technology, volume 11 (1996), Springer-Verlag).

With the aim of increasing the activity of catalysts hydrobromide seems, therefore, important to improve control over the various stages of the preparation of catalysts of hydrobromide, in particular the interactions between the carrier and the precursor of the active phase. Thus, in respect of the catalysts obtained classically by using heptamolybdate ammonium and nitrate of cobalt or Nickel, the decision to eliminate the formation of [Al(OH)6Mo6O18]3-can be used in the Finance molybdenum heteropolyanions phosphorus. The latter is traditionally produced by the introduction of phosphoric acid in the impregnation process, together with the precursors of the active phase. Molybdenum is protected in the form of molybdenum heteropolyanions phosphorus, which is more stable than heteropolyanions [Al(OH)6Mo6O18]3-.

In addition, the specialist is known that catalysts promoted with phosphorus, have improved catalytic activity. Heteropolyanions with the structure of Keggin PMo12O403-, PCoMo11O407-and heteropolyanions P2Mo5O236-continue to be widely used at the present time to obtain catalysts. So, it has been shown in the Journal of American Chemical Society 2004, 126 (44), 14548-14556)that the use of heteropolyanions P2Mo5O236-particularly preferable. This heteropolyanions get with a molar ratio of P/Mo in the impregnating solution is above or equal to 0.4.

However, the introduction of phosphoric acid in the impregnating solution, and the low pH values heteropolyanions solutions lead to more serious consequence: the partial dissolution of the carrier. This is a change of textural characteristics, in particular in the reduction of the specific surface of the WET end of the catalyst (see Applied Catalysis 56 (1989) 197-206, in particular, s). This included the reduction affects the dispersion of the precursors of the active phase on the surface of the carrier and may result in the sintering to the formation of refractory phases of Samoa 4(respectively NiMoO4and Co3O4(NiO, respectively) in the process of possible ignition.

Similar phenomenon is observed with tungsten heteropolyanions phosphorus.

Therefore, experts are interested in finding ways of getting catalysts hydrobromide in General, in particular, catalysts Somer or NiMoP, different from the existing catalysts.

Patent US 4743574 Intevep offers a solution consisting in a preliminary introduction of total phosphorus in the media. The patent describes a method of producing a catalyst for reactions hydrodesulfurised and gidrogenizirovanii containing aluminophosphate or lumbardy the media, which you can use much lower amounts of cobalt. When using media-based alumophosphate (or bismuth), i.e. by adding small amounts of phosphorus in the form of P2About5(or boron in the form of In2About3) to the alumina prior to application of the metal constituting the active phase on the carrier, reduced interaction between these metals and alumina, which reduces the number of metal constituting a given active phase, in particular the number of cobalt, without loss of catalytic activity. However, forming such carriers is a difficult process due to drain the properties of phosphoric anhydride (P 2O5) and does not improve the BET surface of the final catalyst, which reduces the dispersion of the precursors of the active phase on the surface of the media.

The advantage of the invention is to provide a method of producing catalyst hydrobromide, allowing you to enter phosphorus to form phosphorus-containing compounds at the stage of impregnation of the dried and/or calcined catalyst precursor containing at least one element of group VIII and/or at least one element of group VIB and an amorphous medium, and the resulting catalyst hydrobromide has superior catalytic activity compared to catalysts of the prior art.

Another advantage of the present invention is to provide a method of producing catalyst hydrobromide, allowing you to enter a significant amount of phosphorus in the form of a phosphorus-containing compounds at the stage of impregnation of the dried and/or calcined catalyst precursor containing at least one element of group VIII and/or at least one element of group VIB and an amorphous medium, while maintaining a specific surface area in m2per gram of alumina between the source dried and/or calcined catalyst precursor and the final Katalizator is, obtained by the process according to the invention.

Currently, in the framework of the invention a method is proposed for solving the above problems, which is in contrast to prior art allows you to slow down the possible reduction in the BET surface. The present invention describes a method of producing catalyst hydrobromide, comprising the following stages:

a) at least one stage of impregnation of the dried and/or calcined catalyst precursor containing at least one element of group VIII and/or at least one element of group VIB and an amorphous medium, using an impregnating solution consisting of at least one phosphorus-containing compounds, dissolved, at least one polar solvent with a dielectric constant higher than 20;

b) the stage of maturation of the specified impregnated catalyst precursor obtained in stage (a);

c) the stage of drying, without subsequent stage of annealing, the specified catalyst precursor obtained in stage b).

Without reference to any theory, it is assumed that the method according to the invention, in connection with carrying out stage a), which carry at least one impregnation of the catalyst precursor containing at least one element of group VIII and/or group VIB and an amorphous medium, the pre is respectfully alumina, an impregnating solution consisting of at least one phosphorus-containing compounds, dissolved, at least one polar solvent with a dielectric constant higher than 20, avoids direct contact of the amorphous carrier, preferably alumina, with the specified phosphorus-containing compound. Therefore, the method according to the invention allows to avoid the phenomenon of dissolution of amorphous carrier, preferably alumina, in the presence of phosphorus-containing compounds, eliminating, thus, a reduction in the specific surface BET.

Dried and/or calcined precursor of a catalyst containing at least one element of group VIII and/or at least one element of group VIB and an amorphous medium used in stage a) in the method according to the invention and the method thereof are described below.

The specified precursor of the catalyst used in stage a) in the method according to the invention, can be obtained basically by any method known to the expert.

The specified catalyst precursor has a hydro-dehydrating functional group comprising at least one element of group VIII and/or at least one element of group VIB, and optionally contains phosphorus and/or silicon as the promoting element and Amor is hydrated media.

Typically, the amorphous media specified catalyst precursor is chosen from the group formed by alumina and silica-alumina material.

In the case where an amorphous medium is a silica-alumina material, the amorphous medium preferably contains at least 40 wt. % alumina.

Preferably specified amorphous carrier is an alumina, most preferably gamma-alumina.

In the case where an amorphous carrier is alumina, the amorphous media mainly formed in the following way: the matrix consisting of wet alumina gel, such as, for example, hydrated oxyhydroxide aluminum is mixed with the aqueous acid solution, such as, for example, a solution of nitric acid, and then stirred. Is peptidase. After mixing the resulting mass is passed through the die plate with the formation of extruded pellets having a diameter preferably in the range of 0.4-4 mm Extruded pellets are then sent to the stage of drying when the drying temperature of 80 to 150°C. After forming amorphous specified media mainly carry out stage of annealing, at a temperature of annealing from 300 to 600°C.

Hydro-dehydrating function of the specified predecessor rolled atora runs at least one metal of group VIB of the periodic system, selected from molybdenum and tungsten, taken separately or in a mixture, and/or at least one metal of group VIII of the periodic system, selected from cobalt and Nickel, taken separately or in a mixture.

The total content of hydro-dehydrating elements of groups VIB and/or VIII predominantly higher than 2.5 % wt. oxide relative to the total weight of the catalyst.

When you want high activity in the reaction of hydrodesulfurised, metals with hydro-dehydrating function are essentially the Association of cobalt and molybdenum; if you want high activity in the reaction of gidrogenizirovanii, the Association of Nickel and molybdenum or tungsten is preferred.

Predecessors of the elements of group VIB, which can be used are well known to the specialist. For example, among the sources of molybdenum and tungsten can be used their oxides and hydroxides, molybdenum or tungsten acid and their salts, in particular ammonium salts such as ammonium molybdate, heptamolybdate ammonium, ammonium tungstate, phosphomolybdic acid, postwarranty acid and their salts. It is preferable to use molybdenum trioxide or postovulatory acid.

The number of predecessors of the elements of group VIB mainly comprised the focus of 5-35 wt.%. oxide relative to the total mass of the catalyst precursor, preferably 15-30 wt.%, most preferably 16 to 29 wt.%.

Predecessors of elements of group VIII, which can be used mainly selected from oxides, hydroxides, hydroxycarbonate, carbonates and nitrates of the elements of group VIII. When used by an element of group VIII is cobalt, preferably using a hydroxide of cobalt and cobalt carbonate. When used by an element of group VIII is Nickel, it is preferable to use hydroxycarbonate Nickel.

The number of predecessors of elements of group VIII is preferably 1-10 wt.%. oxide relative to the total mass of the catalyst precursor, preferably 1.5 to 9 wt.%, most preferably 2-8 wt.%.

Hydro-dehydrating element of the specified catalyst precursor mainly introduced into the catalyst in different ways and at different stages of preparation of the catalyst.

Specified hydro-dehydrating element mainly you can enter, at least partially, in the process of forming amorphous specified media or preferably named after molding.

When hydro-dehydrating element is injected at least partially in the molding process specified amorphous but is of Italia, it is injected mainly in part only at the time of mixing with the oxide gel selected as a matrix, and the rest of hydrogenating(General) item(s) to impose in this case, after mixing, preferably after annealing the pre-molded carrier. Mainly specified hydro-dehydrating element can also be introduced in full at the time of mixing with the oxide gel selected as the matrix.

Preferably the metal of group VIB is administered simultaneously or immediately after the introduction of the metal of group VIII, regardless of method of administration.

When hydro-dehydrating the element is inserted, at least partially, preferably completely, after forming amorphous specified media, the application of the specified hydro-dehydrating element in amorphous media can be mainly carried out by the method of one or more impregnation solution, taken in excess, molded and calcined carrier, or preferably one or more dry impregnation, the most preferable method of dry impregnation specified molded and calcined carrier with solutions containing salt precursors of metals. Preferably hydro-dehydrating element imposed upon forming amorphous specified media is Ecodom dry impregnation of the specified media using an impregnating solution, containing salt precursors of metals. The introduction of this hydro-dehydrating element can mainly be carried out by the method of one or more impregnations molded and calcined carrier with a solution of precursor (s) of the metal oxide of group VIII, if the predecessor(s) of the metal oxide of group VIB was previously(and) put(s) at the time of mixing media. When items are entered in the result of several impregnations corresponding salts, precursors, typically through an intermediate stage of calcination of the catalyst at a temperature in the range from 250 to 500°C.

Mostly you can also enter a promoter and a catalyst selected from phosphorus, boron, fluorine and silicon, taken separately or in mixtures, preferably specified by the promoter is phosphorus. The specified promoter predominantly administered separately or in a mixture with the metal or metals of group VIB and/or group VIII. Mostly it is administered immediately before or immediately after peptization of the selected matrix, such as, for example, and mainly oxyhydroxide aluminum (boehmite), the precursor of alumina. The specified promoter can also be applied mainly in a mixture with the metal of group VIB or a metal of group VIII, in whole or in part, on the formed amorphous wear the e l e C preferably the alumina in granular form, by dry impregnation specified amorphous carrier with a solution containing salt precursors of the metal and the precursor of the promoter.

Can be used multiple sources of silicon. So, you can use utilitarian Si(OEt)4, silanes, polysilane, siloxanes, polysiloxanes, halogenoalkane, such as forcricket ammonium (NH4)2SiF6or forcricket Na2SiF6. Mainly, it can also be used criminalistica acid and its salts, kremneva.liliya acid and its salts. The silicon may be, for example, impregnated with ethyl silicate, dissolved in a mixture of water/alcohol. Silicon can also be entered, for example, by impregnation of a silicon compound of the type polyalkyloxy in suspension in the water.

The boron source can be boric acid, preferably orthoboric acid (H3BO3Deborah or pentaborate ammonium, boron oxide, esters of boric acid. Boron may be introduced, for example, in the form of a solution of boric acid in a mixture of water/alcohol or in a mixture of water/ethanolamine.

The preferred source of phosphorus is orthophosphoric acid, H3RHO4, but also its salts and esters, such as ammonium phosphates.

Sources of fluoride that can be and is used, well-known specialist. For example, floridayou can be entered in the form of hydrofluoric acid or its salts. These salts formed with alkali metals, ammonium or organic compound. In the latter case, the salt is mainly obtained in the reaction mixture as a result of interaction between the organic compound and hydrofluoric acid. You can also use the hydrolyzable compounds that are capable of releasing water floridamiami, such as forcricket ammonium (NH4)2SiF6or sodium Na2SiF6, tetraploid silicon SiF4. Fluorine can be introduced, for example, by impregnation with an aqueous solution of hydrofluoric acid or ammonium fluoride or diferida ammonium.

The promoter is mainly injected into the catalyst precursor in the amount of the oxide of the specified promoter from 0.1 to 40%, preferably from 0.1 to 30%, even more preferably from 0.1 to 20%, if the specified promoter selected from boron and silicon (% expressed as % wt. oxides).

The promoter can mainly be introduced into the catalyst precursor in the amount of the oxide of the specified promoter from 0 to 20%, preferably from 0.1 to 15%, even more preferably from 0.1 to 10%, if the specified promoter is phosphorus (% expressed as % wt. oxides).

The promoter can mainly be centuries the den in the catalyst precursor in the amount of the oxide of the specified promoter from 0 to 20%, preferably from 0.1 to 15%, even more preferably from 0.1 to 10%, if the specified promoter is fluorine (% expressed as % wt. oxides).

After the introduction of the specified hydro-dehydrating element and, optionally, promoter catalyst or molded and calcined carrier perform primarily a stage of drying, during which the solvent metal salts, precursors of oxide(s) Matala(s) (usually water) is removed at a temperature of from 50 to 150°C.

After the stage of drying the catalyst precursor obtained in this way will not necessarily carry out stage calcination in air at a temperature of from 200 to 500°C, and the specified stage calcination is designed for structuring the oxide phase obtained catalyst precursor and increasing the stability of the specified catalyst precursor, as well as to increase the lifetime of the installation.

It should be noted that this list of operations is not limiting, because you can use them in numerous ways.

According to one preferred variant of the method of obtaining the precursor of the catalyst used in stage a) of the method according to the invention, the precursor is obtained by impregnation with a solution of precursor(s) of the metal oxide of group VIII and/or the precursor(s) of the metal oxide of group VIB molded and calcined carrier, followed by drying at a temperature of 50-150°C. Thus obtained catalyst precursor is dried catalyst precursor.

According to a particularly preferred variant of the method of obtaining the precursor of the catalyst used in stage a) of the method according to the invention described above impregnating solution also contains at least one promoter selected by their phosphorus and silicon, taken separately or in a mixture.

According to another preferred variant of the method of obtaining the precursor of the catalyst used in stage a) of the method according to the invention, the catalyst precursor is obtained by impregnation with a solution of precursor(s) of the metal oxide of group VIII and/or precursor(s) of the metal oxide of group VIB molded and calcined carrier, followed by drying at a temperature of 50-150°C and annealed in air at a temperature of 200-500°C. thus Obtained catalyst precursor is calcined catalyst precursor.

According to another particularly preferred variant of the method of obtaining the precursor of the catalyst used in stage a) of the method according to the invention described above impregnating solution also contains at least one promoter selected from phosphorus and silicon, statehooders or in a mixture.

Thus obtained dried and/or calcined precursor of the catalyst is used then at the stage a) of the method according to the invention.

In accordance with stage a) of the method according to the invention the dried and/or calcined precursor catalyst contains at least one element of group VIII and/or at least one element of group VIB and an amorphous medium.

According to a preferred variant implementation of stage a) of the method according to the invention specified dried and/or calcined precursor catalyst contains at least one element of group VIII selected from cobalt and Nickel, taken separately or in a mixture, and/or at least one element of group VIB, selected from molybdenum and tungsten, taken separately or in mixture of at least one promoter selected from the group consisting of phosphorus and silicon, taken separately or in mixture, and amorphous carrier selected from alumina and silica-alumina material.

According to a particularly preferred variant of the implementation of stage a) of the method according to the invention specified dried and/or calcined precursor catalyst contains at least one element of group VIII , where the specified element of group VIII is cobalt, and at least one element of group VIB, where the specified element of the group VIB is molybdenum, phosphorus as a promoter and amorphous alumina carrier.

According to another particularly preferred variant of the implementation of stage a) of the method according to the invention specified dried and/or calcined precursor catalyst contains at least one element of group VIII, where the specified element of group VIII is Nickel, and at least one element of group VIB, where the specified element of group VIB is molybdenum, phosphorus as a promoter and amorphous alumina carrier.

According to another particularly preferred variant of the implementation of stage a) of the method according to the invention specified dried and/or calcined precursor catalyst contains at least one element of group VIII, where the specified element of group VIII is Nickel, and at least one element of group VIB, where the specified element of group VIB is tungsten, phosphorus as a promoter and amorphous alumina carrier.

In accordance with stage a) of the method according to the invention specified dried and/or calcined precursor of the catalyst is impregnated with an impregnating solution consisting of at least one phosphorus-containing compounds, dissolved, at least one polar solvent with a dielectric constant higher than 20.

Fosforsoderzhashchie connected to the e impregnating solution, used in stage a) of the method according to the invention, primarily selected from the group consisting of orthophosphoric acid, H2RHO4, metaphosphoric acid and phosphorous pentoxide or phosphoric anhydride R2About5or R4About10taken separately or in mixtures, preferably specified phosphorus-containing compound is phosphoric acid, H3RHO4.

Fosforsoderzhashchie connection impregnating solution used in stage a) of the method according to the invention can mainly be selected from the group formed by dietilfosfat, triisobutylaluminum, simple and complex phosphate esters, singly or in a mixture.

Fosforsoderzhashchie connection impregnating solution used in stage a) of the method according to the invention can mainly be selected from the group formed by ammonium phosphate NH4H2PO4, diammonium phosphate (NH4)2HPO4and ammonium polyphosphate (NH4)4P2O7taken separately or in a mixture.

Specified fosforsoderzhashchie connection mainly injected into the impregnating solution used in stage a) of the method according to the invention, in an amount corresponding to a molar ratio of P to metal (metals) of group VIB of the specified PressTV is nice catalyst in the range from 0.001 to 3 mol./mol., preferably 0.005 to 2 mol./mol., preferably 0.005 to 1 mol./mol., particularly preferably from 0.01 to 1 mol./mol.

In accordance with stage a) of the method according to the invention fosforsoderzhashchie compound is introduced into the dried and/or calcined precursor of the catalyst with at least one stage impregnation, preferably a single-stage impregnation with an impregnating solution of the specified dried and/or calcined catalyst precursor described above.

Specified fosforsoderzhashchie connection may be caused primarily by either suspension impregnation or impregnation excess solution, or by dry impregnation, or by any other means known to the expert.

According to a preferred variant implementation of stage a) of the method according to the invention, stage a) is the only stage dry impregnation.

In accordance with stage a) of the method according to the invention impregnating solution of stage a) consists of at least one phosphorus-containing compounds, preferably of a single phosphorus-containing compounds, dissolved, at least one polar solvent with a dielectric constant higher than 20.

When specified impregnating solution of stage a) of the method according to the invention sostoi is, at least one phosphorus-containing compounds, dissolved in more than one polar solvent, i.e. in a mixture of polar solvents, each solvent forming a mixture of polar solvents, has a predominantly dielectric constant higher than 20, preferably above 24.

According to the first preferred variant of the implementation of stage a) of the method according to the invention specified impregnating solution consists of at least one phosphorus-containing compounds, preferably of a single phosphorus-containing compounds, dissolved in a single polar solvent with a dielectric constant higher than 20.

More preferably specified impregnating solution consists of at least one phosphorus-containing compounds, preferably of a single phosphorus-containing compounds, dissolved in a single polar solvent with a dielectric constant higher than 24.

According to the second preferred variant of the implementation of stage a) of the method according to the invention specified impregnating solution consists of at least one phosphorus-containing compounds, preferably of a single phosphorus-containing compounds, dissolved in a mixture of two polar solvents, where each of the two polar solvent which has a dielectric constant greater than 20.

More preferably specified impregnating solution consists of at least one phosphorus-containing compounds, preferably of a single phosphorus-containing compounds, dissolved in a mixture of two polar solvents, where each of the two polar solvent has a dielectric constant higher than 24.

According to a third preferred variant of the implementation of stage a) of the method according to the invention specified impregnating solution consists only of at least one phosphorus-containing compounds, preferably only of a single phosphorus-containing compounds, dissolved, at least one polar solvent not containing a metal and having a dielectric constant higher than 20.

Preferably specified impregnating solution consists only of at least one phosphorus-containing compounds, preferably only of a single phosphorus-containing compounds, dissolved in a single polar solvent not containing a metal and having a dielectric constant higher than 20.

More preferably specified impregnating solution consists of at least one phosphorus-containing compounds, preferably only of a single phosphorus-containing compounds, dissolved in a mixture of two polar races is varicela, not containing metals, where each of the two polar solvent has a dielectric constant greater than 20.

According to a third more preferred variant implementation of stage a) of the method according to the invention specified impregnating solution consists of at least one phosphorus-containing compounds, preferably only of a single phosphorus-containing compounds, dissolved, at least one polar solvent not containing a metal and having a dielectric constant higher than 24.

Preferably specified impregnating solution consists of at least one phosphorus-containing compounds, preferably only of a single phosphorus-containing compounds, dissolved in a single polar solvent not containing a metal and having a dielectric constant higher than 24.

More preferably specified impregnating solution consists of at least one phosphorus-containing compounds, preferably only of a single phosphorus-containing compounds, dissolved in a mixture of two polar solvents not containing metals, where each of the two polar solvent has a dielectric constant higher than 24.

The specified polar solvent used in stage a) of the method according from what retenu, mainly chosen from the group of proton polar solvents selected from methanol, ethanol, water, phenol, cyclohexanol, 1,2-ethanediol, taken separately or in a mixture.

The specified polar solvent used in stage a) of the method according to the invention can mainly be selected from the group formed by propylene carbonate, dimethylsulfoxide or sulfolane, taken separately or in a mixture.

Preferably use proton polar solvent.

List of the used polar solvents and their dielectric permittivity can be learned from books Solvents and Solvent Effects in Organic Chemistry, C.Reichardt, Wiley-VCH, 3-eme édition, 2003, p.472-474).

According to a preferred variant implementation of stage a) of the method according to the invention it is possible to carry out several successive stages of impregnation using an impregnating solution comprising at least one phosphorus-containing compounds, preferably of a single phosphorus-containing compounds, dissolved in a polar solvent, similar to those described above.

In accordance with stage b) of the method according to the invention impregnated with the catalyst precursor obtained in stage impregnation), direct to the stage of maturation, which is especially important for the present invention. Stage Asrian is I b) specified impregnated catalyst precursor, obtained in stage a), carried out mainly at atmospheric pressure and at a temperature in the range from room temperature to 60°C for ripening time from 12 hours up to 340 hours, preferably 24 hours to 170 hours. The ageing period mainly depends on the temperature at which carry out this stage. A method of controlling a period of time sufficient for curing, is the distribution of phosphorus in the impregnated catalyst precursor obtained in stage a) of the method according to the invention, which is defined by various methods such as a method of Castaing microprobe and obtaining the distribution profile of various elements, electron transmission microscopy in combination with x-ray analysis of the catalyst components or the cartographic method of distribution of elements present in the catalyst, using electron microprobe. In particular, if too short maturation phosphorus is distributed in the form of a crust on the catalyst precursor when the precursor contains phosphorus.

In accordance with stage C) of the method according to the invention, the catalyst precursor obtained in stage b), is directed through the drying stage without subsequent calcination of the catalyst precursor obtained in the study is (b).

The purpose of this phase is primarily the removal of all or part of the solvent, due to which was applied the specified fosforsoderzhashchie connection. Stage drying) of the method according to the invention is mainly carried out by any method known to the expert. Stage drying) according to the invention is mainly carried out in a drying oven at atmospheric or reduced pressure at a temperature of 50-200°, preferably 60-190°C., more preferably 60-150°, during the time interval from 30 minutes to 4 hours, preferably from 1 hour to 3 hours. Drying can be advantageously carried out in the movable layer using air or any other hot gas. Preferably, if the drying is carried out in a fixed bed, the used gas is either air or inert gas, such as argon or nitrogen.

The output from stage C) of the method according to the invention receive the dried catalyst, which does not refer to any next stage of annealing.

Before use the catalyst appropriate to convert the catalyst to the metal included therein in oxide form, crossed the sulfide form for the formation of the active phase. This phase activation or sulfonation is carried out mainly in sulfo-reducing atmosphere in the presence of toroda and hydrogen sulfide are known to the specialist methods.

After his release from stage C) of the method according to the invention obtained dried catalyst mainly subjected to the stage of sulfonation (d), without resorting to an intermediate stage of annealing.

Specified the dried catalyst obtained in stage C) of the method according to the invention, mainly sulfurous by the method of ex situ or in situ. Sulfurously agents are predominantly gas H2S or any other compound containing sulfur that is used for activation of hydrocarbons with the aim of sulphurization of the catalyst. These sulfur-containing compounds chosen mainly from alkylsulfides, such as, for example, dimethyl disulfide, alkylsulfate, such as, for example, dimethyl sulfide, n-butylmercaptan, polysulfide compounds of the type tert-nonpolished, such as, for example, TPS-37 or TPS-54 marketed by the company ARKEMA, or any other well-known specialist connection, which allows to achieve a high degree of sulphurization of the catalyst.

The dried catalyst obtained by the method according to the invention and a pre-sulfated at the stage d), used mainly in the Hydrotreating reactions and hydroconversion hydrocarbons such as petroleum fractions, fractions, obtained from carbon or hydrocarbon products derived from natural gas is, more specifically, in the hydrogenation reactions, gidrogenizirovanii, hydrodeoxygenation,hydrodearomatization,hydrodesulfurised, hydrodemetallization and hydroconversion hydrocarbon feedstock containing aromatic compounds and/or olefinic and/or naphthenic and/or paraffinic compounds, and specified raw materials contains optional metals and/or nitrogen and/or oxygen and/or sulfur. When used for these purposes catalysts obtained by the method according to the invention and optionally sulfonated at the stage d), show improved activity compared to catalysts of the prior art.

Amorphous dried catalysts obtained by the method according to the invention and a pre-sulfated at the stage of sulfonation (d), can also be advantageously used in the hydrocracking reactions.

More specifically, the raw material used in the ways in which carry out the reaction of Hydrotreating and hydroconversion hydrocarbons described above are mainly gasolines, gas oils, vacuum gas oils, atmospheric residues of distillation, vacuum distillation residues,distillates atmospheric distillation, vacuum distillates, heavy fuel oil, liquid oils, waxes and paraffins, used oil, neasfaltirovanyj residues or neasfaltirovanyj crude oil, raw materials, POS is waysee from thermal or catalytic conversion methods, taken separately or in a mixture. They contain mainly heteroatoms, such as sulfur, oxygen and nitrogen and/or at least one metal.

Working conditions used in the ways in which carry out the reaction of Hydrotreating and hydroconversion hydrocarbons described above are usually the following: temperature is mainly range 180-450°C, preferably 250-440°C, the pressure is mainly the range of 0.5 to 30 MPa, preferably 1 to 18 MPa, volumetric hourly rate is mainly the range 0.1 to 20 h-1, preferably 0.2 to 5 h-1the ratio of hydrogen/feedstock, expressed in volume of hydrogen, measured under normal conditions of temperature and pressure, the volume of the liquid raw material, is mainly the range of 50 l/l-2000 l/l

The dried catalyst obtained by the method according to the invention and a pre-sulfated at the stage of sulfonation (d), can also be advantageously used in the process of pre-treatment of the feedstock of catalytic cracking and the first stage hydrocracking or soft hydroconversion. In this case, they are usually used on acidic zeolite or not a zeolite catalyst used in the second stage of processing.

The following examples show a significant increase in the catalyst activity, p is obtained by the method according to the invention, compared with catalysts of the prior art and describes a specific implementation of the invention without limiting its scope.

EXAMPLES

In all examples, the preparation of the catalysts according to the present invention, the alumina is used as a carrier.

Example 1: Preparation of dried catalyst C1' and calcined catalyst C1 type Somer (not relevant to the invention)

Use a matrix composed of ultrafine-grained layered boehmite gel or alumina produced is marketed under the name SB3 by the firm Condéa Chemie GmbH. This gel is mixed with an aqueous solution containing 66%nitric acid (7% wt. acid per gram of dry gel)then mixed for 15 minutes. After stirring the resulting slurry is passed through the die plate with a cylindrical hole of diameter equal to 1.6 mm, Then the resulting extruded pellets are dried overnight at 120°C. then calcined at 540°C for 2 hours in moist air containing 40 g of water per kg of dry air. Thus receive the extruded granules of cylindrical shape with a diameter of 1.2 mm, having a specific surface area of 300 m2/g porous volume 0,70 cm2/g and modal distribution of pore size, centered about 93 Å. Matrix analysis by diffraction of x-rays for p is found, that it consists exclusively of cubic gamma-aluminum oxide with low crystallinity.

On an alumina carrier, described above, which is "ekstrudirovaniya" form (67,9 g), are cobalt, molybdenum and phosphorus. An impregnating solution prepared by dissolving by heating molybdenum oxide (24,34 g) and cobalt hydroxide (5.34 g) in an aqueous solution of phosphoric acid (7.47 g) (V=57,0 cm2). After dry impregnation of extruded pellets leave to ripen in the atmosphere saturated with water for 12 hours, then dried overnight at 120°C. the Thus obtained dried catalyst is a catalyst C1'. The final calcination of the catalyst C1' at 450°C for 2 hours in an atmosphere of dry air leads to the calcined catalyst C1. The final content of the metal oxide and a specific surface area of catalysts C1' and C1 (determined by the method of WET, well-known specialist) the following:

- Moo3: 23,4 (% wt.)

- Soo: 4,1 (% wt.)

- R2About3: 4,6 (% wt.)

- Specific surface (SBET): 180 (m2/g of catalyst), i.e. 273 m2/g of alumina in the catalyst C1

- R ls./Mo 0,563 mol./mol.

Example 2: Preparation of dried catalyst C2' and calcined catalyst C2 type Somer (not relevant to the invention)

Prokhladny the catalyst C2 is prepared in the same way, as calcined catalyst C1, based on the molded alumina (70,7 g), molybdenum trioxide (24,23 g), cobalt hydroxide (to 5.21 g), and lower amounts of phosphoric acid (3.25 g).

In the same way as in example 1, the catalyst C2' corresponds to the dried catalyst obtained after the stage of drying. The final content of the metal oxide and a specific surface area of catalysts C2' and C2 in this case are as follows:

- Moo3: 23,3 (% wt.)

- Soo: 4,0 (% wt.)

- R2About3: 2,0 (% wt.)

- Specific surface (SBET): 203 (m2/g of catalyst), i.e. 287 m2/g of alumina in the catalyst C2

- R ls./Mo 0,174 mol./mol.

It is noted that a lower phosphorus content in the impregnating solution allows to obtain a calcined catalyst C2 with higher specific surface WET than the specific surface area of the calcined catalyst C1. This trend is more clearly visible when the specific surface area BET is expressed in g of the alumina present in the catalyst.

Example 3: Preparation of dried catalyst C3' and calcined catalyst C3 type SNF (not in accordance with the invention)

The calcined catalyst C3 is prepared in the same way that the calcined catalysts C1 and C2, but using different impregnating solution based heteropolyanions type of Co Mo10About38H46-. The receipt of such impregnating solution described in the patent application EP 1 393802 (A1). In the same way as in examples 1 and 2, catalyst C3' corresponds to the dried catalyst obtained after the stage of drying. The final content of the metal oxide and a specific surface area of catalysts C3' and C3 in this case are as follows:

- Moo3: 23,0 (% wt.)

- Soo: 5,3 (% wt.)

- Specific surface (SBET): 214 (m2/g of catalyst), i.e. 298 m2/g of alumina present in the catalyst C3

- R ls./Mo is 0 mol./mol.

It is noted that the catalyst not containing phosphorus in an impregnating solution has a specific surface higher than the specific surface area S2, and even higher than the specific surface of the catalyst C1.

Example 4: Preparation of catalyst C4 and catalyst C4' by impregnation of the calcined catalyst C1 and, accordingly, the dried catalyst C1' (according to the invention)

Catalyst C4 (and, accordingly, the catalyst C4') is obtained by impregnation, in accordance with stage a) of the method according to the invention, the calcined catalyst Amor C1 (and, accordingly, the dried catalyst C1') so that the amount of phosphorus introduced at this stage impregnation, was to 0.05 mol. R)/(mol. Mo, located on the calcined precursor catalysis the torus S1 and the dried catalyst precursor C1'). Used by the predecessor of phosphorus is phosphoric acid dissolved in a polar solvent which is a mixture of water/ethanol 50/50 by volume, and each of the components of this mixture has a dielectric constant higher than 20 (dielectric constant of water is 78,4 and the dielectric constant of ethanol is 24.5). After ripening stages within 48 hours of extruded pellets are dried at 120°C for 2 hours under a pressure of 100 mbar. The final content of the metal oxide, the specific surface area of catalysts C4 and C4' and the molar ratio of phosphorus to metal Society. P/Mo deposited on the calcined catalyst C4 and the dried catalyst C4'are in this case the following:

- Moo3: 23,3 (% wt.)

- Soo: 4,1 (% wt.)

- R2About3: 5,1 (% wt.)

- Specific surface (SBET): 179 (m2/g of catalyst), i.e. 273 m2/g of alumina present in the catalyst C4

- R ls./Mo 0,613 mol./mol.

It is noted that this catalyst contains more phosphorus, but its specific surface area BET only slightly changed by adding phosphorus introduced by impregnation with a solution of catalysts C1 and C1' in accordance with stage a) of the method according to the invention.

Example 5. Preparation of catalyst C5 and catalyst C5' by impregnation of a calcined katal the congestion C2 and accordingly, the dried catalyst C2' (according to the invention)

The catalyst C5 (and, accordingly, the catalyst C5') is obtained by impregnation, in accordance with stage a) of the method according to the invention, the calcined catalyst Amor C2 (and, accordingly, the dried catalyst C2') so that the amount of phosphorus introduced at this stage impregnation, was of 0.44 mol. R)/(mol. Mo, located on the calcined catalyst precursor C2 and the dried catalyst precursor C2'). The molar ratio of total phosphorus to the metal Ptot./Mo deposited on the calcined catalysts C4 and C5 and dried catalysts C4' and C5'is identical, i.e. equal 0,613 (mol P/mol Mo). Used by the predecessor of phosphorus is phosphoric acid dissolved in a polar solvent which is a mixture of water/ethanol 50/50 by volume, and each of the components of this mixture has a dielectric constant higher than 20 (dielectric constant of water is 78,4 and the dielectric constant of ethanol is 24.5). After ripening stages within 48 hours of extruded pellets are dried at 120°C for 2 hours under a pressure of 100 mbar. The final content of the metal oxide, the specific surface area of catalysts C5 and C5' and the molar ratio of phosphorus to metal R about the./Mo, deposited on the calcined catalyst C4 and the dried catalyst C4'are in this case the following:

- Moo3: 22,6 (% wt.)

- Soo: 3,9 (% wt.)

- R2About3: 5,0 (% wt.)

- Specific surface (SBET): 193 (m2/g of catalyst), i.e. 287 m2/g of alumina present in the catalyst C5

- R ls./Mo 0,614

It is noted that these catalysts have the same final composition as catalysts C4 and C4', with one exception that the catalyst has a higher content of phosphorus introduced in stage a) of the method according to the invention. Its specific surface area higher than the specific surface of the catalyst C4, in particular, when this surface is expressed in grams of alumina present in the catalyst.

Example 6. Preparation of catalyst C6 and catalyst C6' by impregnation of catalyst C3 and, accordingly, catalyst C3' (according to the invention)

The catalyst C6 (and, accordingly, the catalyst C6') is obtained by impregnation, in accordance with stage a) of the method according to the invention, the catalyst Amor C3 (and, accordingly, catalyst C3') so that the amount of phosphorus introduced at this stage impregnation, was 0,613 (mol. R)/(mol. Mo, located on the calcined catalyst precursor C3 and dried precursor catalysators'). Thus, the molar ratio of total phosphorus to the metal Ptot./Mo calcined in C6 and dried C6' catalysts is identical to the ratio of calcined in C4 and C5 and dried S and C5' catalysts, i.e. equal 0,613 (mol. R)/(mol. Mo, initially present on the catalyst precursor). Used by the predecessor of phosphorus is phosphoric acid dissolved in a polar solvent which is a mixture of water/ethanol 50/50 by volume, and each of the components of this mixture has a dielectric constant higher than 20 (dielectric constant of water is 78,4 and the dielectric constant of ethanol is 24.5). After ripening stages within 48 hours of extruded pellets are dried at 120°C for 2 hours under a pressure of 100 mbar. Standardized end-of oxides of metals and specific surface area of catalysts C6 and C6' are in this case the following:

- Moo3: 21,9 (% wt.)

- Soo: 5,0 (% wt.)

- R2About3: 4,8 (% wt.)

- Specific surface (SBET): 200 (m2/g of catalyst), i.e. 298 m2/g of alumina present in the catalyst C6

- R ls./Mo 0,613

It is noted that these catalysts C6 and C6' are the molar ratio of Society. P/Mo, identical to this ratio in the catalysts C4, C4', C5 and C5' with one exception, that is, and have a higher amount of phosphorus, introduced in stage a) of the method according to the invention. Its specific surface area higher than the specific surface area of catalysts C5 and C5' and especially catalysts C4 and C4'.

Example (not according to invention)

Catalysts C6 and C6' calcined in an atmosphere of dry air at 450°C for two hours. The catalysts obtained after calcination, are respectively catalysts C9 and C9'. The final content of the metal oxide and a specific surface area of catalysts C and C9 (determined by the method of WET, well-known specialist) are in this case the following:

- Moo3: 21,4 (% wt.)

- Soo: 4.9m (% wt.)

- R2About3: 4,8 (% wt.)

- Specific surface (SBET): 185 (m2/g of catalyst), i.e. 276 m2/g of alumina present in the catalyst C9

- R ls./Mo 0,613 mol./mol.

Note that an additional step of annealing, the input for the transition catalysts C6 and C6' to the catalysts C9 and C9', it is not possible to maintain a high specific surface area of catalysts C6 and C6', corresponding to the invention, since the surface of the catalysts C9 and C9' close to the surface of the catalysts C1 and C1'.

Example 7: a Comparative test of catalysts C1, C2, C3, C1', C2', C3', C4, C4', C5, C5', C6 and C6', C9 and C9' in the process of hydrogenation of toluene in cyclohexane under pressure and in presets the accordance of hydrogen sulfide

The catalysts described above, sulfurous in situ in a dynamic process in a tubular reactor with stationary moving bed pilot plant type Catatest (developed by Géomécanique), and streams circulate from top to bottom. Measurement hydrogenating activity carried out immediately after the sulfonation under pressure without air through hydrocarbon boot, which is designed for sulphurization of the catalyst.

Sulfurously download intended for testing consists of 5.8% of dimethyl disulfide (DMDS), 20% toluene and 74.2% cyclohexane (by weight). Measure stable catalytic activity equal volumes of the catalysts in hydrogenation reactions of toluene.

The conditions under which measures the activity, the following:

- Total pressure: 6,0 MPa

The pressure of toluene: 0,38 MPa

The pressure of cyclohexane: 1,55 MPa

- Pressure hydrogen: 3,64 MPa

- Pressure H2S: 0,22 MPa

- The amount of the catalyst: 40 cm3

- Consumption load: 80 cm3per hour

- Hourly spatial speed: 2 h-1

The flow rate of hydrogen: 36 l/h

The temperature of sulfonation and testing: 350°C

Sample liquid effluent analyzed by chromatography in the gaseous phase. Determination of molar concentrations of unconverted toluene (T) and concentrations of the products of the hydrogenation of methyl is of clohexane (MCS), ethylcyclopentane (ETCs) and dimethylcyclopentane (DMCS)) allow to calculate the degree of hydrogenation of toluene XGUIDEaccording to the formula:

Since the reaction of hydrogenation of toluene refers to the reaction of the order of 1 used in the test conditions, and the reactor operates as an ideal piston reactor, hydrogenation activity AndGUIDEcatalyst calculated using the formula:

AndGUIDE=In(100/(100 - XGUIDE))

Table 1 compares the relative hydrogenating activity of the above catalyst, equal to the ratio of the activity in question of the catalyst to the activity of the catalyst C3, is not relevant to the invention and is selected as a reference (an activity of 100%).

Table 1
The relative activity of the calcined catalysts in the hydrogenation process
The composition of
With/Moo3/
P2About5
The share of R entered
at the stage a) of the method
according to the invention
in relation to the total
the number R
SBET(m2/g
catalysis
Torah)
SBET(m2/g
alumina
in
it is talisa-
Torah)
AndGUIDEratio
relatively
against
to C3
Increase
relatively
source
catalyst
C14,1/23,4/4,60180273130-
C24,0/23,3/2,00203287112-
C35,3/230214298100
(standard)
-
C44,1/23,3/5,18%1792731386% relative to C1
C53,9/22,6/5,071%19328714429% relative to C2
C6 5,0/21,9/4,8100%20029814545% relative to C3
C94,9/21,4/4,8100%1852761099% increase relative to the
C3 and losses 25% activity relative to C6

Table 1 shows a significant increase in activity achieved with the catalysts prepared according to the method of the invention, compared with the calcined reference catalysts, is not relevant to the invention, in which the entire quantity of phosphorus was deposited on the catalyst with an impregnating solution. This increase is greater than the higher proportion of phosphorus entered according to the invention, relative to the total phosphorus content.

Table 1 also shows that there has been no reduction of specific surface area, calculated in m2per gram of alumina, between the original catalyst precursor and the final catalyst obtained by the method according to the invention. It remains constant.

States that subsequent calcination of the catalyst C6 to obtain catalyst C9, is not relevant to the invention, prevadid loss benefits associated with the invention, i.e. to the loss of specific surface area, the deterioration dispersion, and loss of activity.

In the same way, table 2 compares the relative hydrogenating activity of the dried catalysts, equal to the ratio of the activity in question of the catalyst to the activity of the catalyst C3', is not relevant to the invention and is selected as a reference (an activity of 100%).

Unexpected was that although the catalysts originally contained phosphorus and was not subjected to annealing, Table 2 shows a significant increase in activity, which is achieved with the dried catalyst obtained by the method according to the invention, in comparison with the reference of the dried catalysts, is not relevant to the invention, in which the entire quantity of phosphorus was deposited on the catalyst with an impregnating solution. It is noted that this increase in activity is greater when the invention is applied to the dried catalysts,not calcined catalysts.

States that subsequent calcination of the catalyst C6' (not relevant to the invention) results in the loss of the advantages inherent in the invention (reduction of the specific surface, the deterioration dispersion, loss of activity of the catalyst C9').

5% compared to C3'.
Loss of 31% compared to the C6'
Table 2
The relative activity of the dried catalysts in the hydrogenation process
CatalystThe composition of the Soo/Moo3/P2About3AndGUIDErelative to C3The increase relative to the original catalyst
C1'4,1/23,4/4,6123-
C2'4,0/23,4/4,6105-
C3'5,3/23100 (control)-
C4'4,1/23,3/5,114812% compared to C1'
C5'3,9/22,6/5,015446% compared to C2'
C6'5,0/21,9/4,815346% compared to C3'
C9'4,9/21,4/4,8105

Example 8: Preparation of calcined catalyst C7 and dried catalyst C7' type NiMoP (not relevant to the invention)

The dried catalyst C7' and calcined option C7 receive in the same way as their homologues C1' and C1, except that the cobalt hydroxide is replaced by hydroxycarbonate Nickel. The number of predecessors of the following: 68,2 g formed of alumina, to 24.02 g of molybdenum trioxide, 11,19 g hydroxycarbonate Nickel and 7.47 g of phosphoric acid.

The final content of the metal oxide and a specific surface area of catalysts C7 and C7' are in this case the following:

- Moo3: 23,1 (% wt.)

- NiO: 4,1 (% wt.)

- R2About3: 4,6 (% wt.)

- Specific surface (SBET): 191 (m2/g of catalyst), i.e. 282 m2/g of alumina present in the catalyst C7.

Example 9: Preparation of catalyst C8 and catalyst S type NiMoP by impregnation of the calcined catalyst C7 and, accordingly, the dried catalyst C7' (corresponding to the invention)

The catalyst C8 (and, accordingly, C8') is obtained by impregnation of the calcined catalyst NiMoP C7 (and respectively dried catalyst C7') so that the amount of phosphorus introduced into the impregnation process in the CE is provided with the stage a) of the method according to the invention, was 0,05 mol. P/mol. Mo present on the catalyst. Used by the predecessor of phosphorus is phosphoric acid, and the solvent is selected according to the document Solvents and Solvent Effects in Organic Chemistry, C.Reichardt, Wiley-VCH, 3rd edition, 2003, str-474 is DMSO with a dielectric constant equal to 46. After maturing within 48 hours of extruded pellets are dried at 120°C for 2 hours under a pressure of 100 mbar.

The final content of the metal oxide and a specific surface area of catalysts C8 and C8' are in this case the following:

- Moo3: 23,0 (% wt.)

- Soo: 4,1 (% wt.)

- R2About3: 5,1 (% wt.)

- Specific surface (SBET): 190 (m2/g of catalyst), i.e. 282 m2/g of alumina present in the catalyst C8.

Example 10: a Comparative test of catalysts C7, C8 and C7', C8' in the process of hydrodesulfurised gasoil

Catalysts C7, C7', C8 and C8', described above, was compared with the test in terms of hydrodesulfurised gasoil, the main characteristics of which are the following:

- Density at 15°C: 0,8522

Sera: 1,44% wt.

- Distillation (modeling):

PI: 155°C

10%: 247°C

50%: 315°C

90%: 392°C

PF: 444°C

Testing was carried out in the pilot isothermal reactor with stationary moving bed, and streams circulate from the bottom up. After sulphonated the I in situ at 350°C in installation under pressure with the investigated gas oil, to which is added 2% by weight of dimethyl disulfide, carried out the test hydrodesulfurised in the following operating conditions:

- Total pressure: 7 MPa

- The amount of the catalyst: 30 cm3

- Temperature: 340°C

The flow rate of hydrogen: 24 l/h

- Consumption load: 60 cm3per hour

Catalytic characteristics of the catalysts are given in Table 3. They are presented as relative activity, which is about 1.5 100% activity of the calcined catalyst C7.

The ratio of binding activity, and conversion in the process of hydrodesulfurised (denoted % SDS), is as follows:

AndSDS= 100/([100-%SDS)]0,5)-1

Table 3
The relative activity of the catalysts with equal amounts of C7, not in accordance with the invention, and C8, corresponding to the invention, in the process of hydrodesulfurised gasoil
CatalystSBET(m2/g of catalyst)SBET(m2/g of alumina in the catalystAndSDSin relation to C7
C7191282 100
C8190282145

Table 3 shows that a significant increase in activity, achieved by using catalysts SOMO also extrapolated using a NiMo catalysts in the process of hydrodesulfurised gasoil. Catalytic characteristics of the investigated catalysts C7'and C8' are shown in Table 4, and the dried catalyst C7' is a reference catalyst.

In addition, table 3 also shows that there has been no reduction of the specific surface, expressed in m2per gram of alumina, calcined between the original catalyst precursor C7 and the final catalyst C8, obtained according to the invention. On the contrary, specific surface area remains constant.

Table 4
The relative activity of the catalysts with an equal volume of C7', not in accordance with the invention, and C8', corresponding to the invention, in the process of hydrodesulfurised gasoil
catalystAndSDSin relation to C7'
C7'100
C8'155

Table 4 shows that a significant increase in activity achieved with the catalysts of SOMO, also extrapolated using a NiMo catalysts in the process of hydrodesulfurised gasoil.

Example 11: the Test conditions hydrobromide vacuum distillate

Catalysts C7 and C8,described above, was also compared with the test in terms of hydrobromide vacuum distillate, the main characteristics of which are the following:

- Density at 20°C: 0,9365

Sera: 2,92% wt.

- Total nitrogen: 1400 hours/million by weight

- Distillation (modeling):

PI: 361°C

10%: 430°C

50%: 492°C

90%: 567°C

PF : 598°C

Testing was carried out in the pilot isothermal reactor with stationary moving bed, and flows circulated from the bottom up. After sulfonation in situ at 350°C in installation under pressure through direct distillation gas oil to which was added 2% by weight of dimethyl disulfide, has been hydrobromide in the following operating conditions:

- Total pressure: 12 MPa

- The amount of the catalyst: 40 cm3

- Temperature: 380°C

The flow rate of hydrogen: 40 l/h

- Consumption load: 40 cm3per hour

Catalytic characteristics of the catalysts are given in Table 5. They are presented as relative activity, which is about 1.5 the t 100% activity of the calcined catalyst C7.

The ratio of binding activity, and conversion in the process of hydrodesulfurised (denoted %SDS), is as follows:

AndSDS=AndSDS=100/([100-%SDS)]0,5)-1

The same ratio applies to the reaction of gidrogenizirovanii (% GDS and aGDS).

In addition, it was estimated conversion of crude oil fraction, having a boiling point of below 380°C, carried out with each catalyst. It is expressed according to the results of simulation of distillation (method ASTM D86) according to the following equation:

Conversion=(% 380+download - %380-effluent)/%380+download

Table 5
The activity of catalysts C7, not in accordance with the invention, and C8, corresponding to the invention, in the process of hydrobromide vacuum distillate
AndSDSin relation to C7AndGDSin relation to C7Conversion of 380°C-(%)
Catalyst10010025
C7135145 29
C8

Table 6 shows a significant increase in activity when working with catalyst obtained according to the invention, compared with the reference catalyst.

Example 12: Preparation of calcined catalyst C9 type SNF (not in accordance with the invention)

The calcined catalyst C9 receive in the same way as calcined catalyst C3, using the same impregnation solution, but diluted with a factor of 1.35. The final content of the metal oxide and a specific surface area of the calcined catalyst C9 are in this case the following:

- Moo3: 17,0 (% wt.)

- Soo: 3,9 (% wt.)

- Specific surface (SBET): 231 m2/g

Example 13. The preparation of the catalyst C10-type SOMO by impregnation of the calcined catalyst C9 (according to the invention)

The catalyst C10 obtained by impregnation of the calcined catalyst C9 so that the amount of phosphorus entered on this transaction impregnation was 0,015 mol. R)/(mol. Mo, on the catalyst). Used by the predecessor of phosphorus is phosphoric acid, and the solvent is selected according to the document Solvents and Solvent Effects in Organic Chemistry, C.Reichardt, Wiley-VCH, 3rd edition, 2003,str-474, which is methanol with a dielectric constant, equal to 33. After maturing within 96 hours of extruded pellets are dried at 120°C for 2 hours under a pressure of 100 mbar. The final content of the metal oxide and the specific surface of the catalyst C10 are in this case the following:

- Moo3: 16,8 (% wt.)

- Soo: 3,9 (% wt.)

- R2About3: 1,0 (% wt.)

- Specific surface (SBET): 228 (m2/g)

Example 14: a Comparative test in the process of selective hydrodesulfurised standard model download, represents the FCC gasoline

Catalysts C9 (not according to invention) and C10 (according to the invention, described above, was investigated in the reaction of selective desulfuromonas standard model download, represents the FCC gasoline. The test was carried out in a reactor of the type Grignard at 200°C and a pressure of 3.5 MPa of hydrogen, constant. Loading consisted of 1000 ppm 3-methylthiophene and 10% wt. 2,3-dimethyl-2-butene in n-heptane. The volume of solution was 210 cm3in a cold condition, and the mass of catalyst was 4 grams (before sulfonation). Before testing the pre-catalyst was sulfurously on the stand of sulfonation in the atmosphere of a mixture of H2S/H2(4 l/h, 15% vol. H2S) at a temperature of 400°C for two hours (at a heating rate of 5C/min, and then reduced the temperature is in the hydrogen atmosphere up to 200°C for two hours. The catalyst is then transferred into the reactor type Grignard,working without access of air.

The rate constant of reaction (standardized per gram of catalyst) is calculated, taking into account that the reaction desulfuromonas (kSDS) is a reaction of order 1, and the reaction of hydrogenation (kGDis the reaction order 0. The selectivity of the catalyst is defined as the ratio of its rate constants of kSDS/kGD. Relative rate constants for catalysts C9 and C10, and their selectivity are shown in Table 6 below.

Table 6
Relative rate constants and selectivity of catalysts C9 (not relevant to the invention) and C10 (according to the invention)
catalystkSDSkGDkSDS/kGD
C9
C10
1,0
1,3
2,32
2,34
0,43
0,56

The catalyst C10 according to the invention is more active in the process of desulfuromonas and more selective than the use of the military the catalyst C9 (not relevant to the invention

Example 15: Preparation of calcined catalyst C11 and dried catalyst C11', is not relevant to the invention

The dried catalyst C11', is not relevant to the invention, obtained by impregnation of the dried catalyst C2' control solution not containing phosphate compound. The solvent is selected according to the document Solvents and Solvent Effects in Organic Chemistry, C.Reichardt, Wiley-VCH, 3rd edition, 2003, str-474 is 1,2-ethanediol with a dielectric constant equal to 38.

The catalyst C11 is a control catalyst, obtained in the same way, but based on the calcined catalyst C2.

Example 15: Preparation of catalyst C12 and catalyst C12' impregnation, respectively calcined C2 and dried C2' catalysts (according to the invention)

The catalyst C12' get method according to the invention by impregnation with a solution containing 0,275 mol of phosphorus per mole of molybdenum, located on the calcined catalyst C2. As phosphorus compounds chosen phosphoric acid. The solvent is selected according to the document Solvents and Solvent Effects in Organic Chemistry, C.Reichardt, Wiley-VCH, 3rd edition, 2003, str-474 is 1,2-ethanediol with a dielectric constant equal to 38. The final content of the metal oxide and the specific surface of the catalyst C12 are in this case the following:

- sub> 3: 22,6 (% wt.)

- Soo: 3,9 (% wt.)

- R2About3: 5,0 (% wt.)

- Specific surface (SBET): 197 (m2/g of catalyst), i.e. 288 m2/g of alumina contained with C12.

Example 16: Preparation of catalyst C13' (not relevant to the invention)

The catalyst C13' is produced by impregnation of a solution containing 0,275 mol. phosphorus per mole of molybdenum on the catalyst C2'. As phosphorus compounds chosen phosphoric acid. The solvent is selected according to the document “Solvents and Solvent Effects in Organic Chemistry, C.Reichardt, Wiley-VCH, 3rd edition, 2003, str-474 is diethyl ether of diethylene glycol with a dielectric constant equal to 5.7. This solvent is highly polar, and therefore does not correspond to the invention. The final content of the metal oxide, restated loss for the combustion of the dried catalyst, the following:

- Moo3: 22,5 (% wt.)

- Soo: 3,8 (% wt.)

- R2About3: 5,1 (% wt.)

Example 17: a Comparative test in the process of hydrodesulfurised gas catalysts C2 (and thus C2'), is not relevant to the invention, C11 (and, accordingly, C11'), is not relevant to the invention, C12 (and accordingly C12') according to the invention and C13' (not relevant to the invention)

The catalysts C2, C2' (not relevant to the invention), C11, C11' (not with testwuide invention), C12, C12' (corresponding to the invention), C13' (not relevant to the invention)described above, compare also when tested under the conditions of hydrodesulfurised gasoil, the main characteristics of which are described in example 10 of this document.

Table 7
The relative activity of the catalysts with an equal volume during hydrodesulfurised gasoil
catalystAndSDSrelatively C12
C11, is not relevant to the invention115
C12 according to the invention145

Table 7 shows that a significant increase in activity obtained with catalysts Somor, associated with the presence of phosphorus compounds, introduced in accordance with the impregnation stage a) of the method according to the invention.

Catalytic characteristics of the tested catalysts C11', C12' C13' are shown in Table 8, and the catalyst C7' is a control catalyst.

Table 8
The relative and the activity of the catalysts with an equal volume of C11', C12' C13' in the process of hydrodesulfurised gasoil
CatalystAndSDSrelatively C7'
C11', is not relevant to the invention135
C12' according to the invention175
C13', is not relevant to the invention97

Unexpectedly, according to Table 5, although the original catalysts contain phosphorus, which has never been subjected to annealing, a significant increase in activity is achieved by adding phosphorus in a polar solvent with a dielectric constant higher than 20, such as 1,2-ethanediol, at the stage of impregnation in accordance with stage a) of the method according to the invention.

The observed increase is much less than with catalyst C11', is not relevant to the invention impregnated with a solution not containing phosphate compound. However, no increase in activity was not observed when adding phosphoric acid, dissolved in a very slightly polar solvent, such as diethyl ether of diethylene glycol.

1. The method of producing catalyst hydrobromide, comprising the following stages: a) at least one stage of impregnation of the dried and/is whether the calcined catalyst precursor, containing at least one element of group VIII and/or at least one element of group VIB and an amorphous medium, using an impregnating solution comprising at least one phosphorus-containing compounds, dissolved, at least one polar solvent with a dielectric constant higher than 20; (b) the stage of maturation of the specified impregnated catalyst precursor obtained in stage (a); and specified stage of ripening is carried out at atmospheric pressure, at a temperature in the range from ambient temperature up to 60°C for ripening period from 12 up to 340 h; (C) the stage of drying, without subsequent stage of annealing, the specified catalyst precursor obtained in stage b), and stage drying) is carried out in a drying oven at atmospheric or at reduced pressure and at a temperature in the range of 50-200°C.

2. The method according to claim 1, wherein said precursor catalyst, dried and/or calcined, contains at least one element of group VIII, where the specified element of group VIII is cobalt, and at least one element of group VIB, where the specified element of group VIB is molybdenum and phosphorus as a dopant and amorphous alumina carrier.

3. The method according to claim 1, wherein said precursor of the catalyst is dried and/or calcined, contains at least one element of group VIII, where the specified element of group VIII is Nickel, and at least one element of group VIB, where the specified element of group VIB is molybdenum and phosphorus as a promoter and amorphous alumina carrier.

4. The method according to one of claims 1 to 3, in which the phosphorus compound impregnating solution of stage a) is chosen from the group formed by phosphoric acid, H3RHO4, metaphosphoric acid and phosphorous pentoxide or phosphoric anhydride (P2About5or R4O10taken separately or in a mixture.

5. The method according to claim 4, in which the phosphorus compound impregnating solution of stage a) is orthophosphoric acid, H3RHO4.

6. The method according to one of claims 1 to 3, in which the specified phosphorus compound is introduced into an impregnating solution in an amount corresponding to a molar ratio of P to metal (metals) of group VIB of the specified catalyst precursor in the range of 0.001 to 3 mol/mol.

7. The method according to claim 6, in which the specified phosphorus compound is introduced into an impregnating solution in an amount corresponding to a molar ratio of P to metal (metals) of group VIB of the specified catalyst precursor in the range of 0.01-1 mol/mol.

8. The method according to one of claims 1 to 3, wherein stage a) is the only stage su the second impregnation.

9. The method according to one of claims 1 to 3, in which the impregnating solution of stage a) consists of a single phosphorus compounds, dissolved in a single polar solvent with a dielectric constant higher than 24.

10. The method according to one of claims 1 to 3, in which the impregnating solution of stage a) consists of a single phosphorus compounds, dissolved in a mixture of two polar solvents, each of the two polar solvent has a dielectric constant higher than 24.

11. The method according to one of claims 1 to 3, wherein said polar solvent is chosen from the group of proton polar solvents selected from methanol, ethanol, water, phenol, cyclohexanol, 1,2-ethanediol, taken separately or in a mixture.

12. The method according to one of claims 1 to 3, wherein said polar solvent is chosen from the group formed by propylene carbonate, dimethylsulfoxide or sulfolane, taken separately or in a mixture.

13. The catalyst obtained by the method according to one of claims 1 to 12, for the implementation of the Hydrotreating reactions and hydroconversion hydrocarbons.

14. Use 13 for the implementation of the hydrogenation reactions, gidrogenizirovanii, hydrodeoxygenation, hydrodearomatization, hydrodesulfurised, hydrodemetallization and hydroconversion hydrocarbons containing aromatic and/and and olefin, and/or naphthenic and/or paraffinic compounds.



 

Same patents:

FIELD: oil and gas industry.

SUBSTANCE: paraffin hydrotreating method involves the first stage at which paraffin with content C21 or higher of normal paraffins 70% wt or higher is used as basic material, and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking, catalyst consisting of metal of group VIII of the Periodic Table, which is put on carrier containing amorphous solid acid; the second stage at which raw material from paraffin is replaced for some time with light paraffin with content C9-20 of paraffins 60% wt or higher, and light paraffin contacts with catalyst at reaction temperature of 120-335 °C in presence of hydrogen for hydrocracking; and the third stage at which raw material of light paraffin is replaced with paraffin and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking. Also, invention refers to method for obtaining material of fuel system, which involves the above method.

EFFECT: use of this invention allows improving activity of hydrocracking catalyst, which deteriorates with time.

6 cl, 1 tbl, 4 ex, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: invention refers to crude product obtaining method involving contact of hydrocarbon raw material, where hydrocarbon raw material has viscosity at least of 500 cSt at 37.8°C, with hydrogen in presence of one or several catalysts so that total product can be obtained, which includes crude product, where crude product represents liquid mixture at 25°C and pressure of 0.101 MPa. At that, crude product has viscosity of not more than 50% of viscosity of hydrocarbon raw material at 37.8°C; and where P-factor of hydrocarbon raw material/total product mixture is at least 1.0. At that, viscosity is determined as per ASTM, method D445, and P-factor is determined as per ASTM, method D7060; where at least one catalyst includes metal (metals) of 6-10 groups in combination with carrier and has pore distribution as per sizes with average pore diameter in the range of 50 to 180 A; at that, catalyst includes at least 0.01 gram of aluminium silicate per 1 gram of catalyst; and where contact conditions are controlled at temperature of 370 to 450°C, partial hydrogen pressure of not more than 7 MPa and volume rate of liquid supply of at least 0.1 h-1. Invention also refers to catalyst for obtaining crude product.

EFFECT: crude product with residue content of not more than 90 percent of residue content in hydrocarbon raw material or reduced viscosity value which represents not more than the half in relation to residue content or viscosity value in hydrocarbon raw material.

14 cl, 27 dwg, 34 ex

FIELD: process engineering.

SUBSTANCE: invention relates to oil processing, in particular, to production of catalyst for extracting sweet oil fraction to be used in oil processing and petrochemistry. Proposed catalyst including commercial molybdenum disulphide and/or tungsten disulphide, as active components, produced by CBC-method with carrier, a nano-sized pseudo-boehmite, in 20:80 ratio or without, subjected to mechanical and chemical effects, promoter, e.g. nanopowders of 3D-metals (Ni, Co, Fe) produced by physical methods at active component-to-promoter ratio of 70:30 with particle size of smaller than 100 nm, and, additionally, gas-phase nanopowder of Ni in pyrocarbon shell with particle size of smaller than 10 nm in amount of 3 wt % of active component. Invention covers method of producing said catalyst in vertical vibration mill by mechanical and chemical activation of components at vacuum of 10-5 torr with frequency and amplitude of vibration of 16 Hz and 2 mm, respectively, and activation time of 4-12 h.

EFFECT: higher activity of catalyst, ultralow content of residual sulfur in hydrodesulfuration products.

2 cl, 2 dwg, 1 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a hydrodemetallation and hydrosulphurisation catalyst, a catalyst system and a method for hydrotreatment of hydrocarbon material. Described is a catalyst containing at least one group VIB metal, at least two group VIII metals designated main promoter VIII-1 and co-promoter VIII-i, where i ranges from 2 to 5, and at least one carrier consisting of a porous refractory oxide, in which group VIII elements are present in proportions determined by atomic ratio [VIII-l/(VIII-l+…+VIII-i)], said ratio ranging from 0.5 to 0.85 and said catalyst containing a group VIB metal or metals in amount of 2-9 wt % of a group VIB metal trioxide with respect to total weight of the catalyst and total content of group VIII metals ranges from 0.3 to 2 wt % of a group VIII metal oxide with respect to total weight of the catalyst. Described is a catalyst system consisting of at least two catalysts described above, in which the first catalyst contains a group VIB metal or metals in amount of 2-9 wt % of a group VIB metal trioxide with respect to total weight of the catalyst and total content of group VIII metals ranges from 0.3 to 2 wt % of group VIII metal oxides with respect to total weight of the catalyst, and the second catalyst contains a group VIB metal or metals in an amount which is strictly more than 9 wt % and less than 17 wt % of a group VIB metal trixode with respect to total weight of the catalyst and total content of group VIII metals is strictly higher than 2 wt % and less than 5 wt % of group VIII metal oxide with respect to total weight of the catalyst, wherein said first and second catalysts have the same atomic ratio. Described is a method for hydrotreatment of heavy hydrocarbon material, involving at least one hydrodemetallation step and at least one hydrodesulphurisation step using at least one catalyst with atomic ratio which is equal at each of the hydrodemetallation and hydrodesulphurisation steps, in which said catalyst is the catalyst described above.

EFFECT: high catalyst activity and degree of conversion of hydrocarbon material.

15 cl, 8 tbl, 9 ex

FIELD: process engineering.

SUBSTANCE: invention relates to catalyst of heavy hydrocarbon desulfurisation, method of its production and method of desulfurisation of heavy hydrocarbons. Proposed catalyst includes calcined mix produced by calcinating formed particle made by grinding the mix containing molybdenum trioxide, nickel compound and inorganic oxide material. Proposed method of producing said catalyst comprises grinding inorganic oxide material, molybdenum trioxide and nickel compound to produce mix to be formed in particle and calcined to obtain aforesaid mix. Method of desulfurisation of heavy hydrocarbon initial stock comprises interaction of the latter with aforesaid catalyst.

EFFECT: purified product with higher stability.

11 cl, 10 tbl, 6 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a composition for use as a catalyst for hydrodesulphurisation of distillate, a method of preparing said composition and a method of obtaining distillate. Described is a method of preparing a composition for use as a catalyst for hydrodesulphurisation of distillate, involving: combined grinding of inorganic substance, molybdenum trioxide particles having size ranging from 0.2 to 150 mcm and a nickel compound to form a mixture; moulding said mixture into particles; and calcining said particles to form a calcined mixture, where said calcination is carried out while controlling temperature conditions such that calcination temperature ranges from approximately 600°C (1112°F) to approximately 760°C (1400°F) for a calcination period of time which is sufficient for obtaining said calcined mixture, having such pore size distribution that at least 70% of total pore volume of said calcined mixture is due to pores of said calcined mixture, having diameter ranging from 70 Å to 150 Å, and where said calcined mixture has molybdenum content ranging from 7 wt % to 22 wt %, where the weight percentages are based on molybdenum in metal form and total weight of the calcined mixture, and content of group VIII metal ranging from 3 wt % to 12 wt %, where the weight percentages are based on group VIII metal in its elementary form and total weight of the calcined mixture. Described is a catalytic composition containing a calcined mixture obtained by calcining a mixture containing an inorganic oxide, molybdenum trioxide particles having the size given above, a group VIII meta with content given above. Described is a method of obtaining distillate with ultralow content of sulphur, involving contact of starting material at suitable desulphation conditions with the composition described above.

EFFECT: obtaining distillate with ultralow content of sulphur, having sulphur concentration less than 50 wt ppm.

14 cl, 4 tbl, 11 ex, 1 dwg

FIELD: oil and gas production.

SUBSTANCE: invention refers to procedure for production of semi-finished product. The procedure consists in contacting oil stock with one or more catalyst at presence of a source of gaseous hydrogen for production of a common product containing a semi-product and gas and in separation of common product into semi-product and gas. The semi-finished product here corresponds to liquid mixture at 25°C and 0.101 MPa and has contents of micro-carbon residue (MCR) as high, as 90% of MCR contents in oil stock wherein contents of MCR amounts to at least 0.0001 gram per gram of oil stock. Also, content of MCR is determined by the method of ASTM D4530. At least one catalyst is the catalyst on base of metal of group 6 of periodic table with average diameter of pores at least 90 Å. Volume of pores with diameter at least 350 Å amounts to as much, as 15% of volume of pores of carrier, wherein diameter of pores and volume of pores is determined by the method of ASTM D4282. Contact is performed at temperature 50-500°C, pressure 0.1-20 MPa, hour volume rate of flow of oil stock 0.05-30 hour-1 and ratio of gaseous hydrogen in source of gaseous hydrogen to flow of oil stock 0.1-100000 nm3/m3. The invention also refers to catalyst for production of semi-finished product and to procedure of production of catalyst for output of semi-finished product.

EFFECT: production of semi-finished product with characteristics more improved, than characteristics of source oil stock.

24 cl, 6 ex, 4 tbl, 8 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for hydrodesulphurisation of naphtha, a method of preparing said catalyst and a method for hydrodesulphurisation of naphtha using said catalyst. Described is a method of preparing the catalyst for hydrodesulphurisation of naphtha and versions thereof, involving: (i) saturating a silicon oxide based support, where the support contains at least approximately 85 wt % silicon oxide and has pore volume between 0.6 and 2.0 cm3/g and average pore size between 150 and 2000 Å, (a) with an aqueous solution of a cobalt salt, (b) an aqueous solution of a molybdenum salt and at least one organic additive. The said organic additive contains at least one organic acid and at least one compound selected from a group consisting of compounds containing at least two hydroxyl group and 2-20 carbon atoms, and (poly)ethers of these compounds, to obtain a catalyst precursor; (ii) drying the catalyst precursor at temperature lower than approximately 350°C to obtain a dry catalyst precursor, and (iii) possibly sulphidation of the dry catalyst precursor, provided that the dry catalyst precursor, or catalyst, is not calcined before sulphidation or use for hydrodesulphurisation. The catalyst for hydrodesulphurisation of naphtha prepared using the method given above is described. Described also is a method for hydrodesulphurisation of naphtha, having olefin content of at least 5 wt % in terms of the weight of naphtha, involving sulphidation of the catalyst and its reaction with naphtha under hydrodesulphurisation conditions.

EFFECT: low degree of saturation of olefins while also minimising loss of octane number and achieving high hydrodesulphurisation activity.

33 cl, 1 tbl, 8 ex, 1 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to method of producing catalytic composition consisting of, at least, one basic metal of VIII group and, at least, one metal of VIB group. Proposed method comprises the following stages: a) dissolving and mixing salts of precursors in solvent, i.e. water, alcohol represented by methanol, ethanol, propyl alcohol, butanol, and/or water-alcohol mix; b) dissolving organic component and/or surfactant in solvent; c) mixing solutions produced at stages (a) and (b); d) adding basic solution of ammonium hydroxide and/or carbonate to solution of stage (c) to pH 5-14, preferably, to pH 8-12; e) increasing temperature of solution produced at stage (d) to 50-200°C, preferably, to 60-100°C; f) homogenising solution of stage (e); g) crystallizing solution of stage (f) by evaporating the solution; h) filtering or centrifuging crystallised suspension of stage (g) to separate crystals and mother solution in case evaporation is not completed; i) rinsing solid substance produced at stage (h) by sufficient amount of deionised water and/or water-alcohol mix; j) drying solid substance produced at stage (i) at 50-300°C, preferably, at 80-150°C, k) thermal treatment of solid substance produced at stage (j) in inert atmosphere, e.g. nitrogen, helium, argon etc., at 200-1000°C, preferably, at 300-600°C; 1) sulphurising substance produced at stage (i) or (j) in gas flow containing 10 vol. % of carbon sulphide, or hydrocarbon fraction containing, at least, 0.2 wt % of sulfur in hydrogen flow at 200-600°C, preferably, at 250-500°C, and pressure of 1-100 kg/cm2. Invention covers also catalytic composition produced as described above.

EFFECT: catalytic composition with high specific activity in hydraulic separation of light and medium fractions.

37 cl, 12 ex, 4 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to production of hydrofining catalysts. Described is a catalyst for hydrofining heavy petroleum cuts which contain active components: [Si·(WO3)12] in amount of 1.0-9.0 wt %; [P-(WO3)12] in amount of 1.0-9.0 wt %; [Si-(MoO3)12] in amount of 4.0-22.0 wt %; [P-(MoO3)12] in amount of 6.0-22.0 wt %; active component promoter - nickel oxide NiO, in amount of 3.0-8.0 wt %; carrier modifier - V2O5 in amount of 0.5-5.0 wt % and SnO2 in amount of 0.1-4.0 wt %; aluminium oxide Al2O3 in amount of 84.4-21.0 wt %. Described also is a method of preparing said catalyst, involving saturation of the carrier with a solution of a molybdenum or nickel compound, involving synthesis and saturation of the modified carrier: V2O5, SnCl4·5H2O, H4[Si(W12O40)]·10H2O, H4[P(W12O40)]·10H2O is added to aluminium hydroxide peptised with a monobasic acid; the mixture of starting compounds is evaporated to residual moisture of 60-70%, moulded in form of extruded articles, dried and calcined, with the final calcination temperature of the carrier equal to 550°C; the calcined extruded articles then undergo one-time saturation with an impregnating solution which contains heteropoly-compounds of molybdenum H4[Si(Mo12O40)]·21H2O, H4[P(Mo12O40)]·14H2O and nickel nitrate Ni(NO3)2·6H2O, with pH of the medium equal to 3.0-5.5, followed by thermal treatment of the ready catalyst.

EFFECT: catalyst characterised by high activity when hydrofining heavy petroleum cuts is obtained.

5 cl, 3 tbl, 7 ex

Composition of fuel // 2414502

FIELD: gas-and-oil producing industry.

SUBSTANCE: here is disclosed composition of fuel with flash point 45°C or more containing synthetic oil Fisher-Tropsh and hydrocarbon mixture A on base of oil with following properties from (1) to (5) at amount from 10 to 30 percents by volume on base of total weight of composition: (1) density at 15°C: 800 kg/cm3 or more and 900 kg/m3 or less; (2) temperature of distillation of 10 vol. % (T10): 150°C or more and 200°C or less; (3) temperature of distillation of 97 vol. % (T97): 270°C or less; (4) contents of aromatic compounds: 40 percents by volume or more and 70 percents by volume or less; and (5) contents of sulphur: 30 shares per million by weight or less.

EFFECT: composition of fuel facilitating decrease of consumption and maintaining excellent properties of exhaust gas of synthetic oil Fisher-Tropsh.

2 cl, 5 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to methylmercaptane synthesis prepared from aluminium oxide, alkali metal wolframate and at least one of ammonium salt containing sulphur or nitrogen with catalyst pH in water suspension 10% being 5.0 - 9.7. The method of methylmercaptanes preparation from methanol and hydrogen sulfide using said catalyst is described also.

EFFECT: enhancing of catalyst activity and selectivity particularly at low hydrogen sulfide/methanol ratios.

6 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts, particularly, to those intended for hydration of vegetable oil and fat and may be used in food, chemical and petrochemical industries. Proposed method comprises preparing granulated catalysts for liquid-phase hydration of vegetable oils and distilled fat acids by hydrogen that represent metallic palladium applied in amount of 0.5-2.0 wt % on carbon carrier of 0.5-6.0 mm-fraction with specific surface of 100-450 m2/g and volume of pores of 0.2-0.6 cm3/g. Hydration is conducted on catalyst stationary bed at 140-210°C, hydrogen pressure of 2 to 12 atm and raw stock consumption of 100 to 1500 g/(kgkt·h).

EFFECT: high hydration rate and stability of technical brands.

4 cl, 1 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for dehydrogenation of paraffin hydrocarbons and methods of producing said catalysts, as well as methods of producing olefin hydrocarbons via catalytic dehydrogenation of corresponding C3-C5 paraffin hydrocarbons and can be used in chemical and petrochemical industry. Described is a catalyst for dehydrogenation of C3-C5 paraffin hydrocarbons, which contains chromium and potassium oxides and optionally zirconium dioxide, deposited on a solid solution of formula ZnxAl2O(3+x) where x=0.025-0.25, with a defective spinel structure. Described is a method of producing the catalyst by hydrating a precursor of the solid solution, saturating with a mixture of solutions of chromic acid, potassium chromate and a zinc salt and optionally zirconyl nitrate, followed by drying and calcination in air, wherein hydration is carried out during the saturation process. A method of dehydrogenating paraffin hydrocarbons in the presence of said catalyst is also described.

EFFECT: high catalytic activity, selectivity and stability with low coke formation.

14 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hydrogen using catalysts. Described is a method of producing hydrogen via direct decomposition of natural or liquefied petroleum gas (LPG), where the catalyst used is based on nickel-iron-gamma-aluminium oxide, prepared through combined adsorption of aqueous solutions of nickel and iron nitrates on gamma-aluminium oxide, carried out in 2-4 steps, where the weight ratio of nickel to iron on the catalyst surface is equal to 1:1 and total weight makes up 20-40%.

EFFECT: high output of hydrogen.

2 cl, 6 ex

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0, oxides of platinum and/or palladium and/or rhenium and/or ruthenium - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium in unipolar water taken in amount that ensures aforesaid content of metal oxide in finished catalyst, drying, tabletting and calcinating.

EFFECT: increase in catalyst activity to 100 wt %, in isooctane selectivity to 75,7 wt % and in yield of target alkyl benzene by 10-15 wt %.

14 cl, 10 ex, 2 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0,oxides of platinum and/or or palladium and/or molybdenum and/or nickel and/or cobalt - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/ or cobalt taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/or cobalt. The process includes two stages: first, cold impregnation at not over 30°C, and, second, at, at least, 70°C, and finally drying, tabletting and calcinating.

EFFECT: increase in catalyst activity approximating to 100 wt %, isotope selectivity approximating to 73.5 wt %, yield of target alkyl benzene by 10-15 wt %.

16 cl, 10 ex, 2 tbl

FIELD: petrochemistry.

SUBSTANCE: invention relates to hydrocarbons cracking catalysts; the method describes modification of zeolitealuminumsilica-base catalyst for hydrocarbons cracking by means of soaking of the catalyst in the organisticmetallosiloxane solution amid cavitation processing with the intensively of the interval rate of injection 0.2-0.5 W/m followed by maturing at the ambient temperature, solvent distilling and high-temperature processing.

EFFECT: cracking catalyst which has high cracking intensity and selectivity was received.

3 cl, 9 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of production of purification catalysts of internal combustion engines exhaust gases; the method of preparation of purification catalysts of internal combustion engines exhaust gases is described herein, the method is characterized by application of cordierite carriers of the cellular structure, formation of the inert layer of aluminum and silicon hydrate on the carrier by means of processing with the caustic soda water solution at the ambient temperature followed by soaking the carrier in the reactor with the inert layer with the cerium salt water solutions and precursor that is represented by perchlorate palladium (II) received directly during the solution of perchlorate palladium (II) in the water in the presence of perchloric acid; thereafter the reduction of palladium by means of hydrogen on the surface of the catalyst is conducted in the above reactor at the atmospheric pressure and ambient temperature.

EFFECT: precipitation and facilitation of the catalysts preparation technology.

1 dwg, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemical and chemical industry, particularly a method of preparing moulded catalysts for conversion of methane into aromatic hydrocarbons and hydrogen in nonoxidative conditions. The invention describes a catalyst for a nonoxidative methane conversion process, containing high-silica zeolite H-ZSM-5, a binding additive - calcium form of montmorillonite, modifying elements - molybdenum and cobalt, where content of the binding additive in the catalyst is not more than 40.0 wt %, while content of molybdenum and cobalt is not more than 3.0 wt % and 1.0 wt %, respectively. Described is a method of preparing a catalyst, involving modification of zeolite with promoting elements through successive wetness impregnation of zeolite H-ZSM-5 with molybdenum and cobalt salt solutions, followed by calcination, and then mixing the zeolite modified with metals with a binding additive suspension in a given proportion to obtain a moulding mass and moulding said mass into granules in a moulding device. The invention also describes a method for nonoxidative conversion of methane in the presence of the catalyst described above.

EFFECT: high efficiency of the nonoxidative methane conversion process owing to high activity and stability of the catalyst.

4 cl, 7 ex, 1 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to catalytic filters for cleaning diesel engine exhaust gases. Proposed filter comprises inlet and outlet and axial length coated by first catalyst comprising platinum group metals on carrier materials and differs from known designs in that said carrier materials are selected from the group including aluminium oxide, silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide and mixes thereof, or mixed oxides. Note here that first catalyst additionally comprises at least one zeolite to accumulate hydrocarbons starting from filter inlet. Note also that section of said filter length is coated by second catalyst that contains no zeolite. Invention covers the method of fabricating said filter wherein both catalyst are applied on said filter as suspension coat. Besides it covers application of said filter for decreasing the content of carbon, hydrocarbon and ash particles in diesel engine exhaust gases.

EFFECT: improved conversion of hydrocarbons into carbon oxide.

10 cl, 2 tbl, 3 ex

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