Catalytic composition for refining hydrocarbon mixtures, method for preparation thereof (options), and method of hydrofining of hydrocarbon mixtures

FIELD: petroleum processing catalysts.

SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.

EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.

40 cl, 2 tbl, 19 ex

 

The present invention relates to catalytic compositions that contain a beta zeolite, a metal of group VIII, a metal of the VI group and possibly one or more oxides as carrier. The catalytic system, in accordance with the present invention, can be used for Hydrotreating of hydrocarbon mixtures and more precisely for the refining of hydrocarbon mixtures boiling in the boiling range of gasoline, ligroin fraction containing sulfur impurities, i.e. when hydrodesulphurization with simultaneous skeletal isomerization and low degree of hydrogenation of the olefins contained in said hydrocarbon mixtures, and the whole process is carried out in one stage. In particular, this catalytic system can be used for refining of mixtures of hydrocarbons boiling in the boiling range of gasoline, ligroin fraction (naphtha) and obtained after the cracking process, preferably mixtures of hydrocarbons having a boiling point in the range of gasoline, ligroin and fraction obtained after the fluid catalytic cracking (FCC).

Hydrocarbons that boil in the range of gasoline, ligroin faction of the oil obtained after the Philippine red cross (i.e. gasoline fraction), use as a component for mixing with obtaining gasoline. To do this they need to have a high octane number and however low the soda is the content of sulphur, to meet imposed by law restrictions, which are becoming more stringent, in order to reduce the emission of pollutants. Actually, the sulfur present in gasoline mixtures, predominantly (>90%) comes from gasoline fraction obtained from the FCC.

This fraction is also rich in olefins, which have a high octane number. In hydrogenations used for desulfurization, hydrogenation of olefins present, with a corresponding significant decrease in the octane number (RON and MON). Therefore there was a need for a catalytic system, which would reduce the sulfur content in hydrocarbon mixtures which boil within the boiling range of gasoline, ligroin faction, and at the same time would reduce the octane loss (RON and MON), which could be achieved, for example, skeletal isomerization of olefins present and/or deceleration of the hydrogenation of olefinic double bonds.

Know the use of zeolites with an average pore size as catalysts for isomerization and subsequent recovery of octane in the downloads already subjected to desulfurization (U.S. patent 5298150, USA 5320742, USA 5326462, USA 53118690, USA 5360532, USA 5500108, USA 5510016, USA 5554274, USA 599439). In these known processes, in order to ensure hydrodesulfurized is with loss of octane number, required two stages, using the first stage catalysts suitable for desulfurization, and the second stage catalyst to restore the octane number.

In U.S. patent 5378352 described single-stage process for the desulfurization of hydrocarbon fractions with boiling points in the range of gasoline fractions, using a catalyst which contains a metal of group VIII, a metal of group VI, a zeolite selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, MCM-22, and mordenite, and a metal oxide as a ligand, with the process temperature is preferably above 340° C.

Some catalytic materials containing metals of group VIII and VI groups of the refractory carrier and a zeolite selected from ZSM-35, ZSM-5, mordenite and tasita described in EP 442159, EP 437877, EP 434123 used isomerization and disproportionation of olefins; in U.S. patent 4343692 - by unit; in U.S. patent 4519900 - by hydrogencitrate; EP 072220 in the two-stage process, consisting of dewaxing and hydrodesulphurization; in U.S. patent 4959140 - held two-stage hydrocracking process.

The authors suddenly discovered a new catalytic system that can be used for Hydrotreating of hydrocarbon mixtures, and more precisely the catalytic system, with which it is possible desulfurization with a high degree of conversiones hydrocarbons, which boil in the range of gasoline, ligroin fraction containing sulfur and olefins, with the simultaneous implementation of the skeletal isomerization of olefins present with a low degree of hydrogenation of the olefinic double bonds. This new catalytic system active at temperatures and pressures that are lower than is preferably used in the known methods of desulfurization.

As skeletal isomerization, and reduced olefin hydrogenation give the possibility of hydrocarbon mixtures boiling in the range of gasoline, ligroin faction, with a very low RON (research octane number) and MON (motor octane number).

The catalytic composition in accordance with the present invention can be used not only for desulfurization of hydrocarbon fractions which boil in the range of gasoline, ligroin fraction (130-250° C), i.e. fractions with low content of olefins, but also raw materials from all over the gasoline-ligroin fraction which boils in the range from 35 to 250° in the case of fractions with a high content of olefins. Actually, the catalytic system of the present invention is highly selective desulfurization compared with hydrogenation, which gives additional benefits in terms of recovery octane in finished gasoline.

Ass is her present invention, therefore, a catalytic composition, which contains a beta zeolite, a metal of group VIII, a metal of the VI group and possibly one or more oxides as carrier.

Beta zeolite is a porous crystalline material, described in U.S. patent 3308069 having a molar composition of oxides corresponding to the following formula:

[(x/n)M(1±0,1-x)Q]AlO2·ySiO2·wH2O

in which: x is less than 1, preferably less than 0,75; y varies in the range from 5 to 100; w ranges from 0 to 4; M is a metal selected from the metals of IA, IIA, IIIA group or transition metal; n is the valency of M and Q is hydrogen ion, ammonium ion, an organic cation or a mixture. Preferably at greater than 5 and less than 50.

In accordance with a preferred variant of the invention the beta zeolite is in the acid form, i.e. in the form in which the cationic centers zeolite mainly occupied by hydrogen ions. More preferably, at least 80% of cationic centers were occupied by hydrogen ions.

In accordance with a variant of the invention, in which the catalytic composition comprises a beta zeolite and metals of the VIII and VI groups, it is preferable that the zeolite is present in the amount of 70 to 90%; when the catalytic composition also contains one or more oxides as carrier, preferably is, to the specified zeolite is present in the amount of 5 to 30% (mass.) in relation to the total weight of the catalyst.

The catalysts used in the present invention preferably contain cobalt or Nickel as the metal of group VIII, while the metal VI group preferably selected from molybdenum or tungsten. According to a preferred variant of the invention using cobalt and molybdenum. The mass content of the metal of group VIII is preferably from 1 to 10% relative to the total weight of the catalyst, still more preferably from 2%to 6%; the weight percent of metal VI group is preferably from 4 to 20% relative to the total weight of the catalyst, still more preferably from 7 to 13%. The mass contents VI metal and a metal of group VIII are metal content, expressed as elemental metal VI group and elementary metal of group VIII; in the resulting catalyst metals VI and VIII groups are in the form of oxides. In accordance with a preferred variant of the invention the molar ratio between the metal of group VIII and VI metal In group less than or equal to 2, preferably less than or equal to 1.

The oxide is used as a carrier, preferably is an oxide of an element Z selected from silicon, aluminum,titanium, zirconium and mixtures thereof. The carrier of the catalytic composition may consist of one or more oxide, and the oxide is preferably aluminum oxide or aluminum oxide, a mixed oxide selected from silicon oxide or zirconium oxide.

The catalytic composition in accordance with the present invention can be prepared by conventional methods, for example by impregnation of a beta zeolite with a solution containing a metal salt VI group and a salt of metal of group VIII, drying, and calcination. The impregnation can also be produced by using a solution containing metal salt VI group, and a solution containing a salt of metal of group VIII.

If the catalyst contains one or more oxides as carrier, it can be prepared by mixing the zeolite with the oxide, followed by extrusion, annealing, possible metabolic process, which reduces the sodium content, drying, impregnation with a solution containing a metal salt VI In groups, drying, calcination, impregnation with a solution of salt of metal of group VIII, drying and roasting.

In accordance with the most preferred implementation of the present invention the catalytic compositions that contain one or more oxides as carrier, is produced by the Sol-gel technology, carry out the following treatment is Ohm:

a) preparing an alcohol dispersion containing a soluble salt of metal of group VIII, beta-zeolite and one or more organic compounds capable of forming the oxide or oxides-media;

b) preparing an aqueous solution containing a soluble salt of the metal VI In groups and, possibly, of tetraalkylammonium hydroxide having the formula R4NOH;

C) an alcohol dispersion and the aqueous solution is stirred and get gel;

g) carry out the aging of the gel at a temperature in the range from 10 to 40° C;

d) the gel is dried;

(e) the gel is calcined.

Catalytic compositions thus obtained have a high surface area (> 200 m2/g) and large pore volume (>0.5 cm3/g) distribution within mesoporous (srednevoljskogo) range.

Operations and preparation of salt of metal of group VIII represents, for example, nitrate, hydroxide, acetate, oxalate, preferably nitrate.

The organic compound capable of forming the oxide or oxides carrier by hydrolysis and subsequent transactions gelation and calcination, is an appropriate alkoxide or alkoxides in which alkoxide the substituents have the formula (R O)-, in which R' is an alkyl containing from 2 to 6 carbon atoms. The alkoxide is preferably an alkoxide of an element Z that is selected from silicon, aluminum, titanium, zirconium and mixtures thereof; in particular, when Z is aluminum, this trialled having the formula (R O)3Al, in which R' preferably represents an isopropyl or secondary butyl; when Z is silicon, this tetraethoxide having the formula (R O)4Si in which R' is preferably an ethyl, and when Z represents Zr, this alkoxide having the formula (R O)4Zr, where R' is preferably isopropyl.

Operations b) a soluble salt of the metal VI group may be an acetate, an oxalate or ammonium salts, and preferably is ammonium salt. Of tetraalkylammonium hydroxide has the formula R4NOH in which R is an alkyl group containing from 2 to 7 carbon atoms. In accordance with a preferred embodiment of the invention the solution to the operations b) also contains formamide (chemical agent regulating drying), which contributes to the stabilization of the porous structure on the operation of drying.

Amounts of reactants selected depending on the composition of the finished catalyst.

Transaction), according to the preferred sequence, the solution obtained in operation b), is added to the suspension obtained in operation (a).

Operations g) obtained gel is maintained at a temperature of from 10 to 40° C is for 15-25 hours.

Operation e) is carried out at a temperature of from 80 to 120° C.

Operation (e) is carried out at a temperature of from 400 to 600° C.

According to another variant implementation of the present invention a catalytic system containing one or more oxides as carrier, can be prepared as follows:

a) preparing an alcohol dispersion containing beta zeolite and one or more organic compounds capable of forming the oxide or oxides-media;

b) preparing an aqueous solution containing of tetraalkylammonium hydroxide having the formula R4PONT;

C) an alcohol dispersion and the aqueous solution is stirred and get gel;

g) carry out the aging of the gel at a temperature of from 10 to 40° C;

d) the gel is dried;

(e) gel calcined;

g) the calcined product is impregnated with a solution containing metal salt VI group, dried, calcined, impregnated with a solution containing a salt of metal of group VIII, dried and calcined.

Amounts of reactants selected depending on the composition of the finished catalyst. Reagents are the same as in the Sol-gel synthesis.

In accordance with another embodiment of the invention the catalytic composition containing an oxide or oxides carrier, can be prepared as follows:

a) prepare Speer the new variance, containing a soluble salt of metal of group VIII and one or more organic compounds capable of forming the oxide or oxides-media;

b) preparing an aqueous solution containing a soluble salt of the metal VI In groups and, possibly, of tetraalkylammonium hydroxide having the formula R4NOH;

C) an alcohol dispersion and the aqueous solution is stirred and get gel;

g) carry out the aging of the gel at a temperature of from 10 to 40° C;

d) the gel is dried;

e) carry out mechanical mixing of the dried product with beta-zeolite;

g) carry out calcination.

Reagents are the same as in the Sol-gel synthesis. Amounts of reactants selected depending on the composition of the finished catalyst.

According to the following alternative implementation of the present invention the catalytic compositions containing one or more oxides as carrier, can be prepared as follows:

a) impregnation of a carrier comprising one or more oxides, metal salt VI group and a salt of metal of group VIII;

b) drying and calcining the material obtained in operation (a);

C) mixing the impregnated oxide obtained in operation b), with beta-zeolite.

Amounts of reactants selected depending on the composition of the finished catalyst.

Impregnation operations and carried the t in any traditional way, metal salts VI and VIII groups are in aqueous solutions. When using a separate aqueous solutions of VI metal and a metal of group VIII, the operation of drying and calcination may be introduced between the two impregnations. Before surgery) impregnated oxide may be pulverized and sieved to a particle size of <0.2 mm, and then, at operation), mixed with the zeolite by physical mixing or dispersion of the particles in an organic solvent type cyclohexane or cyclohexanol. The solvent is evaporated and the catalyst particles are dried and calcined. Mixing operations) can be made by mixing and homogenization of the solid mixture containing impregnated oxide (particle size <0.2 mm), zeolite, the ligand and possibly flammable organic polymers.

Thus obtained mixture may be mixed with peptizyde acid solution, extruded, dried and calcined in any traditional way. Alternatively, the paste may be granulated, dried and calcined in any traditional way.

The catalysts used in the method according to the present invention, can be used as such or preferably extruded in accordance with known technology, for example using peptizing agent, such as a solution of acetic acid, and the possibility is about, ligand pseudoboehmite type to be added to the catalyst to obtain a paste, which can be ekstradiroval. In particular, when the catalysts are prepared by Sol-gel method, the addition of the ligand during the extrusion process is optional.

The products of the present invention can be used as catalysts for Hydrotreating of hydrocarbon mixtures and more precisely for the refining of hydrocarbon mixtures which boil in the range of gasoline, ligroin faction.

The present invention, therefore, is also the Hydrotreating of hydrocarbon mixtures, characterized by the use of a catalytic composition which comprises a beta zeolite, a metal of group VIII, a metal of the VI group and possibly one or more oxides as carrier.

In accordance with this preferred embodiment of the invention relates to a hydrodesulphurization of hydrocarbon mixtures having ranges of boiling points in the range of from about 35 to 250° containing olefins and at least 150 million hours (ppm) of sulfur, while skeletal isomerization of these olefins, which comprises contacting such mixtures in the presence of hydrogen with a catalytic composition which comprises a beta zeolite, a metal of group VIII, a metal of the VI group and possibly one or more the oxides as a carrier.

When using a catalytic composition comprising a beta zeolite, a metal of the VI group and the metal of group VIII, the method in accordance with the present invention is carried out at a temperature of from 220 to 360° C, preferably between 300 and 350° C, under pressure, comprising from 5 to 20 kg/cm2with a bulk velocity (WHSV)constituting from 1 to 10 h-1. The amount of hydrogen exceeds 100-500 times the amount of hydrocarbons present (norm. l/l).

When the catalytic composition also contains one or more oxides as carrier, the hydrodesulphurization process with simultaneous skeletal isomerization of olefins present is carried out at a temperature of from 220 to 320° C, preferably between 250 and 300° C, under pressure, comprising from 5 to 20 kg/cm2and with a bulk velocity (WHSV) of between 1 and 10 h-1. The amount of hydrogen exceeds the amount of hydrocarbons present (NORML/l) 100-500 times.

Hydrocarbon mixture, which can be desulfuricans in accordance with the present invention, contains more than 150 million hours of sulfur. For example, a hydrocarbon mixture with a sulfur content greater than 600 million hours or even above 10,000 million hours may be subject hydrodesulphurization.

Hydrocarbon mixtures, which are preferably subjected to a hydrodesulphurization, boil in the range of C 5to about 220° C, where C5refers to the boiling point of the mixture of hydrocarbons with five carbon atoms.

The catalysts of the present invention activate before using solifidianism according to known methods. In accordance with a preferred embodiment of the present invention it is possible to carry out the process of desulfurization and isomerization reactor in which the catalytic composition is divided into two layers: the first, containing a beta zeolite, and the second containing the remaining catalytic component containing a metal VI group metal of group VIII and one or more oxides as carrier.

EXAMPLE 1 - preparation of the catalyst And

1,17 g Co(NO3)2·6H2O (CoN) dissolved in 53,32 g VION at room temperature. Add 0,79 g of beta-zeolite (acid form, has the formula H+(AlO2)-·13,2 SiO2i.e. x=0, Q=H, y=13,2, w=0, with the ratio of SiO2/Al2O3=26,3 prepared in accordance with U.S. patent 3308069), which is suspended in an alcohol solution, heating to 60° C for 10 minutes. 30,33 g Al(OS4H9)3(second-piperonyl aluminum) are added to the resulting suspension, which is heated to 60° C for 20 minutes, obtaining a suspension of A1.

Used beta zeolite obtained put the m mixing 11.6 g of sodium aluminate NaAIO 2and 116 ml 2,58 N. hydroxide solution of tetraethylammonium, TEON, to the mixture was added 290,7 g Sol of silicic acid (30% SiO2, Ludox LS) with formation of a dense gel, subjected to heating in an autoclave at 150° C for 6 days with the formation of a crystalline substance, which was filtered and dried in the air. From the obtained beta-zeolite in the form containing the sodium in the amount of 2.9% based on the sodium oxide by ion exchange with a 2% aqueous solution of ammonium chloride for 48 h followed by washing and calcination (3 h at 540° (C) received beta-zeolite in acid form, almost do not contain sodium (sodium content of 0.07%).

1.66 g (NH4)6Mo7O24·4H2(Heptamolybdate ammonium EMA) is dissolved in 19,60 g (C3H7)4PONT (hydroxide of tetrapropylammonium, TRAIN, 19.2% solution) at room temperature to obtain a solution of A2 (pH 10).

Solution A2 slowly poured to suspension A1 while heating and stirring, getting a very viscous liquid which is maintained at a temperature of 80° C for 1 hour. After that, spend aging at room temperature for 21 hours, drying in a vacuum oven at a temperature of 100° C for 6 hours, calcining in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); PA is for 200° With 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to room temperature. Material properties are shown in table 1, where Asurfdenotes the surface area and Vporesdenotes the pore volume.

EXAMPLE 2 - preparation of the catalyst In

1,37 g CoN dissolved in 36,28 g VION at room temperature. Add 2,05 g of beta-zeolite of example 1, which is suspended in an alcohol solution, heating to 50° C for 10 minutes. 32,26 g Al(OS4H9)3(second-piperonyl aluminum) are added to this suspension, which is heated to 60° C for 20 minutes, obtaining a suspension of B1.

1,61 g EMA dissolved in 18,60 g TRAIN (19.2% solution) at room temperature, obtaining a solution of B2 (pH 10).

Solution B2 slowly poured to suspension B1 while heating and stirring, getting a very viscous liquid which is maintained at a temperature of 80° C for 1 hour. After that, spend aging at room temperature for 19 hours, drying in a vacuum oven at 100° C for 6 hours and calcination in a muffle furnace at temperature conditions described in example 1. Material properties are given in table 1.

EXAMPLE 3 - Preparation of the catalyst (comparative)

Comparative catalyst prepared as described in EP 748652. 1.04 g CoN dissolved in 47,16 g VION when on the th temperature. Add 1,03 g Si(OS2H5)4(tetraethylorthosilicate) and 26,53 g Al(OS4H9)3(second-piperonyl aluminum) and the mixture heated to 60° C for 10 minutes, obtaining a suspension of C1.

1.47 g EMA dissolved in 17,56 g TRAIN (19.2% solution) at room temperature, obtaining a solution of C2 (pH 11).

Solution C2 slowly poured to suspension S1 while heating and stirring, getting a very viscous liquid which is maintained at a temperature of 60° C for 1 hour. After that, spend aging at room temperature for 21 hours, drying in a vacuum oven at 100° C for 6 hours and calcination in a muffle furnace at temperature conditions described in example 1. Material properties are given in table 1.

EXAMPLE 4 - Preparation of catalyst D (comparative)

Comparative catalyst prepared as described in EP 748652. 3,30 g CoN dissolved in 47,48 g VION, with a temperature of 60° With support for 15 minutes. Add a 1.00 g of Si(OC2H5)4(tetraethylorthosilicate) and 25,10 g Al(OS4H9)3(second-piperonyl aluminum) and the mixture heated to 60° C for 15 minutes, getting the suspension D1.

3,20 g EMA dissolved in 33,00 g TRAIN (19.2% solution) at room temperature, obtaining a solution of D2 (pH 11).

The solution D2 slowly poured to suspension D1 while heating and stirring, the floor, the tea is very viscous liquid, which is maintained at a temperature of 60° C for 1 hour. After that, spend aging at room temperature for 16 hours, drying in a vacuum oven at 100° C for 6 hours and calcination in a muffle furnace under the same conditions as in example 1. Material properties are given in table 1.

EXAMPLE 5 - Preparation of catalyst E (comparative)

1.18 g CoN dissolved in 36,17 g VION at room temperature. Add to 0.63 g of industrial zeolite ZSM-5 (PQ 3070E) and suspended in an alcohol solution, heating to 50° C for 10 minutes. 30,11 g Al(OS4H9)3(second-piperonyl aluminum) are added to this suspension and the mixture is heated to 60° C for 20 minutes, obtaining a suspension E1.

1,67 g EMA dissolved in 19,41 g TRAIN (19.2% solution) at room temperature, obtaining the solution of E2 (pH 10).

Solution E2 slowly poured to a solution of E1 under heating and stirring, getting a very viscous liquid which is maintained at a temperature of 80° C for 1 hour. After that, spend aging at room temperature for 22 hours, drying in a vacuum oven at 100° C for 6 hours and calcination in a muffle furnace at the temperature shown in example 1. Material properties are given in table 1.

EXAMPLE 6 a Catalyst F(comparative)

Uses the standard industrial ka is alistar, consisting of a system based on alumina, cobalt and molybdenum. The properties of this catalyst are given in table 1.

TABLE 1
CatalystZeolite (wt.%)CoMoCo/MoAsurfVpores
  (wt.%)(wt.%)(mol.)(m2/g)(cm3/g)
And9,0 beta2,28,10,443801,10
In19,6 beta2,58,20,494651,24
-2,38,90,423600,74
D-6,818,10,614300,72
E7,4 ZSM-52,810,50,454101,05
F-3,2to 12.00,432450,51

TESTING of CATALYSTS ON the pilot DOWNLOADS

The results of the s catalysis, obtained during the processing of raw materials, defined as an experienced boot, representing a sample of the composition of gasoline FCC regarding the content S and olefinic fractions, are presented below. An experienced boot has the following composition:

- 30% (mass.) 1-penten;

- 0,25% (mass.) thiophene (1000 million hours S);

- n-hexane complements to 100.

All catalysts were activated by following the same procedure, in the stream of H2S/H2.

The catalyst activity was determined using the following options:

a) conversion of hydrodesulphurization (HDS %), calculated as:

HDS%=100x(ppm SI-mSo)/ppm SI

b) isomerizing properties ISO%, calculated as:

ISO%=100× (1-pentane + i-pentene)/Σ C5

C) hydrogenating properties, HYD %, calculated as:

HYD%=100× (n-pentaneo/1-pentenI)

EXAMPLE 6: the Catalytic activity of the catalyst And

2 g of catalyst And diluted in corundum were loaded into the reactor (40-70 mesh) and activated in the presence of H2S/H2(10% vol.) up to 400° C for 3 hours; then the system create an atmosphere of hydrogen at pressures up to 10 bar (1 MPa) and serves an experienced raw materials with respect to H2/hydrocarbon loading equal to 300 NORML/HP operating conditions and the results of the catalysis are presented in table 2.

EXAMPLE 7: the Catalytic activity of the catalyst In

2 g produce the RA were treated in the same way, as in example 6 in the part concerning the activation procedure, and then tested on the experimental loading of the operating conditions described in table 2, which also presents the results of the catalysis.

EXAMPLE 8: the Catalytic activity of catalyst D

2 g of catalyst D was treated as in example 6 in the part concerning the activation procedure, and then tested on the experimental loading of the operating conditions described in table 2, which also presents the results of the catalysis.

EXAMPLE 9: the Catalytic activity of catalyst E

2 g of catalyst E was treated as in example 6 in the part concerning the activation procedure, and then tested on the experimental loading of the operating conditions described in table 2, which also presents the results of the catalysis.

EXAMPLE 10: the Catalytic activity of the catalyst F

2 g of catalyst F was treated as in example 6 in the part concerning the activation procedure, and then tested on the experimental loading of the operating conditions described in table 2, which also presents the results of the catalysis.

TABLE 2
CatalystT°)WHSV (h.-1)HDS (%)ISO (%)HDS/HYDHYD/ISO
And 2564,384,115,52,12,6
And29510,096,914,71,7a 3.9
 
2546,691,02,51,229,9
2826,6of 92.72,50,940,4
D273a 3.988,00,71,0120,95
D290a 3.995,00,71,05127,9
E2543,3of 40.313,30,74,5
F2504,089,72,52,415,0

The catalyst in accordance with the present invention (A) increases isomerizing activity by approximately one order of magnitude compared to catalysts without zeolite, regardless of what the content of the metal was the same as in the catalyst, or twice as high in the case of catalyst D. The same is true for industrial catalysts of the and F.

Example 11

1,17 g With(NO3)2·6N2O (CoN) dissolved in 53,32 g BuOH at room temperature. Added 6.6 g of beta-zeolite (acid form with the ratio of SiO2/Al2O3=26,3 prepared in accordance with U.S. patent 3308069), which is suspended in an alcohol solution, heating to 60° C for 30 minutes, obtaining a suspension of A1.

Used beta zeolite obtained by mixing 11.6 g of sodium aluminate NaAIO2and 116 ml 2,58 N. hydroxide solution of tetraethylammonium, TEON, to the mixture was added 290,7 g Sol of silicic acid (30% SiO2, Ludox LS) with formation of a dense gel, subjected to heating in an autoclave at 150° C for 6 days with the formation of crystals, which were filtered and dried in the air. Received beta-zeolite in the form containing the sodium in the amount of 2.9% in the calculation of the sodium oxide, from which, by ion exchange with a 2% aqueous solution of ammonium chloride for 48 h followed by washing and calcination (3 h at 540° (C) received beta-zeolite in acid form, almost do not contain sodium (sodium content of 0.07%).

1.66 g (NH4)6Mo7O24·4H2O (heptamolybdate ammonium EMA) is dissolved in 19,60 g (C3H7)4PONT (hydroxide of tetrapropylammonium, TRAIN, 19.2% solution) at room temperature with obtaining races the thief A2 (pH 10).

Solution A2 slowly poured to suspension A1 while heating and stirring, getting a very viscous liquid which is maintained at a temperature of 80° C for 1 hour. After that, spend aging at room temperature for 21 hours, drying in a vacuum Cabinet at a temperature of 100° C for 6 hours and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; the cooling to room temperature.

Example 12

Prepare an aqueous solution (about 50 ml)containing 7,02 g CoN and 9,96 g EMA. This aqueous solution is impregnated with 4,74 g of beta-zeolite in acid form, having a ratio of SiO2/Al2About3=26,3 obtained in accordance with US 3308069. Then carry out the aging at room temperature for 20 h, drying in a vacuum Cabinet at 100° C for 1 hour and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°C/min); pause at 550° 3 hours; cooling to room temperature.

Example 13

Prepare an aqueous solution (about 30 ml)containing 7,02 g SOP. This aqueous solution is impregnated with 4,74 g of beta-zeolite. Then carry out the aging at whom atoi temperature for 21 h, drying in a vacuum Cabinet at 100° C for 6 hours and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to room temperature.

The calcined solid is impregnated with a solution 9,96 g EMA in water (30 ml).

Example 14

30,33 g Al(OS4H9)3(second-piperonyl aluminum) is dissolved in 53,32 g of butanol (VION) at room temperature followed by heating to 60° C for 20 minutes. Then there is added slowly 19,60 g (C3H7)MON (hydroxide of tetrapropylammonium, TRAIN, 19.2% solution) by heating and stirring to obtain a high-viscosity fluid, which is maintained at 80° C for 1 hour. Then carry out the aging at room temperature for 21 h, drying in a vacuum Cabinet at 100° C for 6 hours and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to the room temperature.

Thus obtained calcined Al2O3after mechanical mixing with 0,79 g of beta-zeolite, such as used in example 1 is impregnated with a solution of the m 1,17 g CoN in water (30 ml). Then carry out the aging at room temperature for 21 h, drying in a vacuum Cabinet at 100° C for 6 h and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to the room temperature.

The calcined product is then impregnated with a second aqueous solution (1.66 g EMA in 40 ml of water), followed by aging at room temperature for 20 h, drying in a vacuum Cabinet at 100° C for 1 hour and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5° /min); pause at 550° 3 hours; cooling to room temperature.

Example 15

2,05 g of beta-zeolite, such as used in example 1 are suspended in 36,28 g of butanol (VION) at room temperature followed by heating to 50° C for 10 minutes. To this suspension add 32,26 g Al(OS4H9)3(second-piperonyl aluminum) followed by heating to 60° C for 20 minutes; then there is added slowly 18,60 g (C3H7)4NOH (hydroxide of tetrapropylammonium, TRAIN, 19.2% solution) by heating and stirring to obtain a high-viscosity fluid is STI, which is maintained at 80° C for 1 hour. Then carry out the aging at room temperature for 19 h, drying in a vacuum Cabinet at 100° C for 6 hours and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to the room temperature.

The calcined product is then impregnated with a solution of 1.61 g of EMA in 30 ml of water, followed by aging at room temperature for 21 h, drying in a vacuum Cabinet at 100° C for 1 hour and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to room temperature.

Then the product is impregnated with a solution of 1.37 g CoN in water (30 ml). Then carry out the aging at room temperature for 21 h, drying in a vacuum Cabinet at 100° C for 6 h and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°C/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to room temperature.

When used in the methods described in examples 14 is 15, the silicon alkoxide or zirconium alkoxide, such as tetraethoxide silicon or tetraisopropoxide zirconium, instead of butoxide aluminum as the organic compounds capable of forming the oxide or oxides-carriers, can be obtained by catalytic compositions containing as carriers of silicon oxide or zirconium oxide.

Example 16

1,37 g CoN dissolved in 36,28 g VION at room temperature followed by heating to 50° C for 10 minutes. To this suspension add 32,26 g Al(OS4H9)3(second-piperonyl aluminum) followed by heating to 60° C for 20 minutes, obtaining a suspension of A1.

of 1.61 g (NH4)6Mo7O24·4H2O (heptamolybdate ammonium EMA) is dissolved in 18,60 g (C3H7)4NOH (hydroxide of tetrapropylammonium, TRAIN, 19.2% solution) at room temperature to obtain a solution of A2 (pH 10).

Solution A2 slowly poured to suspension A1 while heating and stirring to obtain a very viscous liquid, which is maintained at a temperature of 80° C for 1 hour. After that, spend aging at room temperature for 19 h, drying in a vacuum Cabinet at a temperature of 100° C for 6 hours and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pauses the 200° With 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to room temperature.

The calcined product is mechanically mixed with 2,05 g of beta-zeolite, such as used in example 1, and again calcined in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to room temperature.

Example 17

30,33 g Al(OS4H9)3(second-piperonyl aluminum) is dissolved in 53,32 g of butanol (VION) at room temperature followed by heating to 60° C for 20 minutes. Then there is added slowly 19,60 g (C3H7)4NOH (hydroxide of tetrapropylammonium, TRAIN, 19.2% solution) by heating and stirring to obtain a high-viscosity fluid, which is maintained at 80° C for 1 hour. Then carry out the aging at room temperature for 21 h, drying in a vacuum Cabinet at 100° C for 6 hours and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to the room temperature.

Thus obtained calcined Al2About3impregnate what astora 1,17 g CoN in water (30 ml). Then carry out the aging at room temperature for 21 h, drying in a vacuum Cabinet at 100° C for 6 h and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (55°/min); pause at 550° 3 hours; cooling to the room temperature.

The calcined product is then impregnated with a second aqueous solution (1.66 g EMA in 40 ml of water), followed by aging at room temperature for 21 h, drying in a vacuum Cabinet at 100° C for 6 h and calcination in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5° /min); pause at 550° 3 hours; cooling to room temperature.

The product obtained after the last annealing, mechanically mixed with 0,79 g of beta-zeolite, such as used in example 1, and again calcined in a muffle furnace under the following temperature conditions: heating to 200° (5°/min); pause (200° 2 hours; heated to 550° (5°/min); pause at 550° 3 hours; cooling to room temperature.

Example 18

Repeat the conditions of the previous example, except for the last stage of mixing beta zeolite with the product received, the tion after the second impregnation solution, drying and calcination, instead of bringing these two components of the catalytic composition used by their separate placement in the reactor in the form of two layers and carrying out Hydrotreating process in conditions similar to those described above for the other catalysts.

The presence of beta-zeolite increases conversion hydrodesulphurization HDS compared to hydrogenation properties HYD, as reflected in a larger value of the ratio of HDS/HYD, and also reduces the hydrogenation towards isomerization (lower value of the ratio HYD/ISO) compared with both formulations without zeolite (C and D) and catalyst (S)containing zeolite ZSM-5.

In addition, the catalyst in accordance with the present invention also achieves a high HDS at mild temperature (T=256° (C), in particular two times higher in comparison with catalyst E containing ZSM-5.

High value relationships HDS/HYD and low values HYD/ISO (i.e. high desulfuriza activity with reduced hydrogenation activity and high skeletal isomerization) show how the catalysts in accordance with the present invention is able to restore the loss of octane number of the hydrocarbon mixtures which are hydrodesulphurization, having boiling ranges from 35 to 250° containing olefins and at least 150 million including sulfur.

1. Catalytic composition comprising zeolite, the metal of group VIII, a metal of the VI group and possibly one or more oxides as carrier, characterized in that the zeolite used beta-zeolite.

2. The catalytic composition according to claim 1, where the beta zeolite is in the form in which the cationic centers of the zeolite is preferably occupied by hydrogen ions.

3. The catalytic composition according to claim 2, in which not less than 80% cationic centers are occupied by hydrogen ions.

4. The catalytic composition according to claim 1, containing a beta zeolite, a metal of the VI group and the metal of group VIII, in which the specified zeolite is present in an amount of 70 to 90 wt.%.

5. The catalytic composition according to claim 1, containing a beta zeolite, a metal of the VI group and the metal of group VIII and one or more metal oxides, in which the specified zeolite is present in an amount of 5 to 30% by total weight of the catalyst.

6. The catalytic composition according to claim 1, in which the metal of group VIII selected from cobalt and Nickel.

7. The catalytic composition according to claim 1, in which the metal VI group selected from molybdenum and tungsten.

8. Catalytic composition for PP and 7, in which the metal VI group is Mo and the metal of group VIII is Co.

9. The catalytic composition according to claim 1, in which the content of metal of group VIII is from 1 to 10% by total weight of the catalyst.

10. Catalytic composition for the .9, in which the content of metal of group VIII is from 2 to 6% by total weight of the catalyst.

11. The catalytic composition according to claim 1, in which the content of metal VI In the group is from 4 to 20% by total weight of the catalyst.

12. The catalytic composition according to claim 11, in which the content of metal VI In the group is from 7 to 13 wt.%.

13. The catalytic composition according to claim 1, in which the molar ratio of the metal of group VIII to the metal VI In group less than or equal to 2.

14. The catalytic composition according to item 13, in which the molar ratio of the metal of group VIII and VI metal In group less than or equal to 1.

15. The catalytic composition according to claim 1, in which the oxide or oxides used as the carrier, are the oxides of the element Z selected from silicon, aluminum, titanium, zirconium and mixtures thereof.

16. The catalytic composition according to item 15, in which an oxide selected from aluminum oxide or aluminum oxide, a mixed oxide selected from silicon oxide and zirconium oxide.

17. The method of preparation of the catalytic compositions according to claim 1, containing a beta zeolite, a metal of the VI group and the metal of group VIII, by impregnation of a beta zeolite with a solution containing a metal salt VI group and a salt of metal of group VIII, drying and calcination.

18. The method of preparation of the catalytic compositions according to claim 1, containing a beta zeolite, a metal of the VI group and the metal of group VIII, kiuchumi impregnation of the zeolite with a solution, containing metal salt VI group, and a solution containing a salt of metal of group VIII, drying and calcination.

19. The method of preparation of the catalytic compositions according to claim 1, containing a beta zeolite, a metal VI group metal of group VIII and one or more oxides as carrier, comprising mixing the zeolite with the oxide, extrusion, annealing, it is possible metabolic process, which reduces the sodium content, drying, impregnation with a solution containing a metal salt VI In groups, drying, calcination, impregnation with a solution of salt of metal of group VIII, drying and calcination.

20. The method of preparation of the catalytic compositions according to claim 1, containing zeolite, metal VI group metal of group VIII and one or more oxides as carrier, by means of Sol-gel technology as follows:

a) preparing an alcohol dispersion containing a soluble salt of metal of group VIII, a zeolite and one or more organic compounds capable of forming the oxide or oxides-media;

b) preparing an aqueous solution containing a soluble salt of the metal VI In groups and, possibly, of tetraalkylammonium hydroxide having the formula R4NOH;

C) an alcohol dispersion and the aqueous solution are mixed and get gel;

g) carry out the aging of the gel at a temperature of from 10 to 40°C;

d) the gel is dried;

(e) the gel is calcined,

characterized in that the zeolite on the operation and use of beta-zeolite.

21. The method of preparation of the catalytic compositions according to claim 1, containing a beta zeolite, a metal VI group metal of group VIII and one or more oxides as carrier, as follows:

a) preparing an alcohol dispersion containing beta zeolite and one or more organic compounds capable of forming the oxide or oxides-media;

b) preparing an aqueous solution containing of tetraalkylammonium hydroxide having the formula R4NOH;

C) an alcohol dispersion and the aqueous solution are mixed and get gel;

g) carry out the aging of the gel at a temperature of from 10 to 40°C;

d) the gel is dried;

(e) gel calcined;

g) the calcined product is impregnated with a solution containing metal salt VI group, dried, calcined, impregnated with a solution containing a salt of metal of group VIII, dried and calcined.

22. The method of preparation of the catalytic compositions according to claim 1, containing a beta zeolite, a metal VI group metal of group VIII and one or more of oxides, as follows:

a) preparing an alcohol dispersion containing a soluble salt of metal of group VIII and one or more organic compounds capable of forming the oxide or oxides-media;

b) preparing an aqueous solution containing the second soluble metal salt VI group and it is possible, of tetraalkylammonium hydroxide having the formula R4NOH;

C) an alcohol dispersion and the aqueous solution are mixed and get gel;

g) carry out the aging of the gel at a temperature of from 10 to 40°C;

d) the gel is dried;

e) carry out mechanical mixing of the dried product with beta-zeolite;

g) annealing.

23. The method according to PP, 21 or 22, wherein the salt of metal of group VIII is nitrate.

24. The method according to PP, 21 or 22, wherein the organic compound capable of forming the oxide represents the corresponding alkoxide in which the alkoxide substituents have the formula (R O)-, where R’ is an alkyl containing from 2 to 6 carbon atoms.

25. The method according to paragraph 24, wherein using the alkoxide of an element Z selected from silicon, aluminum, titanium, zirconium and mixtures thereof.

26. The method according to PP and 25, in which the use trialled having the formula (R O)3Al, where R’ is an isopropyl or sec-butyl.

27. The method according to PP and 25, in which the use tetraethoxide having the formula (R O4)Si, where R’ represents ethyl.

28. The method according to PP and 25, in which the use tetraethoxide having the formula (R O)4Zr, where R’ represents isopropyl.

29. The method according to PP, 21 or 22, wherein the soluble salt of the metal of group VI In the C the ammonium salt.

30. The method according to PP, 21 or 22, in which of tetraalkylammonium hydroxide has the formula R4NOH, where R is an alkyl group containing from 2 to 7 carbon atoms.

31. The method of preparation of the catalytic compositions according to claim 1, containing a beta zeolite, a metal VI group metal of group VIII and one or more oxides as carrier, including

a) impregnation of the oxide carrier metal salt VI group and a salt of metal of group VIII;

b) drying and calcining the material obtained in operation (a);

C) mixing the impregnated oxide obtained in operation b), with beta-zeolite.

32. The method of Hydrotreating a hydrocarbon mixtures, including the use of the catalytic composition, which contains a zeolite, a metal of group VIII, a metal of the VI group and possibly one or more oxides as carrier, characterized in that the zeolite used beta-zeolite.

33. The method according to p hydrodesulphurization of hydrocarbon mixtures having ranges of boiling points from about 35 to about 250°containing olefins and at least 150 mln sulfur, while skeletal isomerization of these olefins, including the conversion of these compounds into contact in the presence of hydrogen with a catalytic composition comprising a beta zeolite, a metal of group VIII, a metal of the VI group and possibly one or more oxides in ka is este media.

34. The method according to p carried out in the presence of a catalytic composition containing a beta zeolite, a metal VI group metal of group VIII, at temperatures from 220 to 360°C, under a pressure of from 5 to 20 kg/cm2with a bulk velocity (WHSV) of from 1 to 10 h-1with the amount of hydrogen in the 100-500 times the amount of hydrocarbons present (NORML/l).

35. The method according to clause 34, performed at a temperature of from 300 to 350°C.

36. The method according to p carried out in the presence of a catalytic composition containing a beta zeolite, a metal VI group metal of group VIII, one or more oxides as carrier, at a temperature of from 220 to 320°C, under a pressure of from 5 to 20 kg/cm3with a bulk velocity (WHSV) of from 1 to 10 h-1with the amount of hydrogen in the 100-500 times the amount of hydrocarbons present (NORML/l).

37. The method according to p carried out at a temperature of from 250 to 300°C.

38. The method according to p, in which the hydrocarbon mixture, which is subjected to desulfurization, contains more than 600 mln sulfur.

39. The method according to p carried out in the reactor in which the catalytic composition is divided into two layers - the first containing beta zeolite, and the second containing metal VI group metal of group VIII and one or more oxides as carrier.

40. The method according to p in which a hydrocarbon mixture, which is subjected to Herod is culturali, have ranges of boiling points from C5to about 220°C.



 

Same patents:

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 invention relates to the refining and can be used when cleaning the cracking of gasoline from sulfur and unsaturated compounds

The invention relates to catalysts containing on the surface of the carrier compounds of molybdenum and/or tungsten, with or without additives compounds of one or more transition metals, processes for their preparation and may find wide application in the processes of hydroperiod hydrocarbons of petroleum or coal origin
The invention relates to the refining industry, specifically to a method for diesel fuel

The invention relates to the refining and petrochemical industries, in particular to catalysts for Hydrotreating of petroleum distillates

The invention relates to a catalyst based on aluminum, which contains, calculated on the weight content of the oxide 2-10 wt.% of cobalt oxide COO, 10-30 wt.% molybdenum oxide of Moo3and 4-10 wt.% oxide of phosphorus P2ABOUT5with a surface area by BET method in the range of 100 - 300 m2/g crushing strength CSH more than 1.4 MPa and an average diameter of pores in the range of 8-11 nm, the volume of pores of diameter greater than 14 nm is less than 0.08 ml/g, volume of pores with a diameter of less than 8 nm is not more than 0.05 ml/g and a volume of pores with a diameter of 8 to 14 nm in the range 0,20 - 0,80 ml/g

FIELD: hydrocarbon conversion catalysts.

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

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

4 cl, 1 tbl, 8 ex

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

The invention relates to a process for the preparation of catalysts based on copper compounds and zinc for low-temperature conversion of carbon monoxide with water vapor and can be used in the chemical and petrochemical industry, for example, in the production of ammonia and hydrogen, the synthesis of methanol and other industries
The invention relates to the field of petrochemicals

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for the conversion of aliphatic hydrocarbons WITH2-C12in high-octane gasoline and/or aromatic hydrocarbons
Up!