Preparation of catalyst of hydrorefining

FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

 

The technical FIELD

This invention relates to a catalytic hydrotreatment of hydrocarbons

The LEVEL of TECHNOLOGY

Petroleum hydrocarbon streams are characterized by a relatively high content of impurities, including sulfur, nitrogen, coke balance Conradson, aromatic compounds and metals such as Nickel, vanadium and iron. During the catalytic hydroperiod heterogeneous catalysts is introduced into contact with the raw material in the presence of hydrogen under conditions of elevated temperature and pressure in order to reduce the concentration of impurities in the raw material. The Hydrotreating process promotiom such reactions as hydrodesulfurization (SDS), hydrodenitrogenation (GAM), the removal of coke on Conradson, hydrodemetallization (OMM) and the saturation of aromatic compounds, accompanied by a shift within the boil to products with a lower boiling point. While sulfur and nitrogen components are transformed into hydrogen sulfide and ammonia, metals deposited on the catalyst. The result is the production of ecologically pure hydrocarbon products, such as fuel, and protection of other catalysts secondary refining from deactivation. How to remove heteroatoms from commodity flows, as well as catalysts for such removal are known in practice.

Usually rode the congestion of hydroperiod contain active components of metals of group VI and/or VIII, deposited on a porous refractory oxides such as alumina, alumina-silica, silicon dioxide, zeolites, titanium dioxide, zirconium dioxide, boron oxide, magnesium oxide and combinations thereof. Such catalysts are often prepared by combining the active metal with the carrier. The media containing the metal components are usually dried and calcined at temperatures ranging from about 370 to 600°in order to remove any solvent and to translate metals in oxide form. Calcined metal oxide catalysts are then typically activated by contact with a sulfur-containing compound such as hydrogen sulfide, organic sulfur compounds or elemental sulfur, in order to convert the metal oxides in the catalytically active sulfides of metals.

Important and retains its value challenge in the field of catalysts for oil refining is to develop new catalysts hydroperiod with improved characteristics in order to obtain high-quality petroleum products and to improve economic performance refining. To achieve these goals attempted changes in the characteristics of the composition or the method of preparation of catalysts hydroperiod.

In this area it is known that ' green ' catalysts typically provide higher disperser is of active components, improving the activity of Hydrotreating. Essential for ' green ' catalysts is that active components, such as compounds of metals of group VI and/or group VIII, and promoters, such as phosphorus, is not converted into the oxide form during high temperature stage. In other words, the active components are saved without chemical decomposition prior to sulfurization. For example, US 5198100, US 5336654 and US 5338717 describe the method of preparation of Hydrotreating catalyst impregnated refractory carrier salt of metals of group VI and heteropolyacids metal of group VIII. The catalyst is not calcined or not exposed to high temperatures, thereby preserving heteroalicyclic on the media in their original form. However, before sulfurization catalyst required the complete removal of moisture from the catalyst during the stage of drying under a deep vacuum.

In the General case, because the ' green ' activity of the catalyst is increased, the Hydrotreating conditions required to obtain a given product, become softer. More mild Hydrotreating conditions require less capital to produce the desired quality product, such as allowable concentrations of sulfur, nitrogen, coke residue on Conradson, metals and aromatic compounds, and the duration of kata is Isadora increases due to the lower coxworthy and other factors.

It was unexpectedly found that cooking ' green ' catalyst when using a combined stage of reduction of volatile - sulfurization - allows to prepare the catalyst at lower temperatures for smaller stages and without calcination, which gives a catalyst with superior activity and stability during the Hydrotreating.

BRIEF description of the INVENTION

The method according to the invention allows to prepare the catalyst, using a unified stage of reduction of the volatile - sulfurization. The method includes:

providing a porous media;

the connection of the specified media with one or more catalytically active metals, resulting in the formation of the catalyst precursor containing volatile;

reducing the volatile content in the catalyst precursor in one or several stages, where at least one stage of reduction of the volatile carried out in the presence of at least one sulfur-containing compounds;

where the catalyst precursor is not brought to a temperature calcination to the specified at least one combined stage of reduction of volatile - sulfurization.

A method of preparation of a catalyst suitable for Hydrotreating coal-hydride materials, which includes:

connection porous novtel the one or more catalytically reactive metals, selected from the metals of group VI and group VIII of the Periodic table, resulting in the formation of the catalyst precursor containing volatile;

reducing the volatile content in the catalyst precursor in one or several stages, where at least one stage of reduction of the volatile carried out in the presence of at least one sulfur-containing compounds;

where the catalyst precursor is not brought to a temperature calcination to the specified at least one combined stage of reduction of volatile - sulfurization.

Next, a method of Hydrotreating a hydrocarbon feedstock, where the method includes contacting said raw materials at elevated temperature and elevated pressure in the presence of hydrogen with one or more layers of catalyst, where at least one catalyst bed contains a catalyst prepared by the method comprising the connection porous media with one or more catalytically active metals selected from the metals of group VI and group VIII of the Periodic table, resulting in the formation of the catalyst precursor containing volatile; and reducing the volatile content in the catalyst precursor in one or several stages, where at least one stage of reduction of the volatile spend in PR is the absence of one or more sulfur-containing compounds; and where the catalyst precursor is not brought to a temperature calcination to the specified at least one combined stage of reduction of volatile - sulfurization.

Next, a catalyst made by the method comprising the connection porous media with one or more catalytically active metals, resulting in the formation of the catalyst precursor containing volatile; and reducing the volatile content in the catalyst precursor in one or several stages, where at least one stage of reduction of the volatile carried out in the presence of at least one sulfur-containing compounds; where indicated, the catalyst precursor is not brought to a temperature calcination to the specified at least one combined stage of reduction of volatile - sulfurization.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 shows the average temperature of the layer (SVTS)required for 88% SDS activity of the catalyst produced by the method according to the invention in comparison with a catalyst produced in the usual way.

Figure 2 shows CUTS required for 88% SDS activity of the catalyst produced by the method according to the invention, in comparison with the industrial catalyst.

Figure 3 shows the temperature required for the 30% removal of total nitrogen on the catalyst, zgodovina the method according to the invention, in comparison with the industrial catalyst.

Figure 4 shows the temperature required for the 30% removal of the basic nitrogen on the catalyst produced by the method according to the invention, in comparison with the industrial catalyst.

DETAILED description of the INVENTION

Under normal cooking sulfurizing catalysts inorganic carrier is dried, calcined and connect with one or more catalytically active metals to form a catalyst precursor. Then predecessor optional sostarivayut and remove moisture from the pores of the precursor by drying. Then, the catalyst precursor calcined at high temperatures in direct contact with hot gas to remove residual moisture and to convert the metal oxide precursor in the form. "Temperature calcination", as used here shall mean a temperature of calcination from 400 to 600°With which are usually used in practice. After calcining the precursor sulfurized to obtain the catalyst.

In the method according to the present invention the catalyst is prepared by connecting a porous medium with one or more catalytically active metals to obtain a catalyst precursor containing volatile. Then the volatile content in the catalyst precursor reduce C is one or several stages. Reducing the volatile content can be carried out, for example, processing of the precursor to air at temperatures below the temperature calcination or simply dehydration at ambient conditions. At least one stage of reduction of the volatile carried out in the presence of one or more sulfur-containing compounds and to this unified stage of reduction of volatile - sulfurization of the catalyst precursor does not give the ability to reach temperatures of calcination.

United stage (merged phases) of reducing the content of volatile - sulfurization - can be performed in-situ or ex-situ. After reducing the content of volatile and sulfurization catalyst can optionally be activated when using liquid-phase activated at elevated temperatures. For example, if you applied preconference ex-situ, the catalyst can be introduced into contact with easier raw material, to obtain a catalyst with a metal sulfide on the media. For simultaneous receipt of sulfonated catalyst and removal of solvent from the pores of the catalyst can be used many other ways sulfurization. There is no need to usually high temperature calcination of the catalyst or catalyst precursor.

The catalyst undergoes mass loss during processing, nagdadadada volatile compounds, such as solvents and/or organic and inorganic ligands (functional coordination group having one or more pairs of electrons for the formation of coordination bonds with metals). The term "volatile"as used here shall mean the mass loss calculated after keeping the sample in air at 482°within two hours:

The term "catalyst precursor", as used here, means a carrier, which is connected with one or more catalytically active metals, which have not yet been activated.

"Sulfurization"as it is used here, means contacting the catalyst precursor with one or more sulfur-containing compounds. "Sulfonatophenyl catalyst" is a catalyst in which the active metal components are converted, at least partially, in the sulphides of the metals.

In the method according to the invention, the catalyst precursor, i.e. a carrier with delayed active metals and, optionally, a promoter, not calcined. At least one stage of reduction of the volatile carried out in the presence of one or more sulfur-containing compounds. The volatile content in the catalyst precursor is generally at least 0.5%, preferably from 2% is about 25%, more preferably from 3 to 10%, most preferably from 6 to 10% before the catalyst precursor served on the United stage of reduction of the volatile - sulfurization. Calcination of the catalyst precursor is not necessary or performed, and, in fact, the achievement of the precursor catalyst temperature calcination means deterioration of the results of applying the method according to the invention. United stage reduction of volatile - sulfurization - can be performed in-situ in the reactor, where it will be used catalyst) or ex-situ. The obtained catalyst at Hydrotreating substantially improved compared with the catalyst prepared in the usual way, and the method is simplified by eliminating the stage of high temperature calcination of the conventional processes.

The porous substrate is usually used to carry the catalytically active metal (metals). For Hydrotreating catalysts carriers usually are alumina, alumina-silica, silicon dioxide, titanium dioxide, zirconium dioxide, boron oxide, magnesium oxide, zeolites and combinations thereof. Can be used as porous materials based on carbon, such as activated carbon and/or porous graphite. The preferred carriers of this invention are the nose, the prevalence based on aluminum oxide and aluminum oxide-silicon dioxide. The media put a catalytically active metals, usually selected from groups VI and VIII of the Periodic table. Usually the metals selected from molybdenum, tungsten, cobalt, Nickel and mixtures thereof. In combination with catalytically active metals can be used promoters, such as phosphorus. Variations in the methods of preparation of the catalyst include impregnation, joint formation and coprecipitation. The preferred method in this invention is the impregnation, with the most preferred method is the impregnation of the original moisture. The use of aqueous solutions is generally accepted, however, for fat-soluble active components and promoters in the media, you can also use organic solvents, such as aliphatic and aromatic hydrocarbons, alcohols, ketones, etc. Examples of aqueous solutions include solutions containing molybdates (such as di - and heptamolybdate), molybde and wolframite and silicates, polyoxometallate (such as heteroalicyclic and their complexes with transition metal), various complexes, chelates metals, etc. the pH Value of water solution usually lies in the range from 1 to 12. Methods preparation of solutions and impregnation methods well known from the practice.

The volatile content in the catalyst precursor of the present invention can is to be partially reduced in air at temperatures below temperatures of calcination, including environmental conditions, or the catalyst precursor according to the present invention can be submitted directly to the stage sulfurization. Partial reduction of the volatile removal of physically adsorbed solvents (remaining after impregnation stage) facilitates the transportation of the catalyst, if the reduction of volatile should be conducted in-situ.

It is believed, without being bound to a particular theory, that the method according to the invention regulates the formation of bulk phases of metal oxides in the pores of the catalyst by direct interaction of the catalytic metal with sulfur-containing compound at temperatures below temperatures of calcination, so there is a thermal agglomeration of the active component. When the predecessor sulfurized, sulfur compounds displace the solvent and the sulfur reacts with metals, forming highly dispersed sulfides of metals, before they can produce a significant amount of bulk metal oxides. In the method according to the invention, the catalyst precursor containing residual moisture is exposed to sulfur-containing compounds at temperatures that turns the metal precursor of the catalytically active sulfides of metals and removes moisture from the pores of the catalyst.

In a typical sulfurization in situ can IP alsowhat or gaseous hydrogen sulfide in the presence of hydrogen or liquid-phase sulfureuse agents, such as organic sulfur compounds, including alkylsulfate and polysulfides, thiols, sulfoxidov, etc.

When the sulfurization ex-situ catalyst is normally supplied to the user (refiners) "presulfiding" form, where the metal oxides converted, at least partially, in the sulphides of the metals. Industrial methods sulfurization ex-situ include, for example, the process ACTICAT® (CRI International, Inc.), described in US 5468372 and US 5688736, and the process SULFICAT® (Eurecat US Inc.). In the practice of the present invention, sulfurization ex-situ is preferred.

In the present invention described known processes ex-situ and in-situ modified before the contacting of the catalyst with sulfur compounds do not conduct the calcination of the catalyst at high temperatures. At least one stage of reduction of the volatile carried out in the presence of one or more sulfur-containing compounds. Achieved significantly higher activity and stability ' green ' catalyst compared with the catalysts produced according to conventional methods with separate stages of drying, calcination and sulfurization. It is believed that higher activity in Hydrotreating is achieved due to the higher dispersion of active ingredients, since during the preparation of the catalyst does not occur thermal aglomerate is.

The catalysts produced by the method according to the invention can be used in the process of removal of heteroatoms and other contaminants from hydrocarbons, accompanied by a decrease in the boiling point. This process involves the contacting of the catalyst with the feedstock at elevated temperature and elevated pressure in the presence of hydrogen at one or more layers of catalyst. Temperatures are typically in the range from about 200 to about 470°C, the total pressure is typically in the range of from about 443 to about 24233 kPa, and the hourly volumetric velocity of the liquid (OCSI) generally range from 0.05 to 25 h-1.

Examples

Testing the activity of the catalyst

Active Hydrotreating catalysts in the following examples were compared on a volumetric basis when using microreactors jet stream. For each set of test parameters used the same amount of catalyst based on the bulk density of the Packed catalyst. The reactor worked in isothermal mode. To ensure proper irrigation and characteristics of the piston mode, extruded tablets catalyst of the three-brained form diluted SiC size 180-250 microns (80-60 mesh) in a volume ratio of catalyst:diluent or 1:1 (test conditions 1-3), or :2,5 (test conditions 4) and loaded into the reactor four aliquot.

Sulfurization catalyst in situ

For sulfurization of the catalyst used gaseous mixture of 5% H2S in hydrogen. Pressure sulfurization supported about 443 kPa (test conditions 1-3) and 1,128 kPa (test 4). Temperature rise during sulfurization was as follows: from ambient temperature to 204°With speeds of 1.5°C/min, exposure for 2 hours; heated to 316°2°C/min, exposure for 1 hour, heated to 371°With speeds of 3°C/min, exposure for 2 hours; cooling to 204°and With the input of the tested materials.

Preconference catalyst ex-situ

Precultural ex-situ was performed using the process ACTICAT®. A sample of catalyst was treated with the stoichiometric amount of powdered elemental sulfur based on the metal content in the catalyst plus 1.0% of mass. excess calculated on the total weight of the catalyst, followed by heating of the catalyst introduced sulfur in the presence of a liquid olefinic hydrocarbon. Preconvulsive the precursor catalyst was activated in situ using standard liquid-phase activation.

Liquid-phase activation of the catalyst

Ex-situ preconvulsive precursors of the catalyst was placed in the microreactor of the jet stream and activated diesel fuel for the transformation of compounds of CE is s in the pores in the sulphides of the metals. Activation of the catalyst occurred when the pressure in the installation 6307 kPa, flow rate of hydrogen is 220 ml/min and OCSI diesel 1.5 h-1. The temperature was raised to 135°C and maintained for 1 hour, raised with a speed of 24°C/hour up to 371°C and maintained for 1 hour; and was reduced to 204°C and maintained for two hours, after which he entered the tested raw materials.

Test conditions 1:
Catalyst:100 cm3multilayer catalyst
Industrial catalyst OMM - 33,3%. Experimental catalyst - 66,7%
Pressure:13201 kPa
OCSI:0,33 h-1(the whole system)
CUTS:385°
The velocity of the gas:712,4 m3H2/m3
Tested raw materials:The oil is straight race (atmospheric) extended fractional composition:
 Sulfur4,34% of the mass.
Nitrogen0,26% of the mass.
N the Kel 18,5 ppm
Vanadium62,0 ppm
The main nitrogen667 ppm
Microsocopy balance11.4% of the mass.
Density at 15°0.97 g/l
Test conditions 2
Catalyst:50 cm3one layer of catalyst
Pressure:6996 kPa
OCSI:1.5 h-1
CUTS:354°
The velocity of the gas:356,2 m3H2/m3
Tested raw materials:Heavy vacuum gasoil:
Sulfur1.07% of the mass.
Nitrogen0.29% of the mass.
Nickel0.8 h/million
Vanadium0,6 ppm
The main nitrogen930 ppm
Microsocopy balance0.3% of the mass.
Density improvement is ü 15° 0,92 g/l
Test conditions 3
Catalyst:25 cm3one layer of catalyst
Pressure:14580 kPa
OCSI:0,3 h-1
CUTS:385°
The velocity of the gas:356,2 m3H2/m3
Tested raw materials:Demetilirovanny vacuum residue:
Sulfur2,15% of the mass.
Nitrogen0,39% of the mass.
Nickel19,0 ppm
Vanadium33,0 ppm
The main nitrogen1354 h/million
Microsocopy balanceto 12.0 wt. -%
Density at 15°0,98 g/l
Test conditions 4
Catalyst:20 cm3one layer of catalyst
Pressure:11478 kPa
OCSI:2,2 h-1
CUTS:343°and 363°C
The velocity of the gas:623,35 m3H2/m3
Tested raw materials:Straight-run gasoil:
Sulfur1,80% of the mass.
Nitrogen0,0448% of the mass.
Density at 15°0,86 g/l

Example 1

The extrudate alumina (three segmented, 1.2 mm) was dried by air at 482°C for two hours. The extrudate had the following physical properties:

The bulk density of the Packed catalyst value (0.475) g/cm3

The water pore volume of 0.94 cm3/g

The BET surface 296 m2/g

An impregnating solution was prepared by dissolving 39,1 g posterolaterally acid (75%, obtained from ACROS) and 9,72 g NiCO3in 100 g of deionized water at 60°C. After complete dissolution of the added 7,02 grams of 85% H3RHO4. The solution volume was brought up to the equivalent water volume of the pores of the support. 200 g of the carrier was impregnated with a solution and costarelli within 2 hours. The amount of the metals (on dry basis) amounted to 8% of the mass. Mo, 2% of the mass. Ni and 1% of the mass. R.

To remove excess moisture preaches is the owner of catalyst was treated with air at a temperature below 85° C for 1 hour and was diluted volatile to 6%, after which he learned predecessor, still containing residual moisture. Predecessor additionally dehydrational simultaneously with sulfurization during ACTICAT®. No stage calcination is not used. The resulting catalyst is designated as catalyst A.

The catalyst was placed in the microreactor and activated diesel fuel, and then were tested according to test conditions 1. SDS activity of the catalyst And as the weighted average bed temperature (SVTS)required for 88% SDS, shown in figure 1.

Example 2 - comparative

For the preparation of the catalyst used In the extrudate alumina (1.2 mm, three) with the following properties:

The bulk density of the Packed catalyst 0,484 g/cm3

The water pore volume of 0.95 cm3/g

The BET surface 308 m2/g

The catalyst was prepared by impregnation of the pore volume of the carrier, as described in example 1, followed by air drying at 121°C for 4 hours and calcining in a stream of air at 482°C for 2 hours. Then the catalyst was sulfureous in situ in the usual way, using a mixture of 5% H2S in hydrogen, as described below. The catalyst was progulivali and sulfaethidole two separate stages.

The catalyst was tested under the conditions of test 1. SDS active is any catalyst as CUTS, required for 88% SDS, shown in figure 1.

Example 3

For the preparation of the catalyst used industrial 1,3 beated extruded carrier #1.

An impregnating solution was prepared by mixing 21,62 g NiO, of 35.2 g of Moo3, 9,05 g 86.1% of phosphoric acid and deionized water. The volume of the mixture was approximately 168 ml. of the Mixture was heated with stirring to about 99°C for about 3 hours to dissolve the components of the impregnating solution. Then the mixture was cooled to room temperature. The volume of solution was brought to volume then 200 g of the carrier, which was impregnated as described in example 1. The amount of the metals (on dry substance) was 3.8% of the mass. Ni, 13.6% of the mass. Mo and 2.0% of the mass. R.

The catalyst precursor dehydrational air at 99°C for four hours up until the volatile content was 6%. Then, the catalyst precursor was processed according to the method of ACTICAT® without the use of any of the stages of baking. The resulting catalyst is designated as catalyst C.

The catalyst was tested under the conditions of test 1 in comparison with the industrial catalyst treated by the standard method ACTICAT® using the separate stages of calcination and pre-sulfurization (catalyst D). SDS activity of catalysts C and D as CUTS required for 88% SDS, shown in IG.

Example 4

The properties of the extrudate alumina (three segmented, 1.2 mm), used for the preparation of catalysts E and F, were as follows:

The bulk density of the Packed catalyst worn : 0.505 g/cm3

The water pore volume of 0.87 cm3/g

The BET surface 277 m2/g

An impregnating solution was prepared by dissolving the 5.25 g Ni3and 16,67 g dimolybdate ammonium (NH4)2Mo2O7(56,45% of the mass. Mo) in 60 ml of 14.8% solution of NH3in the water. The solution volume was brought up to 87 cm3and soaked 100 g of the carrier, as described in example 1. The amount of the metals (on dry basis) amounted to 2.3% of the mass. Ni and 8.0% of the mass. Mo. The catalyst precursor dehydrational during the night the air at 127°With removal of excess moisture and ammonia, then cooled to room temperature and divided into two equal portions. The first portion was directly precultural using the process of ACTICAT® without any calcination to remove residual moisture and input of sulfur to the catalyst as described in example 3. The resulting catalyst is designated as catalyst E. the Second portion was progulivali as usual at 482°C for 2 hours and was sulfureous in-situ, using a gas mixture of H2/H2S (catalyst F).

Catalyst E was tested in comparison with catalyst F, using the conditions of test 1. Sravnitel the Naya volume SDS activity (determined from the rate constants of the second order for the two catalysts at 400 hours on stream for catalyst E was 25% higher compared with the rate for catalyst F.

Example 5

The catalyst was tested using the test conditions 2, in comparison with the industrial catalyst (catalyst G), which was used as the carrier for catalyst C. Industrial catalyst (pre-calcined) was sulfureous in-situ, using a gas mixture of H2/H2S. the results of the comparative tests are presented in figure 3 and 4.

Example 6

The catalyst was tested in comparison with industrial standard catalyst (the same as catalyst D, except that sulfurization pre-calcined catalyst was performed in situ using a gas mixture of H2/H2S). Industrial catalyst identified as catalyst N.

SDS activity of the two catalysts were compared using the test conditions 3. Comparative volumetric SDS activity (determined from the rate constants of the second order for the two catalysts at 400 hours on the stream of the catalyst was 20% higher compared with the rate for catalyst N.

Example 7

For the preparation of catalyst I used industrial 1,3 beated extruded carrier #2. An impregnating solution was prepared using the procedure described in example 6, however, the metal content (on dry matter) made up 13.0% of the mass. Mo, 3.0% in mass. Ni, 13, 3,2% of the mass. R. Predecessor to the telesfora dehydrational air at 99° With over three hours up until the volatile content was 8%. Then, the catalyst precursor was processed according to the method of ACTICAT® without any additional stages of drying/calcination.

Catalyst I felt when test conditions 4 in comparison with the industrial catalyst (catalyst J), having the same carrier and the same percentage of metals as catalyst I. Industrial catalyst (pre-calcined) was sulfureous in-situ, using a gas mixture of H2/N2S. Comparative volumetric GAM activity (determined from the rate constants of the second order for the two catalysts) for catalyst I was 20% higher compared with the rate for catalyst J at 200 hours on stream at SVTS 343°and 40% higher for catalyst I with 300 hours on stream at SVTS 363°C.

Example 8 is a comparative

Industrial catalyst treated by the standard method ACTICAT® using the separate stages of calcination and sulfurization (catalyst D), compared with the industrial catalyst of the same type, sulfonatophenyl in-situ gas mixture of H2/N2S (catalyst K), using test conditions 1. Catalyst D catalyst To turned out to be statistically indistinguishable by SDS characteristics and GAM during a test run (1400 hours on stream), shows the th, the effects observed due to the method according to the invention, is not due to differences in the way precultural.

As shown in the examples and can be seen from figure 1-4, GDS and GAM activity of catalysts prepared according to the method of the invention (catalysts a, C, E and I), substantially higher than the activity of catalysts prepared by conventional means using the separate stages of drying, calcination and sulfurization. Therefore, combining the stages of drying/sulfurization and the elimination stage calcination allows you to achieve a lower content of sulfur and/or nitrogen in petroleum products. Higher activity of the catalyst makes possible the operation of industrial installations under less severe conditions upon receipt meeting the requirements of the product. This in turn should increase the lifetime of the catalyst and to reduce production costs.

1. Method of preparation of ' green ' catalyst for Hydrotreating contaminated heteroatoms hydrocarbons, including a connection porous media with one or more catalytically active metals selected from group VI and group VIII of the Periodic table, impregnation, co-molding or by coprecipitation with the formation of the catalyst precursor containing volatile compounds, the decrease in the content of volatile compounds in preaches is the owner of catalyst in one or more stages, where at least one stage of reduction of the volatile carried out in the presence of at least one sulfur-containing compounds, where before the specified at least one combined stage reducing the content of volatile compounds - sulfurization - specified catalyst precursor is not brought to a temperature of calcination and the content of volatile compounds in amounts greater than 0.5%.

2. The method according to claim 1, wherein the specified at least one stage of reduction of the content of volatile compounds - sulfurization - complete ex-situ or in-situ.

3. The method according to claim 1 or 2, wherein the specified one or more catalytically active metals selected from molybdenum, tungsten, cobalt, Nickel and their oxides, sulfides and mixtures thereof.

4. The method according to any one of claims 1 to 3, wherein said porous carrier selected from alumina, alumina-silica, silicon dioxide, titanium dioxide, boron oxide, zeolites, zirconium dioxide, magnesium oxide and combinations thereof.

5. The method according to any one of claims 1 to 4, in which prior to the specified at least one combined stage reduce the content of volatile compounds - sulfurization - specified catalyst precursor has a content of volatile compounds in the range of 3-10%.

6. The method according to claim 5, where the specified catalyst precursor has a content of volatile connect the deposits in the range of 6-10%.

7. Method of catalytic Hydrotreating contaminated heteroatoms hydrocarbons comprising contacting said raw materials at elevated temperature and elevated pressure in the presence of hydrogen with one or more layers of catalyst, where at least one layer of catalyst contains ' green ' catalyst prepared according to the method according to any one of claims 1 to 6.

8. The method according to claim 7, in which at least one stage of reduction of the volatile occurs during liquid-phase sulfurization process.

9. 'Green ' catalyst for Hydrotreating contaminated heteroatoms carbon feedstock containing one or more catalytically active metals selected from group VI and group VIII of the Periodic table, and a porous carrier obtained by the method according to any one of claims 1 to 6.

10. The catalyst according to claim 9, in which the specified one or more catalytically active metals selected from molybdenum, tungsten, cobalt, Nickel and their oxides, sulfides and mixtures, and wherein said porous carrier selected from alumina, alumina-silica, silicon dioxide, titanium dioxide, boron oxide, zeolites, zirconium dioxide, magnesium oxide and combinations thereof.



 

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