Catalytic composition for sweetening hydrocarbons with boiling points within ligroin faction

 

(57) Abstract:

The present invention relates to a catalytic composition comprising zeolite ERS-10, a metal of group VIII, a metal of group VI and possibly one or more oxides as carrier. According to a preferred variant of the catalytic composition also includes metal IIB and/or IIIA group. The catalytic composition according to the present invention can be used for sweetening hydrocarbon mixtures having a temperature range of boiling in the range of C4to S, preferably hydrocarbon mixtures boiling within the boiling ligroin fraction and containing impurities of sulfur, i.e., for hydrodesulphurization with simultaneous skeletal isomerization contained in these hydrocarbons, olefins, and the whole process takes place in one stage. Also the claimed methods for the catalytic compositions by impregnation (options) and Sol-gel (options) technology, a method of desulfurization using the claimed catalyst composition and zeolite ERS-10. 8 C. and 43 C.p. f-crystals, 8 PL.

The present invention relates to catalytic compositions containing zeolite ERS-10, a metal of group VIII, a metal of group VI and, possibly, one or more metal IIB and/or IIIA group. The catalytic system according to the present invention is preferably used for refining mixtures of hydrocarbons with boiling points in the range corresponding to ligroin fraction containing sulfur-containing impurities, i.e., when hydrodesulphurization with simultaneous skeletal isomerization of olefins contained in these hydrocarbons, and the whole process is carried out in one stage. This catalytic system can be used, in particular, for manufacture of mixtures of hydrocarbons boiling in the temperature range of the boiling ligroin and fraction obtained by cracking, and preferably mixtures of hydrocarbons boiling within ligroin fraction and obtained by fluid catalytic cracking (FCC).

The hydrocarbons boiling within the boiling ligroin fractions, obtained when the FCC (i.e., a gasoline fraction), used as an integral part of gasoline. This requires that they have a high octane number and a low sulfur content and thus satisfy the existing requirements to reduce emissions of harmful substances, which are becoming tougher. Sulfur, which is part of gasoline, in fact, comes mainly (>90%) of gasoline friktsiyami for desulfurization hydrogenation processes also result in the hydrogenation of olefins and a significant decrease in the octane number (RON or MON). Thus, there is a need to develop a catalytic system for reducing the sulfur content in hydrocarbon mixtures boiling in the range of ligroin fraction and, at the same time as providing you with lower octane number (RON or MON), which can be achieved, for example, due to the skeletal isomerization of olefins present.

It is known the use of zeolites with an average pore size as catalysts for isomerization with the corresponding recovery octane mixtures have undergone desulfurization (U.S. patent 5298150, 5320742, 5326462, 5318690, 5360532, 5500108, 5510016, 5554274, 5599439). According to the above patents for holding hydrodesulphurization with reduced loss of octane number required to carry out the process in two stages with the first stage catalyst, which provides desulfurization, and the second catalyst for the restoration of the octane number.

In U.S. patent 5378352 described one-step process for desulfurization of gasoline fraction hydrocarbons using a catalyst comprising 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 or mordenite, and a metal oxide as a ligand is containing a series of metals VI and VIII groups, refractory carrier and a zeolite selected from ZSM-35, ZSM-5, mordenite or faujasite for isomerization and disproportionation of olefins is described in EP 442159, EP 437877, EP 434123; in U.S. patent 4343692 - generating units in the U.S. patent 4519900 to gidrogenizirovanii, in EP 072220 for the two-stage process, including dewaxing and hydrodesulphuration, in U.S. patent 4959140 - for two-stage hydrocracking.

The authors suddenly discovered a new catalytic system that provides a high degree of desulfurization boiling in the range of ligroin fraction of hydrocarbons containing sulfur and olefins, and simultaneous skeletal isomerization of these olefins. This new catalytic system active at temperatures and pressures lower than those preferably used for desulfurization processes.

Skeletal isomerization allows you to get the hydrocarbons boiling within ligroin faction, with a very slight reduction of the RON (research octane number) and MON (motor octane number).

The results apply not only to the desulfurization of hydrocarbons boiling within the "heavy" ligroin fraction (130-S), i.e. fra the shaft 35 is S, i.e., fractions with a high content of olefins. Indeed, the catalytic system according to the present invention has high desulfurization selectivity with respect to the hydrogenation, which gives additional benefits to increase the octane number of the final gasoline.

The present invention is a catalytic composition which comprises a zeolite ERS-10, a metal of group VIII, a metal of group VI and possibly one or more oxides as carrier.

According to a preferred variant of the present invention, the catalyst includes a metal IIB and/or IIIA group. This metal is preferably on the surface of the zeolite.

Zeolite ERS-10 is a porous crystalline material described in EP 796821, which in the calcined anhydrous form has a molecular composition of oxides corresponding to the following formula:

m m2/nO·z2O3·YO2,

where m is a number from 0.01 to 10, M - H+and/or cation of an alkaline or alkaline-earth metal with valency n, z is a number from 0 to 0.02, X is one or more elements selected from aluminium, iron, gallium, boron, vanadium, arsenic, antimony, chromium or manganese, a Y is one or more alonim spectrum (taken on a vertical goniometer with an electronic pulse counter when using Sika-radiation (=1,54178 A), contains the reflections given in table A.

M is preferably selected from sodium, potassium, hydrogen or mixtures thereof. According to a preferred variant of the invention the zeolite ERS-10 is in the acid form, i.e. in the form in which the cation vacancies zeolite, M, mostly occupied by hydrogen ions. Particularly preferably, when at least 80% of cation vacancies are filled by hydrogen ions. It is preferable to use zeolite ERS-10 based on silicon oxide and aluminium oxide, i.e., zeolite ERS-10, in which X is aluminum, a Y - silicon.

According to one aspect of the present invention in the case where the catalyst includes zeolite ERS-10 and VI and VIII metals of the groups, the contents of the specified zeolite ranges from 70 to 90%, and when the catalyst includes one or more oxides as carrier, the contents of the specified zeolite is from 5 to 30 wt.% from the total mass of the catalyst.

The catalyst according to the present invention preferably contains, as the metal of group VIII cobalt or Nickel and the group VI metal is preferably selected from molybdenum or tungsten. According to the most preferred option is used cobalt and molybdenum. Mass is) from 2% to 6%, mass fraction of the metal of group VI is preferably from 4 to 20% by weight of the total catalyst, more preferably from 7 to 13%. The mass fraction of the metal of group VI and a metal of group VIII correspond to the content of metals VI and VIII groups in the calculation of the elemental metal in the final catalyst metals VI and VIII groups are present in the form of oxides. In accordance with the most preferred molar ratio of the metal of group VIII to group VI metal is less than or equal to 2, preferably less than or equal to 1.

The oxide is used as a carrier, preferably an oxide of an element Z selected from silicon, aluminum, titanium, zirconium, or mixtures thereof. The carrier of the catalytic composition may contain one or more oxides, oxide is preferable to use aluminum oxide or a mixture of aluminum oxide with an oxide selected from silicon oxide and zirconium oxide.

When the catalyst contains a metal IIB and/or IIIA group, the contents of the specified metal in the calculation of the elemental metal is from 0.1 to 5% by weight of the total catalyst, most preferably from 0.1 to 3%. It is preferable to use zinc.

The catalytic composition according to the present invented is the lia VI group and a salt of metal of group VIII, drying and calcination. The impregnation can also be a solution containing a salt of a group VI metal, and a solution containing a salt of metal of group VIII.

By impregnation with a solution containing a salt of the metal YVES and/or IIIA groups, it is possible to prepare a catalyst containing in addition to the zeolite and metals VI and VIII groups, metal IIB and/or IIIA groups.

When the catalyst contains one or more oxides as carrier, it can be prepared by mixing the zeolite with the oxide and subsequent pressing, annealing, auxiliary metabolic process to reduce the content of sodium, drying, impregnation with a solution containing a salt of a metal of group VI, drying, calcination, impregnation with a solution of salt of metal of group VIII, drying and calcination.

According to a particularly preferred variant of the present invention the catalytic compositions containing one or more oxides as carrier, prepared by the Sol-gel technology as follows:

a) preparing an alcohol dispersion containing a soluble salt of metal of group VIII, zeolite ERS-10 and one or more organic compound capable of forming the oxide or oxides native;

b) preparing an aqueous solution, soteriaNOH;

C) an alcohol dispersion and the aqueous dispersion is mixed with a preparation of a gel;

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

d) the gel is dried;

(e) the gel is calcined.

Catalytic compositions thus obtained have a high specific surface area (>200 m2/g) and large pore volume (>0.5 cm3/g), distributed in the range of mesopores.

At the stage a) of this technology is a salt of metal of group VIII represents, for example, nitrate, hydroxide, acetate, oxalate, preferably nitrate. When it is necessary to obtain a catalyst containing a metal IIB and/or IIIA group, salt of this metal must also be present in the alcohol dispersion.

Organic substance capable of forming the oxide or oxides carrier by hydrolysis with subsequent gelation and calcination, preferably an appropriate alkoxide or alkoxides in which alkoxide the substituents have the formula (R O), where R’ is alkyl containing from 2 to 6 carbon atoms. The alkoxide is preferably an alkoxide of an element Z selected from silicon, aluminum, titanium, zirconium, or mixtures thereof; in particular, if Z is aluminum, this trialled,alkoxide, having the formula (R O)4Si, where R’ is preferably ethyl; and if Z is Zr, then this alkoxide having the formula (R O)4Zr, where R’ is preferably isopropyl.

At the stage b) as soluble salts of the group VI metal may be used acetate, oxalate or ammonium salts, preferably ammonium salt. Of tetraalkylammonium hydroxide has the formula R4NOH, where R is an alkyl group containing from 2 to 7 carbon atoms. According to a preferred variant of the solution at the stage b) also contains formamide (chemical agent regulating the drying process) that help to stabilize the porous structure during the drying process.

Amounts of reactants calculated from the composition of the final catalyst.

On stage, in) according to the preferred sequence of operations solution of stage (b) is added to a suspension of stage a).

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

Stage d) is carried out at a temperature of from 80 to 120C.

Stage e) is carried out at a temperature of from 400 to 600C.

According to another variant of the present invention a catalytic system containing one or more oxides as carrier, it is possible p is an organic compound, capable of forming the oxide or oxides native;

b) preparing an aqueous solution containing a hydroxide of tetraalkylammonium, corresponding to the formula R4NOH;

C) an alcohol dispersion and the aqueous dispersion is mixed with a preparation of a gel;

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

Amounts of reactants calculated from the composition of the final catalyst. Use the same reagents as in the case of Sol-gel technology.

According to another variant of the present invention, a catalyst containing an oxide or oxides carrier, can be prepared as follows:

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

b) preparing an aqueous solution containing a soluble salt of the metal of group VI and, possibly, of tetraalkylammonium hydroxide, corresponding to the formula R

d) the gel is dried;

(e) the dried product is mechanically mixed with the zeolite ERS-10;

g) the obtained calcined product.

Use the same reagents as in the case of Sol-gel technology.

Amounts of reactants calculated from the composition of the final catalyst.

The latter preparation is preferred for the synthesis of the catalyst according to the present invention, also containing metal IIB and/or IIIA group on the surface of the zeolite.

In this case, at the stage e) use zeolite ERS-10, on the surface by known technologies impregnation caused by metal IIB and/or IIIA group. Zeolite ERS-10, modified in this way is a new substance and is a separate subject of the present invention.

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

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

b) the material obtained in stage a), is dried and calcined;

b) impregnated oxide obtained in stage b), is mixed with the zeolite ERS-10.

Thus obtained mixture can be mixed with peptizyde acidic solution, subjected to extrusion and calcination by any known method. In another embodiment, the paste may be subjected to granulation, drying and calcination by any known technology.

The catalysts used in the method according to the present invention, can be used as such or preferably extruded by known technologist is doobogatit, which is added to the catalyst to obtain a paste, which can be ekstradiroval. In particular, when the catalysts are prepared by Sol-gel technology, the addition of the ligand in the process of extrusion is not necessary.

The materials according to the present invention can be used as catalysts for the refining of hydrocarbon mixtures boiling within ligroin faction, and, more generally, for mixtures boiling in the range from C4to S.

Thus, the present invention also is a method hydrodesulphurization of hydrocarbon mixtures having a boiling range in the interval from C4to S containing olefins and at least 150 million h (ppm) of sulfur, while skeletal isomerization of these olefins under the action of hydrogen in the presence of a catalyst containing zeolite ERS-10, a metal of group VIII, a metal of group VI and possibly one or more oxides as carrier. According to one variant of the present invention, the catalyst includes a metal IIB and/or IIIA group, preferably deposited on the surface of the zeolite.

When using a catalyst containing a zeolite ERS-10, a metal of group VI, a metal V the range from 220 to 360C, preferably between 300 and 350C, in the pressure range from 5 to 20 kg/cm2when the volumetric velocity (WHSV) of from 1 to 10 h-1. The amount of hydrogen in 100-500 times the amount of hydrocarbons present (norm.l/l).

If the catalyst includes one or more oxides as carrier, the method hydrodesulphurization with simultaneous skeletal present isomerization of olefins is carried out in a temperature range from 220 to S, preferably between 250 and S, in the pressure range from 5 to 20 kg/cm2when the volumetric velocity (WHSV) of from 1 to 10 h-1.The amount of hydrogen in 100-500 times the amount of hydrocarbons present (norm.l/l).

A mixture of hydrocarbons, which can be desulfuricans according to the present invention, contains more than 150 ppm of sulfur. For example, hydrodesulphurization may be subjected to a mixture of hydrocarbons containing more than 600 ppm or even more than 10,000 ppm of sulfur.

Hydrocarbon mixtures, which can be subjected to a hydrodesulphurization according to the present invention, is a mixture having a temperature range of from boiling4to S WITH4corresponds to the boiling temperature of the mixture of hydrocarbons, with the howling of the faction, i.e., with the interval of boiling points from C5up to 220C.

The catalysts according to the present invention before use, activate by sulfatirovnie by known methods. According to one variant of the present invention can be used for processes of desulfurization and isomerization reactor in which the catalytic composition is divided into two layers: the first, comprising the zeolite ERS-10, which may contain metal IIB and/or IIIA group and the second containing the remaining components of the catalyst including a metal of group VI, a metal of group VIII and one or more oxides as carrier.

Different ways of preparation of the catalyst according to the present invention and the results of gentrification as synthetic blends and full ligroin fractions, obtained by way of the FCC described in the examples below. All of the examples used zeolite ERS-10 in the acidic form, prepared according to example 1 of EP 796821 and had a molar ratio of SiO2/Al2O3=67.

EXAMPLE 1 - preparation of the catalyst AND

1,185 g With(NO3)2·6N2O (CON) was dissolved in 36,18 g VION at room temperature. Added 0.74 g of zeolite ERS-10, suspention9)3(sec-butyl aluminum), was heated to 80C for 20 minutes and received a suspension of A1.

1.66 g (NH4)6Mo7O24·4H2(Heptamolybdate ammonium, AMN) was dissolved in 19,41 g (C3H7)4NOH (solution containing 19.2% of the hydroxide of tetrapropylammonium) at room temperature and a solution A2 (pH 10). Solution A2 was slowly poured into the suspension A1 while heating and stirring, the obtained gel, which was kept at 80 ° C for 1 hour (pH 10). Then the gel was subjected to aging at room temperature for 22 hours, dried in a vacuum Cabinet at 100C for 6 hours, progulivali in the muffle according to the following temperature program: heating to 200C (5C/min); exposure at 200C for 2 hours; heated to S (5C/min); exposure at C within 3 hours; natural cooling to room temperature. Characterization of the obtained material are shown in table 1.

EXAMPLE 2 - preparation of the catalyst IN

1,33 g CON was dissolved in 36,19 g VION at room temperature. Added 2,05 g of zeolite ERS-10, suspended in an alcohol solution, and was heated to 60C for 10 minutes. To this suspension was added and 31.7 g of Al(OS4H9)3(sec-butyl aluminol in 19,35 g (C3H7)4PONT (the solution containing 19.2% of the hydroxide of tetrapropylammonium) at room temperature and a solution B2 (pH 10).

Solution B2 was slowly poured into the suspension B1 by heating and stirring and repeating the procedure described in example 1. Characterization of the obtained material are shown in table 1.

EXAMPLE 3 - Preparation of the catalyst WITH

6.5 g of zeolite ERS-10 was impregnated with an aqueous solution containing 1.07 g CON and 1.48 g AMN in 10,35 g of distilled N2O and having a pH of 5. The impregnated product was kept in air at room temperature for 23 hours, then dried in a Cabinet at 100C for 6 hours and was progulivali in the muffle, as described in example 1. Characterization of the obtained material are shown in table 1.

EXAMPLE 4-Preparation of catalyst D

0.88 g CON was dissolved in 33,55 g VION at room temperature. Added 0,99 g of zeolite ERS-10, suspended in an alcohol solution, and was heated to 50C for 10 minutes. To this suspension was added 28,07 g Al(OS4H9)3(sec-butyl aluminum), was heated to 60C for 20 minutes and got the suspension D1.

1.29 g of AMN (heptamolybdate ammonium) was dissolved in 8,89 g H2O if the room is Yu D1 and repeated the procedure, described in example 1. Characterization of the obtained material are shown in table 1.

EXAMPLE 5 - Preparation of catalyst E

0.74 g of zeolite ERS-10 was dispersible in 36,18 g VION and heated to 50C for 10 minutes. To this suspension was added 32,25 g Al(OS4H9)3(sec-butyl aluminum), was heated to 60C for 20 minutes and got the suspension E1.

18,81 g (C3H7)4PONT (the solution containing 19.2% of the hydroxide of tetrapropylammonium solution E2, pH 14) was slowly poured into the suspension E1 while heating and stirring, the obtained gel, which was kept at 80 ° C for 1 hour (pH 13). Then the gel was subjected to aging at room temperature for 21 hours, dried in a vacuum Cabinet at 100C for 6 hours, progulivali as in example 1. A portion of the calcined product of 7.68 g) was impregnated with a solution containing 1,185 g CON and 1.75 g AMN 10.9 g of N2On (pH 5), and then kept for 22 hours in the air.

The impregnated product was dried in a Cabinet at 100C for 6 hours and was progulivali in the muffle, as described in example 1. Characterization of the obtained material are shown in table 1.

EXAMPLE 6 - Preparation of catalyst F

1 g of zeolite ERS-10 saturated water epithany product was kept in air at room temperature for 16 hours, then dried in a Cabinet at 100C for 6 hours and was progulivali in the muffle, as described in example 1. Characterization of the obtained material containing 3.6 wt.% zinc oxide are shown in table 1.

EXAMPLE 7 - Preparation of catalyst G

1,185 g CON was dissolved in 42.5 g iPrOH at room temperature. Added 2,895 g of 70% solution of Zr(OS3H7)4(isopropylate zirconium) and 31.9 per g of Al(OS4H9)3(sec-butyl aluminum), the mixture was heated to 60C for 20 minutes and got the suspension G1.

1.66 g of AMN (heptamolybdate ammonium) was dissolved in 18,77 g (C3H7)4NOH (a solution containing 20% of the hydroxide of tetrapropylammonium) at room temperature and a solution G2, pH 11.

The G2 solution was slowly poured into the suspension G1 with stirring and heating and received the slurry, which was kept at 80 ° C for 1 hour (pH 10). Then the pulp was subjected to aging at room temperature overnight and dried in a vacuum Cabinet at 100C for 6 hours.

8 g of dried thus the catalyst is mechanically mixed in a ball mill with 3,43 g of zeolite ERS-10 and the mixture was then progulivali as in example 1. Characterization of the obtained material are shown in table 1.

2H5)4(tetraethylorthosilicate) and 29,92 g Al(OS4H9)3(sec-butyl aluminum), the mixture was heated to 60C for 20 minutes and received a suspension of N1.

1,76 g AMN (heptamolybdate ammonium) was dissolved in 18.3 g (C3H7)4NOH (a solution containing 20% of the hydroxide of tetrapropylammonium) at room temperature and a solution of H2, pH 10.

A solution of N2 was slowly poured into a suspension of N1 with stirring and heating and received the slurry, which was kept at 80 ° C for 1 hour (pH 10). Then the pulp was subjected to aging at room temperature overnight and dried in a vacuum Cabinet at 100C for 6 hours.

of 8.27 g of the dried product was mechanically mixed in a ball mill with 3,505 g of zeolite ERS-10, and the mixture was progulivali as in example 1. Characterization of the obtained material are shown in table 1.

EXAMPLE 9 - Preparation of the catalyst TO

1.04 g CON was dissolved in 47,16 g VION at room temperature. Added 1,03 g Si(OC2H5)4(tetraethylorthosilicate) and 26,53 g Al(OS4H9)3(sec-butyl aluminum), the mixture was heated to 60C for 10 minutes and got the suspension 11.

1.47 g of AMN (heptamolybdate is I) at room temperature and a solution of 12, pH 11.

Solution 12 was poured into the suspension 11, and then repeating the procedure described in example 1. Characteristics of the resulting material, called the material I presented in table 1.

Catalytic composition For mechanically mixing the product I with zeolite ERS-10 containing Zn, prepared analogously to example 6 (catalyst F). The catalytic composition To contain F in the amount of 30 wt.% from the total mass of the catalyst.

EXAMPLE 10 (comparative) Preparation of catalyst L

1.18 g CON was dissolved in 42,52 g iPrOH at room temperature. Added to 2.99 g of 70% solution of Zr(OS3H7)4(isopropylate zirconium) in iPrOH and 30 g of Al(OS4H9)3(sec-butyl aluminum), the mixture was heated to 60C for 20 minutes and received a suspension of L1.

1.66 g of AMN (heptamolybdate ammonium) was dissolved in 19,06 g (C3H7)4NOH (solution containing 19.2% of the hydroxide of tetrapropylammonium) at room temperature and a solution of L2 (pH 11).

The solution L2 was poured into a suspension of L1, and then repeating the procedure described in example 1. Characterization of the obtained material are shown in table 1.

EXAMPLE 11 (comparative) Preparation of the catalyst M

=32,3, in acidic form) suspended in this solution when heated (60C for 10 minutes, pH 7) was added 30,11 g Al(OS4H9)3(sec-butyl aluminum); the mixture was heated to 60C for 20 minutes and got the suspension M1.

1,67 g AMN (heptamolybdate ammonium) was dissolved in 19,41 g (C3H7)4NOH (solution containing 19.2% of the hydroxide of tetrapropylammonium) at room temperature and a solution M2, pH 10. The solution M2 was slowly poured into the suspension M1 while heating and stirring, the obtained gel, which was kept by heating (80 ° C for 1 hour, pH 9). Then the gel was subjected to aging at room temperature for 22 hours, dried in a vacuum Cabinet at 100C for 6 hours and was progulivali as described in example 1. Characterization of the obtained material are shown below in table 1.

TESTING of CATALYSTS FOR ARTIFICIAL MIXTURES

Below are the results obtained during testing of catalysts in a mixture called artificial corresponding to the composition of the gasoline fraction obtained by the method of the FCC, sulfur and olefins. Artificial mixture had the following composition:

30 wt.% 1-pentene;

0.25 wt.% thiophene (1000 ppm S);2
S/H2.

The catalytic activity was evaluated by the following parameters:

Degree hydrodesulphurization HDS=100(ppmSbeg-ppmSKon)/ppmSbeg.

The degree of isomerization ISO=100(i-pentane+i-penten)/C5.

The degree of hydrogenation HYD=100(n-pentaneKon/1-pentenbeg).

EXAMPLE 12: the catalytic activity of the catalyst AND

1.5 g of catalyst And diluted with corundum, loaded into the reactor (30-50 mesh) and activated in the presence of H2S/H2(10 vol.%) up to 400C for 3 hours; after that the system has created a hydrogen pressure of 10 bar was applied artificial mixture ratio hydrogen/hydrocarbons (N2/NS), equal to 300 standards.l/L. the process Conditions and the results of the catalysis are shown in table 2.

EXAMPLE 13: the catalytic activity of the catalyst IN

1.5 g of the catalyst was treated as in example 9, in part, on the activation procedure, and then tested on artificial mixture with the process conditions listed in table 2. Table 2 also shows the results of the catalysis.

EXAMPLE 14: the catalytic activity of catalyst D

1.5 g of catalyst D was treated as in example 9. Process conditions and R"ptx2">

1.5 g of catalyst E was treated as in example 9. Process conditions and results of the catalysis are shown in table 2.

EXAMPLE 16: the catalytic activity of the catalyst G

1.5 g of catalyst G was processed as in example 9. Process conditions and results of the catalysis are shown in table 2.

EXAMPLE 17: the catalytic activity of the catalyst N

1.5 g of catalyst H was treated as in example 9. Process conditions and results of the catalysis are shown in table 2.

EXAMPLE 18 - (comparative)

The catalytic activity of the catalyst I

1.5 g of catalyst I, not containing zeolite component was treated as in example 9. Process conditions and results of the catalysis are shown in table 2.

EXAMPLE 19 - (comparative)

The catalytic activity of the catalyst L

1.5 g of the catalyst L, not containing zeolite, treated as in example 9. Process conditions and results of the catalysis are shown in table 2.

EXAMPLE 20 - (comparative)

The catalytic activity of the catalyst M

1.5 g of catalyst M containing ZSM-5 as a component of the catalyst was treated as in example 9. Process conditions and results of the catalysis of previdencia, regarded as the result of a combination of variables of the process, the catalysts according to the present invention allows to obtain a much higher degree of desulfurization than catalysts with a catalytic composition comprising a zeolite other than zeolite ERS-10 (katalysator M). In particular, at low temperatures (250-S) obtained values of the degree of desulfurization at least twice as long as similar values are obtained with a catalytic composition comprising ZSM-5. At these temperatures the degree of isomerization was obtained when using catalyst M, comparable with those obtained by use of the catalysts according to the present invention, however, at higher temperatures (280-S) the degree of isomerization was obtained using katalizatorov according to the present invention, much higher than obtained when using the known catalyst containing zeolite ZSM-5. Taken for comparison catalysts I and L, not containing zeolite, provide a high degree of desulfurization, however, the degree of isomerization in their use is very low. In addition, under the same reaction conditions, catalysts according to the present invention have bol values, shown in column HYD/ISO table 2.

EXAMPLE 21: the catalytic activity of the catalyst

1.5 g of the catalyst was treated as in example 9 in part, on the activation procedure, and then tested on an artificial charge under the following process conditions:

T=S

WHSV=4,8 h-1

H2/HC=300 standards. l/l

The following results are obtained catalysis:

HDS(%): 89,4

ISO(%): 61,5

HDS/HYD: 8,6

HYD/ISO: 0,2

From the above data it follows that at high temperatures the catalyst in addition to a good ability to desulfurization demonstrates a good ability to isomerization with simultaneous low activity hydrogenation (HYD/ISO=0,2), thus preventing the decrease of the octane number in the case of desulfurization of gasoline fraction obtained by the method of the Philippine red cross.

TESTING of CATALYSTS FOR REAL MIXTURE

Below are a few examples of the action of the catalysts according to the present invention when processing a full gasoline fraction obtained by way of the FCC, the composition and characteristics of which are given in table 3.

EXAMPLE 22

1.5 g of the catalyst, R is 0C for 3 hours; the system then created a hydrogen pressure of 10 bar and loaded full of gasoline fraction obtained by the method of the FCC, the composition of which is given in table 3, when the ratio hydrogen/hydrocarbons (N2/NS) from 300 to 500 norms. l/l

The machining conditions, the results obtained, expressed as characteristics, and the composition of the gasoline are given in table 4.

EXAMPLE 23

2.2 g of the catalyst, diluted with corundum, loaded into the reactor (30 -50 mesh) and activated in the presence of N2S/N2(10 vol.%) up to 400C for 3 hours; after that the system has created a hydrogen pressure of 10 bar and download full the gasoline fraction obtained by way of the FCC, the composition of which is given in table 3, when the ratio hydrogen/hydrocarbons (N2/NS), equal to 300 standards. l/L. the process Conditions and the results are shown in table 5.

EXAMPLE 24

0.6 g ERS-10 and 1.4 g of material I have loaded in the reactor (30 - 50 mesh) in two different layers: the zeolite ERS-10 downloaded first, and the product I in the second. Zeolite ERS-10 was 30% of the total mass of the catalyst.

Activation was carried out as in the previous examples, and downloaded the FCC gasoline having the composition shown in table 3.

1,65 g catalytic composition G, diluted with corundum, loaded into the reactor (30-50 mesh) and activated in the presence of H2S/H2(10 vol.%) up to 400C for 3 hours; after that the system has created a hydrogen pressure of 10 bar and download full the gasoline fraction obtained by way of the FCC, the composition of which is given in table 3, when the ratio hydrogen/hydrocarbons (N2/NS), equal to 300 standards.l/L. the Parameters of the process and the results are shown below in table 7.

1. Catalytic composition for hydrodesulphurization of mixtures of hydrocarbons with boiling points within ligroin fractions containing zeolite ERS-10, a metal of group VIII, a metal of group VI and possibly one or more oxides as carrier.

2. The catalytic composition under item 1, additionally containing a metal IIB and/or IIIA group.

3. The catalytic composition under item 2, in which the metal IIB and/or IIIA group deposited on the surface of the zeolite.

4. The catalytic composition under item 2 or 3, in which the metal is zinc.

5. The catalytic composition under item 1 or 2, in which the zeolite ERS-10 is in the form in which the cation vacancies in the zeolite mainly filled with hydrogen ions.

7. Catalytic composition for PP.1, 2 or 5, in which the basis of zeolite ERS-10 are the oxides of silicon and aluminum.

8. Catalytic composition for p. 1 containing zeolite ERS-10, a metal of group VI and a metal of group VIII, in which the specified zeolite ranges from 70 to 90 wt.%.

9. Catalytic composition for p. 1 containing zeolite ERS-10, a metal of group VI, a metal of group VIII and one or more metal oxides, in which the specified zeolite is from 5 to 30 wt.% from the total mass of the catalyst.

10. The catalytic composition under item 1, in which the metal of group VIII selected from cobalt and Nickel.

11. The catalytic composition under item 1, in which the group VI metal is selected from molybdenum and tungsten.

12. The catalytic composition under item 10 or 11, in which the group VI metal is molybdenum, and the metal of group VIII is cobalt.

13. The catalytic composition under item 1, in which the mass fraction of the metal of group VIII is from 1 to 10% by weight of the total catalyst.

14. The catalytic composition under item 13, in which the mass fraction of the metal of group VIII is from 2 to 6% by weight of the total catalyst.

15. The catalytic composition under item 1, in which the mass fraction of the metal of group VI with the new share of the group VI metal is from 7 to 13%.

17. The catalytic composition under item 1, in which the molar ratio of the metal of group VIII and group VI metal is less than or equal to 2.

18. The catalytic composition under item 1, in which the molar ratio of the metal of group VIII and group VI metal is less than or equal to 1.

19. The catalytic composition under item 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.

20. The catalytic composition according to p. 19, in which an oxide selected from aluminum oxide or aluminium oxide is mixed with silicon oxide or zirconium oxide.

21. The composition according to p. 2, in which the content of metal IIB and/or IIIA group is from 0.1 to 5 wt.% from the total mass of the catalyst.

22. The composition according to p. 21, in which the content of metal IIB and/or IIIA group is from 0.1 to 3 wt.% from the total mass of the catalyst.

23. The method of preparation of the catalytic compositions according to p. 1 containing zeolite ERS-10, a metal of group VI and a metal of group VIII, including impregnation of the zeolite ERS-10 with a solution containing a salt of a group VI metal, and a solution containing a salt of metal of group VIII, drying and calcination.

24. The method according to p. 23, in which ispolzuesh under item 23 or 24, including impregnation with a solution of metal salt IIB and/or IIIA group.

26. The method according to p. 23, further comprising mixing the zeolite with one or more oxides as carrier, extrusion, annealing, possible metabolic process, reduce sodium, and dried before impregnation with a solution containing a salt of a metal of group VI, with additional drying and calcination prior to impregnation with a solution containing a salt of metal of group VIII, drying, and calcination.

27. The method of preparation of the catalytic compositions according to p. 1 containing zeolite ERS-10, a metal of group VI, a metal of group VIII and one or more oxides as carrier, the following Sol-gel technology: (a) preparing an alcohol dispersion containing a soluble salt of metal of group VIII, zeolite ERS-10 and one or more organic compound capable of forming the oxide or oxides carrier; b) preparing an aqueous solution containing a soluble salt of the metal of group VI and, possibly, of tetraalkylammonium hydroxide, corresponding to the formula R4NOH, where R is an alkyl group containing from 2 to 7 carbon atoms; b) an alcohol dispersion and the aqueous dispersion is mixed with a preparation of a gel; the gel is subjected to aging at a temperature of from 10 to 40 ° C; d) gel litter alcohol dispersion additionally contains a salt of the metal IIB and/or IIIA group.

29. The method of preparation of the catalytic compositions according to p. 1 containing zeolite ERS-10, a metal of group VI, a metal of group VIII and one or more oxides as carrier, as follows: (a) preparing an alcohol dispersion containing zeolite ERS-10 and one or more organic compound capable of forming the oxide or oxides carrier; b) preparing an aqueous solution containing a hydroxide of tetraalkylammonium, corresponding to the formula R4NOH, where R is an alkyl group containing from 2 to 7 carbon atoms; b) an alcohol dispersion and the aqueous dispersion is mixed with a preparation of a gel; the gel is subjected to aging at a temperature of from 10 to 40C; d) the gel is dried; (e) the gel is calcined; W) of calcined product is impregnated with a solution containing a salt of a metal of group VI, dried, calcined, impregnated with a solution containing a salt of metal of group VIII, dried and calcined.

30. The method of preparation of the catalytic compositions according to p. 1 containing zeolite ERS-10, a metal of group VI, a metal of group VIII and one or more oxides as carrier, as follows: (a) preparing an alcohol dispersion containing a soluble salt of metal of group VIII and one or more organic compound capable of forming the oxide or oxides carrier; b) prepare volnuyushie the formula, R4NOH, where R is an alkyl group containing from 2 to 7 carbon atoms; b) an alcohol dispersion and the aqueous dispersion is mixed with a preparation of a gel; the gel is subjected to aging at a temperature of from 10 to 40C; d) the gel is dried; (e) the dried product is mechanically mixed with the zeolite ERS-10; f) the obtained calcined product.

31. The method according to PP.27, 29 or 30, in which the salt of metal of group VIII is nitrate.

32. The method according to PP.27, 29 or 30, in which the organic compound, capable of forming oxide is the corresponding alkoxide, in which alkoxide groups correspond to the formula (R O), where R' is alkyl containing from 2 to 6 carbon atoms.

33. The method according to p. 32, which use the alkoxide of an element Z selected from silicon, aluminum, titanium, zirconium and mixtures thereof.

34. The method according to p. 33, in which the use trialled corresponding to the formula (R O)3Al, where R' is isopropyl or sec-butyl.

35. The method according to p. 33, in which the use tetraethoxide corresponding to the formula (R O)4Si, where R' is ethyl.

36. The method according to p. 33, in which the use tetraethoxide corresponding to the formula (R O)4Zr, where R' is isopropyl.

37. The method according to PP.27, 29 or 30, in which a water soluble salt of the metal which correspond to the formula R4NOH, where R is an alkyl group containing from 2 to 7 carbon atoms.

39. The method according to p. 30 to obtain a catalytic composition according to p. 3, in which the zeolite ERS-10 use zeolite ERS-10, on the surface of which is applied by impregnation metal IIB and/or IIIA group.

40. The method of preparation of the catalytic compositions according to p. 1 containing zeolite ERS-10, a metal of group VI, a metal of group VIII and one or more oxides as carrier, including: a) impregnation of the oxide carrier salt of a group VI metal and a salt of metal of group VIII; b) drying and calcination of the product obtained in stage a); C) mixing the impregnated oxide obtained in stage b), zeolite ERS-10.

41. Method of desulfurization of hydrocarbon mixtures having a boiling point in the range from C4to S containing olefins and at least 150 million-1sulfur, while skeletal isomerization of these olefins, comprising bringing the above-mentioned mixture in the presence of hydrogen into contact with activated by sulfatirovnie catalyst composition comprising a zeolite ERS-10, a metal of group VIII, a metal of group VI and possibly one or more oxides as carrier.

42. The method according to p. 41, in which rode the IIA group deposited on the surface of the zeolite.

44. The method according to p. 41 or 42, which is carried out in the presence of a catalytic composition containing zeolite ERS-10, a metal of group VI, a metal of group VIII and possibly metal IIB and/or IIIA group, at a temperature of from 220 to 360S, at a pressure of from 5 to 20 kg/cm2when the volumetric velocity (WHSV) of from 1 to 10 h-1when the amount of hydrogen in the 100-500 times the amount of hydrocarbons present (norm. l/l).

45. The method according to p. 44, which is carried out at a temperature of from 300 to 350C.

46. The method according to p. 41 or 42, which is carried out in the presence of a catalytic composition containing zeolite ERS-10, a metal of group VI, a metal of group VIII, one or more oxides as carrier, and possibly metal IIB and/or IIIA group, at a temperature of from 220 to S, at a pressure of from 5 to 20 kg/cm2when the volumetric velocity (WHSV) of from 1 to 10 h-1when the amount of hydrogen in the 100-500 times the amount of hydrocarbons present (norm. l/l).

47. The method according to p. 46, which is carried out at a temperature of from 250 to S.

48. The method according to p. 41, in which a mixture of hydrocarbons subjected to desulfurization, contains more than 600 million-1sulphur.

49. The method according to p. 41, which is carried out in a reactor in which the catalytic composie, and the second contains a metal of group VI, a metal of group VIII and one or more oxides as carrier.

50. The method according to p. 41, in which a mixture of hydrocarbons subjected to desulfurization, have intervals of boiling points in the range of C5up to 220C.

51. Zeolite ERS-10, on the surface of which is coated with the metal IIB and/or IIIA group.

 

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