Sulfur-resistant catalyst for hydrodesulfurization processes and motor fuel hydrogenation (options)

FIELD: desulfurization and hydrogenation catalysts.

SUBSTANCE: invention relates to preparing hydrodesulfurization and dearomatization catalysts useful in processes of deep purification of motor fuels from sulfur-containing compounds and aromatics. A sulfur-resistant catalyst is provided including active component deposited on porous inorganic support including montmorillonite or alumina and characterized by that support is composed of zeolite H-ZSM-5 with Si/Al atomic ratio 17-45 (80-65%) and montmorillonite or alumina (20-35%), while active component is platinum or palladium, platinum and palladium in quantities, respectively, 0.2-2.0, 0.2-1,5. and 0.4-0.2% based on the total weight of catalyst. Described is also catalyst comprising platinum (0.2-2.0%) or palladium (0.2-1.5%), or platinum and palladium (0.4-2.0%) supported by Ca or Na form of montmorillonite, and also catalyst with the same active components supported by zeolite H-ZSM-5 with Si/Al atomic ratio 17-45.

EFFECT: increased sulfur-caused deactivation resistance of catalyst at moderate temperatures and under conditions efficiency in hydrodesulfurization and aromatics hydrogenation processes.

8 cl, 4 tbl, 30 ex

 

The invention relates to the field of chemistry, namely the preparation of catalysts for hydrodesulphurization unit and dearomatization used for deep cleaning of motor fuels from sulfur-containing compounds (thiophene, benzothiophene, dibenzothiophen and others) and aromatic compounds. The temperature of the implementation of these processes is 200-400°C. the Concentration of sulfur-containing compounds in motor fuels can achieve ˜1% vol. in the calculation of the elemental sulfur, which specifies the requirement for high serologically catalysts at low temperatures.

Traditionally, processes for deep cleaning of motor fuels use two-stage process where in the first stage using Co-Mo and Ni-Mo catalysts on the basis of Al2About3spend the hydrodesulphurization unit oil fractions, in the second stage using the Pt(Pd)-containing catalysts conduct the hydrogenation of aromatic compounds.

Deep cleaning of motor fuels from sulfur-containing compounds can provide catalysts having high catalytic activity and resistance to deactivation by hydrogen sulfide. For processes hydrogenolysis of sulfur-containing compounds included in the composition of petroleum fractions, use of bimetallic Co-Mo and Ni-Mo catalysts on the basis of Al2About3. Ni-Mo catalyst is reavley high activity in the hydrogenolysis of thiophene, benzothiophene and dibenzothiophene at low partial pressure of hydrogen sulfide, but are subject to rapid deactivation at high partial pressures of hydrogen sulfide. On the other hand, Co-Mo catalyst having greater resistance to deactivation by hydrogen sulfide has a low activity in the reaction hydrodesulphurization unit. To solve these problems offers a variety of technological solutions, in particular the variation of the type and structure of the media, the nature of the active component and method of its application to the media.

U.S. patent 5686374, B 01 J 29/10, 11.11.97 describes the catalyst hydrodesulphurization unit of hydrocarbon raw materials, including metal VI and/or VIII gr, deposited on a refractory inorganic substance selected from the group comprising alumina, a mixture of aluminum oxide and silicon oxide and/or magnesium oxide and/or calcium oxide and/or zeolite, and/or zinc oxide, and, if necessary, the boron compound. The catalyst shows high activity in reactions of cracking and desulfurization and has an increased service life.

U.S. patent 6267874, 31.07.2001 describes a Hydrotreating catalyst, which uses mixed oxide aluminum-silicon carrier and an active component based on the items VIII (Co, Ni, Ru, Rh, Pd, It, Pt) and/or VI (Mo, W) group of the periodic table. In the composition of the medium can be introduced additive oxide is titanium, Zirconia, zeolite, clay. The main distinctive property of the medium is high dispersion of silicon oxide and pentecosta acidity, not less than 50 ╬╝mol/g, the Catalyst is characterized by high resistance to deactivation by hydrogen sulfide, high activity in the hydrodesulphurization unit, and displays considerable efficiency in the process of deep hydrodesulphurization unit sour hydrocarbon fuels. The catalyst shows high efficiency hydrocracking, hydrodearomatization, hydroisomerization. However, in the patent serves expensive technology synthesis kremniikarbidnoi media, in particular the use as precursors of alkoxides of silicon and aluminum, or high temperatures (40-90° (C) for carrying out the stages of co-precipitation and aging of gels in the case of using inorganic compounds of silicon and aluminum.

It is known that platinum catalysts in which the platinum is deposited on various oxide media such as aluminum oxide, silicon oxide, and others, are effective catalysts for the hydrogenation of various aromatic hydrocarbons. The main disadvantage of these catalysts is their low resistance to decontamination of sulfur-containing compounds. In addition, it is known that increasing the acidity of the medium, for example IP is use as a carrier of zeolites of different structural types, has a positive effect on serologist of platinum-containing catalysts.

In U.S. patent 4777308, C 07 C 002/24, 11.10.88 described the use in the process of hydrogenation of hydrocarbons containing sulfur compounds and nitrogen compounds, catalysts, including Pt or Pd supported on zeolite ZSM-20 or dealuminated zeolite Y. These catalysts are not susceptible to poisoning by nitrogen and sulphur.

U.S. patent 5308814, B 01 J 29/10, 03.05.94 describes a catalyst for the hydrogenation of petroleum fractions, including the media, zeolite Y, which caused platinum and palladium in an amount of 0.1-2.0 wt.% each (relative to the weight of the catalyst). The zeolite may contain 1.5 to 8 wt.% of sodium. The catalyst has a high activity in reactions of dearomatization, desulfurization, denitrification, and raises the cetane number of distillate.

Closest to the technical nature of the claimed catalyst is described in U.S. patent 4378308, B 01 J 037/02; B 01 J 035/10, 29.03.1983. The stability of the catalyst hydrodesulphurization unit, in particular the COO or NiO (2-6 wt.%) and of Moo3(8-16 wt.), deposited on Al2About3achieved by coating the surface of the catalyst hydrated mineral clays (montmorillonite, bentonite, kaolin, aluminum oxide, silicon oxide, or their mixture. The content of protective components in the range 0.1-10 wt.%.

The catalyst of the prototype is prepared by immersing industrial catalyst HDS-1441 (95 g) in a suspension of montmorillonite, bentonite, kaolin (2.375 g 86.7 g of water), hydrated for 24 hours at 180 F, or hydrosols of aluminum or silicon. The film is adsorbed on the catalyst surface for 6 hours, then dried and made red-hot at 1000 F for 10 hours. The content of the film in the catalyst is 2 wt.%.

The main disadvantage of this catalyst is the low catalytic activity in the reaction, hydrogenolysis of sulfur-containing compounds, in particular thiophene, and the lack of hydrogenating ability in relation to aromatic compounds.

The problem solved by the invention, the stability of the catalysts at moderate temperatures using them to decontamination of sulfur-containing organic compounds with simultaneous increase of their efficiency in reactions hydrodesulphurization unit and hydrogenation of aromatic compounds and lifetime of the catalyst.

This is achieved by the fact that as the carrier of the catalyst contains a zeolite with the addition of montmorillonite or aluminum oxide, in particular, zeolite H-ZSM-5 with different atomic ratio Si/Al, and as the active component is platinum and/or palladium in the following ratio, wt.%: H-ZSM-5 - 80-65, montmorillonite or hydroxy is aluminum - 20-35, platinum - 0,2-2,0%, palladium and 0.2 to 1.5% by weight of the carrier.

The total content of platinum and palladium is 0.4-2.0 % by weight of the carrier. The atomic ratio Si/Al zeolite can be varied in the range of 17-45. The catalyst contains Ca - or Na-form of montmorillonite. The catalyst mainly performed in blocks of honeycomb structure. The catalyst may be performed, for example, in the form of spherical or annular pellets.

The presence in the medium of montmorillonite increases acidity of the medium in comparison with zeolite H-ZSM-5 and the formation of finely dispersed platinum compounds (palladium) in oxidation state +δ. In addition, the structure of this carrier is characterized bidisperse distribution of pore sizes. The microporous structure of the media organized by the channels of zeolite H-ZSM-5 (5Å), mesoporous (up to 45Å) is formed at the stage of synthesis and heat treatment of the carrier and arranged pores between particles of zeolite, coated with a thin film of montmorillonite. The increasing acidity of the medium ensures the formation of fine particles of platinum in oxidation state +δthat allows to provide high catalytic activity in hydrogenation reactions of aromatic compounds (e.g. benzene and thiophene). Bimodal pore distribution media size can improve the stability of the utilizator to organic sulfur-containing compounds by limiting diffusion of large organic molecules in the pores of the zeolite H-ZSM-5, in which platinum particles flows through the activation of molecular hydrogen, participating in later in the hydrogenation of aromatic compounds. The above-described morphology of the proposed catalyst can increase the stability of the catalyst to deactivation in the presence of organic sulfur compounds, and hence the service life of the catalyst in the processes of deep cleaning of motor fuels. Described variant of the catalyst is preferred for hydrogenation processes of motor fuels.

The second variant of the inventive catalyst. As a carrier, the catalyst contains a zeolite, in particular zeolite H-ZSM-5 with different atomic ratio Si/Al, and as the active component is platinum and/or palladium in the following ratio, wt.%: platinum - 0,2-2,0, palladium 0,2-1,5, media - rest. The atomic ratio Si/Al zeolite can be varied in the range of 17-45.

The total content of platinum and palladium is 0.4-2.0 % by weight of the carrier. The catalyst may be performed, for example, in the form of spherical or annular pellets.

The third variant of the inventive catalyst. As a carrier, the catalyst contains Ca - or Na-form of montmorillonite, and as the active component is platinum and/or palladium in the following ratio, wt.%: platinum - 0,2-2,0, palladium 0,2-1,5, Eitel - the rest of it. The total content of platinum and palladium is 0.4-2.0% by weight of the carrier. The catalyst mainly performed in blocks of honeycomb structure. The catalyst may be performed, for example, in the form of spherical or annular pellets.

Among the reactions taking place during the hydrodesulphurization unit oil fractions, are the slowest reaction, hydrogenolysis of thiophene and its derivatives, because of the aromatic nature of the thiophene ring hinders the elimination of sulfur molecules. Therefore, the hydrogenolysis of thiophene and its derivatives is a common test to study the properties of the catalysts of the hydrodesulphurization unit and hydrogenation of motor fuels. The process hydrodesulphurization unit is usually carried out at temperatures of 300-400°C, hydrogen pressure of 2-10 MPa, and the ratio of partial pressures of hydrogen/feedstock, 50-150. In accordance with this selected conditions testing of catalysts.

To assess the stability of the catalysts to sulfur-containing compounds measured the activity of catalysts in the hydrogenolysis reaction (hydrodesulphurization unit) of thiophene. The activity of the catalyst in the reaction, hydrogenolysis of thiophene characterized a total conversion of thiophene (XC4H4S, %) and the observed rates of conversion of thiophene and hydrogenation of thiophene to tetrahydrothiophene (WC4H4Sand WC4H6S, mol4H4S/mo the R Me· h, respectively). Thiophene selected as model sulfur-containing compounds on the basis that the catalysts that provide high efficiency in the hydrogenation of thiophene - very small in size and very resistant to hydrogenation of sulfur-containing hydrocarbons, are active in the hydrogenation reactions of other sulfur-containing organic hydrocarbons and must possess a high resistance to sulfur-containing compounds. The tests were carried out in running the installation under the following conditions: the addition of catalyst (10 mg, initial concentration C4H4S - about 0.03. % hydrogen space velocity of the feed gas mixture to 10 cm3temperatures of 300°C and pressure of 20 ATM. Before measuring the activity of the catalyst was recovered in a stream of hydrogen at 300°C for 30 minutes

The activity of the catalysts in the reaction of hydrogenation of benzene was characterized by a total conversion of benzene to cyclohexane and Methylcyclopentane. Additionally, they studied the activity of the catalysts in the reaction of hydrogenation of benzene in the presence of thiophene (1.2 wt.% S). The tests were carried out in running the installation under the following conditions: the addition of catalyst (10 mg, the initial concentration of C6H6- About 0.03. % hydrogen space velocity of the feed gas mixture to 10 cm3temperatures of 300°and pressure - 0 bar. Before measuring the activity of the catalyst was recovered in a stream of hydrogen at 300°C for 30 minutes

The invention is illustrated by the following examples.

EXAMPLE 1 (comparative).

10 g of SiO2with a specific surface area (Sbeats) 300 m2/g, having a water-holding capacity (V) 0.85 ml/g, soaked in water holding capacity solution of hexachloroplatinic acid selected concentration. The impregnated sample dried at 110°C for 1.5 h, and then calcined at a temperature of 400°C for 4 h in air atmosphere.

The content of platinum in the catalyst is 1.0 wt.% (here and below per Pt).

EXAMPLE 2 (comparative), the prototype).

10 g of the industrial catalyst TH-70 (Example 2A, With˜3.1 wt.%, Mo˜10 wt.%, Al2About3- else) with a specific surface area (Sbeats200 m2/g and a water capacity of 0.6 cm3/g is placed in a suspension containing 0.25 g of Ca - montmorillonite in 9.1 ml of water, gidratirovannuyu at 50°C for 4 h Stirred for 6 h at room temperature. The impregnated sample dried at 110°C for 1.5 h, and then calcined at a temperature of 540°C for 6 h in air atmosphere.

The Co content in the catalyst is 3.1 wt.%, molybdenum - 9.3 wt.%. Specific surface area is 169 m2/g pore Volume is 0.58 cm3/year

EXAMPLE 3 (VA iant 1).

10 g of a block of ceramic carrier of honeycomb structure, which includes zeolite H-ZSM-5 (65 wt.%) with the atomic ratio Si/Al=17, and CA-montmorillonite (35 wt%), pre-calcined at 600°C for 4 h and having a specific surface area (Sbeats) - 265 m2/g and a water capacity of 0.28 cm3/g, soaked in water holding capacity solution of hexachloroplatinic acid selected concentration. The impregnated sample dried at 110°With the flow of air within 2 hours After the stage of drying, the catalyst was calcined at a temperature of 400°C for 4 h in air atmosphere. The content of platinum in the catalyst is 1.13 wt.%.

EXAMPLE 4 (option 1).

Similar to example 3. The difference is that for cooking take 10 g of a block of ceramic media, which includes zeolite H-ZSM-5 with an atomic ratio Si/Al=30 (Sbeats=290 m2/g, V=0.26 cm3/g).

The content of platinum in the catalyst is 1 wt.%.

EXAMPLE 5 (option 1).

Similar to example 3, but the original block of ceramic media contains zeolite H-ZSM-5 with an atomic ratio Si/Al=45 (Sbeats=250 m2/g, V=0.36 cm3/g).

The content of platinum in the catalyst is 1.06 wt.%.

EXAMPLE 6 (option 1).

Analogous to example 5, but the content of platinum in the catalyst is 1.85 wt.%.

WHEN IS EP 7 (option 1).

Similar to example 3. The difference is that for the preparation of the catalyst using the method of ion exchange medium with an aqueous solution tetraammineplatinum (II) chloride, Pt(NH3)4Cl2. For this purpose, 10 g of a block of ceramic media 65%H-ZSM-5(Si/Al=17)+35% CA - montmorillonite (Sbeats=265 m2/g, V=0.28 cm3/g) is immersed in 50 ml of an aqueous solution tetraammineplatinum chloride with the concentration of platinum 2.5 mg/ml After carrying out the ion exchange catalyst is washed with distilled water, dried and calcined at 400°C for 4 hours

The content of platinum in the catalyst is 1.65 wt.%.

EXAMPLE 8 (option 1).

Similar to example 7, but for cooking take a block of ceramic media containing zeolite H-ZSM-5 with a ratio Si/Al=30.

The content of platinum in the catalyst is 1.61 wt.%.

EXAMPLE 9 (option 1).

Similar to example 7, but for cooking take a block of ceramic media containing zeolite H-ZSM-5 with a ratio Si/Al=45.

The content of platinum in the catalyst is 1.61 wt.%.

EXAMPLE 10 (option 1).

Similar to example 5. The difference is that for cooking take 10 g of a block of ceramic media, which includes zeolite H-ZSM-5 with an atomic ratio Si/Al=45 (65 wt.%) and Na-montmorillonite (35 wt%), having a specific surface area of 220 m /g and a water capacity of V=0.4 cm3/year

The content of platinum in the catalyst is 1.26 wt.%.

EXAMPLE 11 (option 1).

Similar to example 10. The difference is that for the preparation of the catalyst using the method of ion exchange media containing H-ZSM-5 with an atomic ratio Si/Al=45 (65 wt.%) and Na-montmorillonite (35 wt%), with a water solution tetraammineplatinum chloride, Pt(NH3)4Cl2.

The content of platinum in the catalyst is 1.16 wt.%.

EXAMPLE 12 (option 1).

Similar to example 10, but for the preparation of the catalyst take a block of ceramic media containing zeolite H-ZSM-5 with a ratio Si/Al=45 (75 wt.%) mixed with 25 wt.% Na-montmorillonite (Sbeats=280 m2/g, V=0.5 cm3/g).

The content of platinum in the catalyst is 0.93 wt.%.

EXAMPLE 13 (option 1).

Similar to example 10, but for the preparation of the catalyst take a block of ceramic media containing zeolite H-ZSM-5 with a ratio Si/Al=30 and Na-montmorillonite in the ratio of 84 wt.% : 16 wt.%, (Sbeats=330 m2/g, V=0.36 cm3/g). The content of platinum in the catalyst is 0.97 wt.%.

EXAMPLE 14 (option 1).

10 g of a block of ceramic carrier of honeycomb structure, which includes zeolite H-ZSM-5 (65 wt.%) with the atomic ratio Si/Al=17, and CA-montmorillonite (35 wt%), the pre is on calcined at 600° C for 4 h and having a specific surface area (Sbeats) - 265 m2/g and a water capacity of 0.28 cm3/g, soaked in water holding capacity solution paradichlorobenzene acid (H2PdCl4specified concentration. The impregnated sample dried at 110°With the flow of air within 2 hours After the stage of drying, the catalyst was calcined at a temperature of 400°C for 4 h in air atmosphere.

The palladium content in the catalyst is 1.15 wt.%.

EXAMPLE 15 (option 1).

Similar to example 14. The difference is that for cooking take 10 g of a block of ceramic media, which includes zeolite H-ZSM-5 with an atomic ratio Si/Al=30 (Sbeats=290 m2/g, V=0.26 cm3/g).

The palladium content in the catalyst is 1.05 wt.%.

EXAMPLE 16 (option 1).

Analogous to example 14, but the original block of ceramic media contains zeolite H-ZSM-5 with an atomic ratio Si/Al=45 (Sbeats=250 m2/g, V=0.36 cm3/g).

The palladium content in the catalyst is 1.21 wt.%.

EXAMPLE 17 (option 1).

Similar to example 16. The difference is that for the preparation of the catalyst using the method of ion exchange medium with an aqueous solution tetraamminepalladium chloride Pd(NH3)4Cl2. For this purpose, 10 g of a block of ceramic media 65%H-ZSM-5(Si/Al=5) + 35% CA-montmorillonite (S beats=250 m2/g, V=0.36 cm3/g) is immersed in 50 ml of an aqueous solution tetraamminepalladium chloride with the concentration of palladium 2.5 mg/ml After carrying out the ion exchange catalyst is washed with distilled water, dried and calcined at 400°C for 4 h, the Content of palladium in the catalyst is 1.35 wt.%.

EXAMPLE 18 (option 1).

10 g of a block of ceramic carrier of honeycomb structure, which includes zeolite H-ZSM-5 (65 wt.%) with the atomic ratio Si/Al=45 and CA-montmorillonite (35 wt%), pre-calcined at 600°C for 4 h and having a specific surface area (Sbeats) - 250 m2/g and a water capacity of 0.36 cm3/g, soaked in water holding capacity solution of hexachloroplatinic acid selected concentration. The impregnated sample dried at 110°With the stream of air for 2 h and calcined at a temperature of 400°C for 4 h in air atmosphere. The sample was then impregnated on capacity solution paradichlorobenzene acid selected concentration and subjected to drying and heat treatment under similar conditions.

The content of platinum in the catalyst is 1.22 wt.%, palladium - 0.57 wt.%.

EXAMPLE 19 (option 1).

Analogous to example 18. The difference is that the content of platinum in the catalyst is 1.22 wt.%, palladium - 0.25 wt.%.

EXAMPLE 0 (option 1).

Analogous to example 18. The difference is that for the preparation of the catalyst using the method of ion exchange with solutions tetraammineplatinum chloride and tetraamminepalladium chloride. For this purpose, 10 g of a block of ceramic media 65%H-ZSM-5(Si/Al=45) + 35% CA-montmorillonite (Sbeats=250 m2/g, V=0.36 cm3/g) is immersed in 50 ml of an aqueous solution tetraammineplatinum chloride with the concentration of platinum 2.5 mg/ml After carrying out the ion exchange catalyst is washed with distilled water, dried and calcined at 400°C for 4 hours the sample was Then immersed in 50 ml of an aqueous solution tetraamminepalladium chloride with the concentration of palladium 2.5 mg/ml After carrying out the ion exchange catalyst is washed with distilled water, dried and calcined at 400°C for 4 hours

The content of platinum in the catalyst is 0.94 wt.%, palladium - 1.16 wt.%.

EXAMPLE 21 (option 2).

10 g of the zeolite powder with the structure of H-ZSM-5 and the atomic ratio Si/Al=45, pre-calcined at 550°C for 4 h and having a specific surface area (Sbeats) - 380 m2/g and a water capacity of 1.0 cm3/g, soaked in water holding capacity solution of hexachloroplatinic acid selected concentration. The impregnated sample dried at 110°With the flow of air within 2 hours After the stage of drying, the catalyst was calcined at te is the temperature of 400° C for 4 h in air atmosphere. The content of platinum in the catalyst is 1.22 wt.%.

EXAMPLE 22 (option 2).

Similar to example 21. The difference is that for the preparation of the catalyst using the method of ion exchange medium with an aqueous solution tetraammineplatinum chloride Pt(NH3)4Cl2. For this purpose, 10 g of powder of zeolite H-ZSM-5 (Si/Al=45) immersed in 50 ml of an aqueous solution tetraammineplatinum chloride with the concentration of platinum 2.5 mg/ml After carrying out the ion exchange catalyst is washed with distilled water, dried and calcined at 400°C for 4 hours

The content of platinum in the catalyst is 1.22 wt.%.

EXAMPLE 23 (option 3).

10 g of the powder of CA-montmorillonite, pre-calcined at 550°C for 4 h and having a specific surface area (Sbeats) - 23 m2/g and a water capacity of 0.12 cm3/g, soaked in water holding capacity solution of hexachloroplatinic acid selected concentration. The impregnated sample dried at 110°With the flow of air within 2 hours After the stage of drying, the catalyst was calcined at a temperature of 400°C for 4 h in air atmosphere.

The content of platinum in the catalyst is 0.51 wt.%.

EXAMPLE 24 (option 3).

Analogous to example 23. The difference is that for the preparation of the catalyst using the method of ion exchange is osites with an aqueous solution tetraammineplatinum chloride Pt(NH 3)4Cl2. For this purpose, 10 g of powder of CA-montmorillonite immersed in 50 ml of an aqueous solution tetraammineplatinum chloride with the concentration of platinum 2.5 mg/ml After carrying out the ion exchange catalyst is washed with distilled water, dried and calcined at 400°C for 4 h, the Content of platinum in the catalyst is 0.12 wt.%.

EXAMPLE 25 (option 1).

10 g of a block of ceramic carrier of honeycomb structure, which includes zeolite H-ZSM-5 (65 wt.%) with the atomic ratio Si/Al=45 γ-Al2About3(35 wt%), pre-calcined at 600°C for 4 h and having a specific surface area (Sbeats) - 304 m2/g and a water capacity of 0.43 cm3/g, soaked in water holding capacity solution of hexachloroplatinic acid selected concentration. The impregnated sample dried at 110°With the flow of air within 2 hours After the stage of drying, the catalyst was calcined at a temperature of 400°C for 4 h in air atmosphere. The content of platinum in the catalyst is 1.91 wt.%.

EXAMPLE 26 (option 1).

10 g of a block of ceramic carrier of honeycomb structure, which includes γ-Al2O3(Sbeats=180 m2/g, 65 wt.%) and CA - montmorillonite (35 wt%), pre-calcined at 600°C for 4 h and having a specific surface area (Sbeats) - 160 m2/g and water is technology 0.35 cm 3/g, soaked in water holding capacity solution of hexachloroplatinic acid selected concentration. The impregnated sample dried at 110°With the flow of air within 2 hours After the stage of drying, the catalyst was calcined at a temperature of 400°C for 4 h in air atmosphere. The content of platinum in the catalyst is 0.87 wt.%.

EXAMPLE 27 (option 1).

10 g of a block of ceramic carrier of honeycomb structure, which includes SiO2(Aerosil-350, Sbeats=350 m2/g, 65 wt.%) and CA-montmorillonite (35 wt%), pre-calcined at 600°C for 4 h and having a specific surface area (Sbeatsis 195 m2/g and a water capacity of 0.78 cm3/g, soaked in water holding capacity solution of hexachloroplatinic acid selected concentration. The impregnated sample dried at 110°With the flow of air within 2 hours After the stage of drying, the catalyst was calcined at a temperature of 400°C for 4 h in air atmosphere. The content of platinum in the catalyst is 0.92 wt.%.

EXAMPLE 28 (option 1).

10 g of a block of ceramic carrier of honeycomb structure, which includes zeolite NaY (Si/Al=3.3, Na - 5.3 wt.%, Sbeats=200 m2/g, 65 wt.%) and CA - montmorillonite (35 wt%), pre-calcined at 600°C for 4 h and having a specific surface area (Sbeatsto 120 m2/g and plague the bone 0.44 cm 3/g, soaked in water holding capacity solution of hexachloroplatinic acid selected concentration. The impregnated sample dried at 110°With the flow of air within 2 hours After the stage of drying, the catalyst was calcined at a temperature of 400°C for 4 hours in air atmosphere. The content of platinum in the catalyst is 0.80 wt.%.

EXAMPLE 29 (option 2).

10 g of the zeolite powder with the structure of H-ZSM-5 and the atomic ratio Si/Al=45, pre-calcined at 550°C for 4 h and having a specific surface area (Sbeats) - 380 m2/g and a water capacity of 1.0 cm3/g, soaked in water holding capacity solution paradichlorobenzene acid selected concentration. The impregnated sample dried at 110°With the flow of air within 2 hours After the stage of drying, the catalyst was calcined at a temperature of 400°C for 4 h in air atmosphere. The palladium content in the catalyst is 0.88 wt.%.

EXAMPLE 30 (option 2).

Analogous to example 27. The difference is that for the preparation of the catalyst using the method of ion exchange medium with an aqueous solution tetraamminepalladium chloride Pd(NH3)4Cl2. For this purpose, 10 g of powder of zeolite H-ZSM-5 (Si/Al=45) immersed in 50 ml of an aqueous solution tetraamminepalladium chloride with the concentration of palladium 2.5 mg/ml After carrying out the ion exchange can produce the R washed with distilled water, dried and calcined at 400°C for 4 h, the Content of palladium in the catalyst is 1.22 wt.%.

In tables 1 and 2 presents data on the catalytic activity of platinum and/or palladium catalysts based on zeolite-containing block media cell patterns in the reactions of conversion of thiophene (XC4H4S,%; W, mole, s4H4S/mol Pt·the hours; the ratio of C4H10/C4H8S): 1) hydrogenolysis of thiophene to C4-hydrocarbons and hydrogen sulfide; and (2) hydrogenation to tetrahydrothiophene (teofane).

From tables 1 and 2 shows that according to the invention, the total conversion of thiophene achieved on Pt and/or Pd-containing catalysts based media (65-84% H-ZSM-5 and 16-35% montmorillonite), regardless of silicate module zeolite and cationic forms of montmorillonite, close to or even exceeds the conversion of thiophene, which is on industrial Pt-containing sample (sample No. 1), and significantly higher than in the comparative Co-Mo-containing sample (sample No. 2)prepared in conditions close to one of the examples described in the prototype.

From the data of tables 1 and 2 also shows that regardless of silicate module zeolite and cationic forms of montmorillonite, Pt-containing catalysts (examples No. 3-13) based media (65-84% H-ZSM-5 and 16-35% montmorillonite), including modified dobavlialsea (examples No. 18 and 20), are more active in the reactions of conversion of thiophene compared with Pd-containing catalysts on the same media (examples No. 14-17). It should be noted that the bimetallic Pt-Pd-containing catalysts (examples No. 18 and 20) provide both high hydrogenating ability in relation to the sulfur-containing compound, in particular, thiophene, and high reactivity toward hydrogenolysis of thiophene (ratio4H10/Tofana varies in the range 0.53-1.2),

From table 1 it is seen that according to the invention the increase in the content of montmorillonite in the composition of the medium (16 wt.% up to 35 wt.%) leads to the decrease of the ratio With4H10/Tofana (products of complete and incomplete hydrogenolysis of thiophene, 0.59 to 0.43, examples No. 10, 12 and 13), indicating increased hydrogenating ability of the catalyst relative to the sulfur-containing compounds.

From table 1 it is seen that according to the invention used as a precursor of the active component of hexachloroplatinic acid helps to achieve higher correlations With4H10/Tofana (0.28-0.43, examples No. 3-6 and 10), compared with samples, for which synthesis was used tetraammineplatinum chloride (C4H10/Tofana = 0.22-0.24, examples No. 7-9, 11).

Table 2 shows that according invented the Yu use as a precursor of the active component paradichlorobenzene acid contributes to the achievement of lower correlations With 4H10Tofana (0.4-0.68, examples No. 14-16 and 18, 19), compared with samples, for which synthesis was used tetraamminepalladium chloride (C4H10/Tofana = 1.2-1.6, samples No. 17 and 20).

Table 3 summarizes the activity of the samples (sample No. 21-24, 29-30), for synthesis which used media containing only one component: zeolite or montmorillonite. From table 3 it can be seen that according to a variant of the invention, the total conversion of thiophene and the speed of its transformation, achieved on Pt and/or Pd-containing catalysts based media H-ZSM-5, close to the conversion of thiophene obtained on Pt and/or Pd - containing samples (samples No. 3-20) based media (65-84% H-ZSM-5 and 16-35% montmorillonite).

Table 3 shows data on the activity of the sample (sample No. 25), for synthesis which used the media, instead of montmorillonite containing alumina (γ-Al2About3). Shows that ceteris paribus synthesis using aluminum oxide instead of Ca-montmorillonite (see example No. 25 and No. 6) leads to the decrease of catalytic activity in the reaction hydrogenolysis of thiophene, in the reaction of hydrogenation of thiophene, while there is an increase in the ratio With4H10/C4H8S twice (from 0.33 to 0.63).

Table 3 shows data on the activity of the samples (sample No. 26-8), for synthesis which used the media, instead of containing zeolite H-ZSM-5 zeolite another brand, in particular NaY with Si/Al=3.3, or Al2About3or SiO2. From the data of table 3 shows that ceteris paribus synthesis using oxide compounds of aluminum and/or silicon instead of zeolite H-ZSM-5 (see example No. 26-28 and No. 3-5) leads to decreased activity of the Pt-containing catalysts in the reactions of thiophene hydrodesulphurization unit. The increase in the content of aluminum oxide in the composition of the medium (see example No. 26-28) leads to an increase in the total activity of the catalyst in the reactions hydrodesulphurization unit and contributes to its moisturizing ability, which is accompanied by a decrease in the ratio With4H10/C4H8S 0.99-1.02 to 0.4.

Table 4 presents data on the activity of a number of catalysts in the reaction of hydrogenation of benzene, including in the presence of thiophene. From table 4 it is seen that according to the invention, the conversion of benzene formed on Pt-containing catalysts (examples No. 3-5) based on the media (65-84% H-ZSM-5 and 16-35% montmorillonite), approximate conversion of benzene reached on industrial Pt-containing sample (sample No. 1), and significantly higher than in the comparative Co-Mo-containing sample (sample No. 2)prepared in conditions close to one of the examples described in the prototype. The kata is isatori proposed composition (sample No. 3-5) provide substantially higher conversion of benzene in the presence of thiophene (18-25%), that indicates their high resistance to decontamination of sulfur-containing compounds, in particular thiophene.

Thus, according to the invention may provide a high activity of Pt and/or Pd-containing catalysts of the proposed composition of the hydrogenation reactions of aromatic compounds, including themselves sulfur-containing compounds, in particular thiophene, and the high stability of the catalyst to deactivation relative to the thiophene. Thus the variation of the ratio of Pt/Pd and zeolite/montmorillonite allows you to adjust hydrogenating and gidroobesserivaniya the ability of the catalyst relative to the sulfur-containing compounds.

Table 1

Catalyst composition and activity in the hydrogenolysis reaction (hydrodesulphurization unit) thiophene
ExampleThe composition of the mediaThe content of Pt(Pd), wt.% PredecessorConversion (X %) and the rate of conversion of thiophene (W, mole, s4H4S/mol Pt·h) at 300°With (initial/stationary conditions) reactions
C4H4S+H2→hydrogenolysis (C4H10+H2S)+hydrogenation (C4H8S) C4H4S+2H2→C4H8S
XC4H4SWC4H10/C4H8SXC4H8SW
1SiO21%, H2PtCl646/4418150.300/24985
2ATH-70 (3%, 10% Mo)-28/2557Only With4H1000
2Himself/TH-70 (3%, 9.3%Mo)-16/1014Only With4H1000
365%H-ZSM-5-17* +35%Ca-M**1.13%, H2PtCl649/4035000.3012/201690
465%H-ZSM-5-30+35%Ca-M1.0%, H2PtCl638/3329000.3014/232050
565%H-ZSM-5 to 45+35%Ca-M1.06%, H2PtCl650/3531000.2812/211860
665%H-ZSM-5 to 45+35%Ca-M1.85%, H2PtCl6 48/4521900.335/241190
765%H-ZSM-5-17+35%Ca-M1.65%, Pt(NH3)4Cl257/4124000.228/221300
865%H-ZSM-5-30+35%Ca-M1.61%, Pt(NH3)4Cl260/4325900.238/241400
965%H-ZSM-5 to 45+35%Ca-M1.61%, Pt(NH3)4Cl252/4017600.249/20870
1065%H-ZSM-5 to 45+35%Na-M1.26%, H2PtCl643/2510900.4317/17740
1165%H-ZSM-5 to 45+35%Na-M1.16%, Pt(NH3)4Cl241/2411200.2418/221000
1275%H-ZSM-5-45+25%Na-M0.93%, H2PtCl642/3217450.5314/201095
1384%H-ZSM-5-30+16%Na-M0.97%, H2PtCl634/2412800.5914/16885
* the Vedeno designation zeolites: cation (N) - structural type zeolite (ZSM-5) is the atomic ratio Si/Al (17)
** CA (or Na) - any form of montmorillonite

Table 2

Catalyst composition and activity in the hydrogenolysis reaction (hydrodesulphurization unit) thiophene (Content of platinum and palladium indicated in the examples)
ExampleThe composition of the mediaThe content of Pt(Pd), wt.% PredecessorConversion (X %) and the rate of conversion of thiophene (W, mol C4H4S/mol Pt-Pd·h) at 300°With (initial/stationary conditions) reactions
C4H4S+H2→hydrogenolysis (C4H10+H2S)+hydrogenation (C4H8S)C4H4S+2H2→C4H8S
X4H4SWC4H10/C4H8SXC4H8SW
1465%H-ZSM-5-17+35%Ca-M1.15%,H2PdCl429/217300.689/12420
1565%H-ZSM-5-30+35%Ca-M 1.05%,H2PdCl444/145300.464/11420
1665%H-ZSM-5 to 45+35%Ca-M1.21%,H2PdCl435/185800.415/13422
1765%H-ZSM-5 to 45+35%Ca-M1.35%,Pd(NH3)4Cl241/255201.616/8175
1865%H-ZSM-5 to 45+35%Ca-M1.22%,H2PtCl6, 0.57%, H2PdCl441/258350.663/12402
1965%H-ZSM-5 to 45+35%Ca-M1.22%,H2PtCl6, 0.25%, H2PdCl433/207570.537/15563
2065%H-ZSM-5 to 45+35%Ca-M0.94%, Pt(NH3)4Cl2,

1.16%,Pd(NH3)4Cl2
52/367751.22/12262

Table 3

Composition and activity in the hydrogenolysis reaction (hydrodesulphurization unit) thiophene (platinum concentration indicated in the examples)
ExampleThe composition of the mediaSod is neigh Pt(Pd), wt.% PredecessorConversion (X %) and the rate of conversion of thiophene (W, mol C4H4S/mol Pt·h) at 300°With (initial/stationary conditions) reactions
C4H4S+H2→hydrogenolysis (C4H10+H2S)+hydrogenation (C4H8S)C4H4S+2H2→C4H8S
XC4H4SWC4H10/C4H8SX4H8SW
21H-ZSM-5-451.22%, H2PtCl658/4636600.2311/292355
22H-ZSM-5-451.22%, Pt(NH3)4Cl262/5031000.3821/271660
23CaM0.51%, H2PtCl630/67000.050/6700
24CaM0.12%, Pt(NH3)4Cl237/1267900.080/94940
25(65%H-ZSM-5 to 45+35%Al2O3)1.91%, N2PtCl636/267100.67-0.713/14380
26(65%Al2O3+35%Itself)0.87%, N2PtCl633/2213450.412/12760
27(65%SiO2+35%CaM)0.92%, H2PtCl623/167600.99-1.024/7330
28(65%NaY+35%CaM)0.80%, H2PtCl623/1810450.636/9510
29H-ZSM-5-450.88%, H2PdCl434/226451.204/9270
30H-ZSM-5-451.22%Pd(NH3)4Cl248/317201.046/14325

Table 4

The catalyst composition and the activity in the reaction of hydrogenation of benzene (Content of platinum and palladium indicated in the examples)
ExampleThe composition of the mediaThe content of Pt(Pd), wt.% PR is sestonic Conversion of benzene (X, %) in hydrogenation reactions at 300°
without C4H4Swith C4H4S
1SiO21.0%, H2PtCl61002
2ATH-70 (3.1%, 10% Mo)-8-
2CaM/ST-70 (3.1%, 9.3% Mo)-100
365%H-ZSM-5-17*+35%Ca-M**1.13%, H2PtCl610025
465%H-ZSM-5-30+35%Ca-M1.0%, H2PtCl610018
565%H-ZSM-5 to 45+35%Ca-M1.06%, H2PtCl610025
1465%H-ZSM-5-17+35%Ca-M1.15%, H2PdCl4803
1565%H-ZSM-5-30+35%Ca-M1.05%, H2PdCl41005
1665%H-ZSM-5 to 45+35%Ca-M1.21%, H2PdCl4391

1. Serologically catalyst for processes hydrodesulphurization unit and hydrogenation motor that is Liv, includes active component deposited on a porous inorganic carrier, including montmorillonite or aluminum oxide, characterized in that as the media it contains zeolite H-ZSM-5 with an atomic ratio Si/Al constituting 17-45, when the mass ratio, wt.%: zeolite 80-65, montmorillonite or aluminum oxide 20-35, as the active component is platinum and/or palladium in the following ratio, wt.%: platinum 0,2-2,0 or palladium 0.2 to 1.5, or platinum and palladium 0,4-2,0, media - rest.

2. The catalyst according to claim 1, characterized in that it contains Ca - or Na-form of montmorillonite.

3. The catalyst according to claim 1, characterized in that it is made in the form of blocks of cellular structure.

4. Serologically catalyst for processes hydrodesulphurization unit and hydrogenation of motor fuels, including active component deposited on a porous inorganic carrier, characterized in that as the media it contains zeolite H-ZSM-5 with an atomic ratio Si/Al constituting 17-45, and as the active component is platinum and/or palladium in the following ratio, wt.%: platinum 0,2-2,0 or palladium 0.2 to 1.5, or platinum and palladium 0,4-2,0, zeolite - rest.

5. Serologically catalyst for processes hydrodesulphurization unit and hydrogenation of motor fuels, including active component deposited on a porous neorg the technical media, characterized in that in the media it contains Ca - or Na-form of montmorillonite, and as the active component is platinum and/or palladium in the following ratio, wt.%: platinum 0,2-2,0 or palladium 0.2 to 1.5, or platinum and palladium 0,4-2,0, montmorillonite - rest.

6. The catalyst according to claim 5, characterized in that it is made in the form of blocks of cellular structure.

7. The catalyst according to claim 5, characterized in that the carrier may additionally contain aluminum oxide at a mass ratio of components, wt.%: aluminum oxide 65, montmorillonite 35.

8. The catalyst according to claim 5, characterized in that the carrier may contain additional silicon oxide at a mass ratio of components, wt.%: the silicon oxide 65, montmorillonite 35.



 

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