Sverhchistoty catalyst and method of hydroisomerization n - paraffins with its use

 

Usage: petrochemistry. Essence: described sverhchistoty catalyst with a porosity in the range from 0.1 to 0.30 cm3/g, consisting of at least 70% of pores with a diameter in the range from 1 to 4 nm, comprising zirconium oxide, consisting of crystallites of pure tetragonal phase with a size less than 300 angstroms. On the surface of zirconium oxide are sulfate groups in an amount corresponding to the complete coating the surface of zirconium oxide by a monolayer of these sulfate groups. The catalyst was prepared by a process comprising hydrolysis able to hydrolysis derivative of zirconium in basic medium in the presence of tetraalkylammonium hydroxide (TAA), sulfuric acid and acetylacetone (ASAS); drying of the product obtained in operation (a), and calcining the dried material at a temperature in the range from 250 to 650°C; it is possible that the processing of the product obtained in operation (b), an aqueous solution of the compound of the noble metal, drying and calcination of the treated product. Spend the hydroisomerization of n-paraffins using a specified catalyst. Effect: increase the activity of the catalyst. 2 N. and 16 C.p. f-crystals, 1 Il.

This invention relative to odny metal, obtained in the presence of acetylacetone. This catalyst is effective in acid-catalyzed processes and hydroisomerization n-paraffins.

Catalysts based on sulfated oxides of zirconium, titanium, iron, having sverhkorotkimi characteristics, known in accordance with the definition Gillespie, as described, for example, K. Arata, Adv. Catal., 37, 165, 1990. These sverhchistoty catalysts are usually obtained through a well-designed synthesis, including a large number of operations. For example sulfated zirconium oxide (ZrO2/SO-24) are usually obtained in the following way:

1) the deposition of fresh hydroxide of zirconium oxide;

2) drying;

3) impregnation sulfurous agent;

4) calcination.

Operation (3) can be performed in various ways: through the point of absorption of moisture, as described in EP 520543; by processing the stream of gaseous H2S or SO2as described by J. R. shop, H. W. Kim, J. Mol. Catal., 52, (1989), 361; or by treatment in solution (R. Le Van Mao, S. Xiao T Si Le, Catal. Lett., 35, (1995), 107; D. Farcasiu, J. Qi Li, Appl. Cat. A, 128, (1995), 97). All operations of this receipt are critical: zirconium precursor, drying temperature, sulfureuse agent, the concentration ispolzuemogo proizvoditeli difficult. Recently implemented a simplified synthesis of ZrO2/SO2-4including one stage. For example, H. Arata et al. used as a precursor Zr(SO4)2(Bull. Chem. Soc. Jpn., 63, (1990), 244): this method, however, does not allow to control the sulfur content and its distribution. U. Ciesla et al. precipitated zirconium hydroxide in the presence of alkyl sulphonates or sulfonates (EUROPACAT II Congress, 3-8 September 1995). Crystallization of amorphous phase begins at very high temperatures above 650C. Other one-step method of synthesis is a method based on the transformation of the gel Zr(OS3H7)4dispersed in propanol, in an acidic environment with the help of NGO3/N2SO4. This material before calcination should be dried in supercritical conditions (D. A. Ward, E. I. Ko, J. Cat. 150, (1994), 18).

In the work of D. Tichit et al., Cat. Let., 38 (1996) 109-113, Zr(OS3H7)4dispersed in propanol, turns into a gel in the acidic environment using H2SO4. The materials obtained after calcinations at 650S, consists of a tetragonal phase with a small amount of monoclinic phase. Patent application MI97A00358 describes the catalyst sulfated oxide circus is radinovo process. This sverhchistoty catalyst comprising zirconium oxide on the surface is the presence of sulfate groups in an amount corresponding to a complete closure of the surface of zirconium oxide by a monolayer of these sulfate groups, characterized in that its porosity is in the range from 0.1 to 0.3 cm3/g and comprises at least 70% of pores with a diameter in the range from 1 to 4 nm. In accordance with a preferred aspect, the material may further comprise a noble metal, preferably platinum, in an amount in the range of from 0.1 to 3 wt.%.

These materials get through a method, which includes:

(a) hydrolysis in alkaline medium capable of hydrolysis of zirconium compounds in the presence of tetraalkylammonium hydroxide (TAA) and sulfuric acid,

(b) drying the resulting product and its calcination at a temperature in the range from 250 to 650C.

The materials obtained in operation (b), can be impregnated with a solution of the compound of the noble metal to obtain sulfated zirconium oxide, the surface of which is deposited noble metal in an amount which varies from 0.1 to 3 wt.%. The presence sverhchistoty centers in these materials was podtverjdeno.Tanabe et al., Successful Design of Catalysts, T. Inui Ed., (1988), 616, it was found that sulfated Zirconia has an intense IR band at about 1370 cm-1attributed to asymmetric stretching vibrations of S=O. Adsorption of pyridine causes a corresponding displacement signal, and the essence of this shift is associated with sverhkorotkimi material properties and their catalytic properties. The material described in MA, gives a shift in the range of from 50 to 60 cm-1compared with the maximum value, which according to the literature data is 50 cm-1.

Such catalysts based on sulfated zirconium oxide are sverhchistoty solid and, thus, can be used in acid-catalyzed reactions. If, in addition, they contain a noble metal, they are bifunctional catalysts that can be used in the process of hydroisomerization n-paraffins for the conversion of these hydrocarbons with a linear chain hydrocarbons from branched chain. In accordance with a preferred aspect, light n-paraffins are particularly prone to undergo hydroisomerization obtaining hydrocarbons from branched chain, having a higher octane number of such sulfonated zirconium oxide in the presence of acetylacetone obtained catalysts based on zirconium oxide, on the surface involving sulfate groups with improved sverhkorotkimi characteristics, and who, consequently, are more active in acid catalyzed reactions.

Thus, the present invention relates to sverhchistoty catalysts. comprising zirconium oxide on the surface is the presence of sulfate groups in an amount corresponding to a complete closure of the surface of zirconium oxide by a monolayer of these sulfate groups, having a porosity in the range from 0.1 to 0.30 cm3/g, consisting of at least 70% of pores with a diameter in the range from 1 to 4 nm, possibly containing a noble metal in an amount in the range of from 0.1 to 3 wt.%, and received by means of:

(a) hydrolysis in alkaline medium capable of hydrolysis of zirconium compounds in the presence of tetraalkylammonium hydroxide (TAA), sulfuric acid and acetylacetone;

(b) drying the resulting product and annealing it at a temperature in the range from 250 to 650;

(C) may process the received operations (b) product with an aqueous solution of a noble metal, drying and calcination.

The presence on stage of the synthesis (a) of acetylacetone (ASAS) allows to obtain a sulfonated which has been created by the acid reactions.

Operations (a) method of obtaining material for this invention of tetraalkylammonium hydroxide selected from hydroxides of the type R1R2R3R4PONT, where R1, R2, R3and R4identical or different, represent alkyl groups, preferably containing from 1 to 6 carbon atoms; capable of hydrolysis of a derivative selected from zirconium aloxiprin, nitrate, sulfate; preferably it is tetrapropylammonium. Sulfuric acid is used in the form of an aqueous solution with a concentration in the range of from 0.01 to 10 M Molar ratio in the mixture for operations (a) are as follows:

AcAc/Zr=0,00-0,5

TAA/Zr=0,05-0,25

ROH/Zr=10-100

H2SO4/Zr=0,1-0,5

H2O/Zr=2-100

In accordance with a preferred aspect, a compound of zirconium is dispersed in the alcohol ROH, where R is alkyl containing from 1 to 6 carbon atoms, preferably propanol; then to this mixture add acetylacetone, and then of tetraalkylammonium hydroxide in aqueous solution, preferably a hydroxide of tetrapropylammonium, and the resulting solution was incubated under stirring for several hours before adding a solution of sulfuric acid. Received heavy suspension, which should b) the resulting product, after the proposed concentration, dried at a temperature in the range from 80 to 150C, and then calcined at a temperature in the range from 250 to 650C, preferably from 400 to 600C.

In accordance with a preferred aspect, the catalytic material according to this invention may further comprise a noble metal, preferably platinum, in an amount in the range of from 0.1 to 3 wt.%. These catalysts are obtained by processing of the material obtained in the previous operation (b), an aqueous solution of the compound of the noble metal, drying and calcination. Preferably, the material obtained in operation (b), according to impregnate a well-known method of “uptake” aqueous solution of a compound of a noble metal, preferably platinum, with the application of the noble metal in a quantity in the range from 0.1 to 3 wt.%. For this purpose, preferably hexachloroplatinic acid and ammonium complexes of tetravalent platinum. This is followed by a drying at a temperature in the range from 80 to 150C and calcination at a temperature in the range from 400 to 600C.

The materials on this of iscsid Zirconia tetragonal modification, having a size of less than 300 angstroms, typically from 50 to 150 angstroms. The surface area of these materials exceeds 302/g, is preferably from 60 to 120 m2/, sulphate can be determined by chemical analysis and corresponds to theoretical value that can be calculated, based on the fact that the surface of the zirconium oxide is completely covered with a monolayer of sulfate groups, as described P. Nascimento et al. in "New Frontiers in Catalysis", Proceedings of the 10thInternational Congress on Catalysis (L. Guczi et al., EDS.), p.1185, Elsevier (1993). For values of surface area between the previously indicated preferred meanings, the sulfur content in the catalyst, corresponding to a monolayer of sulfate groups is from 1 to 3 wt.%.

Sulfate groups are attached to the zirconium oxide by means of hydroxyl groups on its surface, and, thus, the possibility of obtaining a monolayer of sulfate groups, which corresponds to a maximum acidity of the material, associated with the presence of a sufficient number of hydroxyl groups on the surface of zirconium oxide.

Catalysts based on sulfated zirconium oxide according to this invention are sverhkorotkimi solids that bol is utilizaton in the mixture for synthesis. They are materials that can be used in acid-catalyzed reactions and, in particular, if they additionally contain a noble metal, they are bifunctional catalysts with increased activity in the process of hydroisomerization n-paraffins for the conversion of these hydrocarbons with a linear chain hydrocarbons from branched chain, that is, they give a much higher conversion and comparable selectivity compared to the sulfonated zirconium oxide obtained without acetylacetone.

In accordance with a preferred aspect the best results possible, in particular, be obtained if light n-paraffins containing from 4 to 10 carbon atoms, subjecting hydroisomerization for obtaining hydrocarbons from branched chain, having a higher octane number, for use as fuel.

Exposing hydroisomerization C5-C6n-paraffins or a mixture obtained by distillation of light fractions in the case of direct distillation receive light gasoline with a high octane number. On the other hand, exposing hydroisomerization C6-C8n-paraffins or mixtures thereof, can be obtained heavy gasoline with a high octane number.

Redoctane between 50 and 130With, and at a pressure in the range from 0.5 to 8 MPa (5 to 80 bar, preferably from 2 to 5 MPa (20 to 50 bar). The noble metal is preferably platinum.

Space velocity (h-1), expressed in g of paraffin g of catalyst per hour, is from 0.01 to 1, and the molar ratio of hydrogen/paraffin is from 5 to 30.

In accordance with another aspect, these bifunctional catalysts can be used in the processes of hydroisomerization waxes (n-paraffins with the number of carbon atoms equal to or greater than 12) to improve temperature fluidity and viscosity index with the aim of obtaining basics of lubricating oils.

EXAMPLE 1

66 g of Zr(OS3H7)4at a concentration of 70 wt.% in propanol, 0.14 g of acetylacetone and 10 g of a hydroxide of tetrapropylammonium in the form of a 40 wt.% the aqueous solution was added to 364 g of h3H7HE. After aging for two hours with stirring, was added 50 g of 0.44 M aqueous solution of H2SO4. The mixture was kept under stirring for four hours at room temperature, and then for a further 4 hours at 60C. the Sample was dried for 8 hours at 100With, and then progulivali for 5 hours at 550

The final sulfur content determined by chemical analysis, was 1.5%, which corresponds to complete coverage of the surface by a monolayer of sulfate groups.

EXAMPLE 2

10 g of the material obtained in example 1 was impregnated by way of moisture absorption of 1.6 ml of an aqueous solution of H2PtCl6containing 0,031 g Pt in 1 milliliter.

The obtained product was dried at 100With and progulivali at 550C. the resulting catalyst with a total Pt content of 0.5 wt.%.

EXAMPLE 3

10 g of the material obtained in example 1 was impregnated by way of moisture absorption of 1.6 ml of an aqueous solution of H2PtCl6containing 0,063 g Pt Jr. on the Obtained product was dried at 100With and progulivali at 550C. the resulting catalyst with a total content of Pt 1 wt.%.

EXAMPLE 4 (comparative)

Sulfated Zirconia was obtained as described in MI97A0038: 33 g Zr(OS3H7)4in the form of a 70 wt.% solution in propanol and 5 g of a hydroxide of tetrapropylammonium in the form of an aqueous 40 wt.% solution added to 182 g n-C3H7HE. After camping left under stirring for four hours at room temperature, and then another four hours at 60C. the Sample was dried for 8 hours at 100With, and then progulivali for 5 hours at 550C. the Material obtained after calcination consisted of pure tetragonal phase, and the crystallites had a diameter of 85 angstroms, a surface area phase was 103 m2/g, pore volume - rate £ 0.162 cm3/g and the pore diameter with a maximum of 35 angstroms.

The final sulfur content determined by chemical analysis, was 1.7%, which corresponds to complete coverage of the surface by a monolayer of sulfate groups.

EXAMPLE 5 (comparative)

10 g of the material obtained in example 4 was impregnated by way of moisture absorption of 1.6 ml of an aqueous solution of H2PtCl6containing 0,031 g Pt in ml.

The obtained product was dried at 100With and progulivali at 550C. the resulting catalyst with a total content of Pt is about 0.5 wt.%.

EXAMPLE 6 (comparative)

10 g of the material obtained in example 4 was impregnated by way of moisture absorption of 1.6 ml of an aqueous solution of H2PtCl6containing 0,063 g Pt Jr. on the Obtained product was dried at 100With and progulivali at 550

A sample of catalyst, synthesized as described in example 2 was loaded into a tubular reactor with a fixed catalyst bed and tested in the reaction of hydroisomerization n-heptane under the following process conditions:

T=100

PH2=5 MPa (50 bar)

H2/n7=18 mol/mol

1/vol. speed=1-15 hours

The drawing shows the dependence of the conversion of n-heptane from the time of contact, expressed in 1/vol. speed. Parameter flow rate calculated as (g n-C7/(cat.hour). The following products hydroisomerization: methylhexane, dimethylpentane and trimethylbutane. The selectivity of hydroisomerization is over 90%.

COMPARATIVE EXAMPLE 8

Sulfated zirconium oxide containing 0.5 wt.% platinum and marked Zr1 obtained as follows. To 182 g n-C3H7HE added 33 g of Zr(OS3H7)3in the form of a 70% solution in propanol and 5 g of a hydroxide of tetrapropylammonium in the form of a 40% aqueous solution. After 2 hours of aging under stirring was added 25 g of 0.44 M aqueous solution of N2SO4. The mixture was left to mix for 4 h at room temperature, then for 4 h at 60C. the Sample was dried in racial, obtained after calcinations, consists of pure tetragonal phase with a crystallite diameter of 85 angstroms, a surface area of 103 m2/g, pore volume rate £ 0.162 cm3/g and a distribution of pore diameters around 3,5 nm. The final sulfur content determined by chemical analysis, is 1.7%, which corresponds to complete coverage of the surface by a monolayer of sulfate groups. Analysis by the method of IR-spectroscopy with Fourier transform showed a shift of 60 cm-1signal at 1370 cm-1after interaction with pyridine.

10 g of the material obtained was subjected to impregnation 1.6 ml of an aqueous solution of H2tCl6containing 0,031 g Pt in 1 ml, by way of absorption of moisture. The obtained product was dried at 100With and progulivali at 550C. Received the catalyst with a platinum content of 0.5 wt.%.

This sample was compared in the reaction of isomerization of n-heptane with a sample of sulfated zirconium oxide obtained in accordance with example 2 of this application containing the same amount of platinum and marked Zr2. Conditions for the reaction were as follows:

T = 70

PH2= 5 MPa (50 bar)

H2/n7=18 mol/mol

Vol. scorese (%) =12.

It is seen that under the same process conditions, the catalyst Zr2 corresponding to the invention, has a activity, 3 times the activity of the catalyst Zr1.

Claims

1. Sverhchistoty catalyst for reactions catalyzed by acids, in particular for hydroisomerization n-paraffins, with porosity in the range of 0.1 to 0.30 cm3/g, consisting of at least 70% of pores with a diameter in the range of 1 to 4 nm, comprising zirconium oxide, consisting of crystallites of pure tetragonal phase with a size less than 300possibly containing a noble metal in an amount in the range of 0.1 to 3 wt.%, and on the surface of zirconium oxide are sulfate groups in an amount corresponding to the complete coating the surface of zirconium oxide by a monolayer of these sulfate groups, obtained by a method that includes (a) hydrolysis able to hydrolysis derivative of zirconium in basic medium in the presence of tetraalkylammonium hydroxide (TAA), sulfuric acid and acetylacetone (ASAS); (b) drying the product obtained in operation (a), and calcining the dried material at a temperature in the range of 250 to 650°C; (b) may, product handling, Polo product.

2. The catalyst p. 1 having a surface area in the range of 60 to 120 m2/g and the weight percent sulfur based on the weight of catalyst in the range of 1 - 3%.

3. The catalyst p. 1, in which the noble metal is platinum.

4. The catalyst p. 1, in which the of tetraalkylammonium hydroxide selected from the hydroxides of the type R1R2R3R4NOH, where R1, R2, R3and R4are alkyl groups, the same or different.

5. The catalyst p. 4, in which the alkyl groups contain from 1 to 6 carbon atoms.

6. The catalyst p. 5, which of tetraalkylammonium hydroxide is a hydroxide of tetrapropylammonium.

7. The catalyst p. 1, which is capable of hydrolysis of a derivative selected from zirconium aloxiprin, nitrate, sulfate.

8. The catalyst according to p. 7, which is capable of hydrolysis derivative of zirconium is tetrapropylammonium.

9. The catalyst p. 1, in which sulfuric acid is used in the form of an aqueous solution with a concentration in the range of 0.01 - 10 M

10. The catalyst p. 1, in which the molar ratio in the mixture for operations (a) are as follows:

AcAc/Zr=0,001-0,5

TAA/Zr=0,05-0,25

ROH/Zr=10-100

H2SO4/Zr=0,1-0,5

H2O/Zr=2-1 is erachi (in) material, obtained in operation (b), impregnated according to the method of "uptake" aqueous solution of the compound of the noble metal for deposition of the noble metal in an amount of 0.1 - 3 wt.%.

12. How hydroisomerization n-paraffins, wherein the n-paraffins or a mixture of n-paraffins is brought into contact under conditions of hydroisomerization with sverhchistoty a catalyst containing a noble metal according to any one of paragraphs.1-11.

13. The method according to p. 12, characterized in that the n-paraffin wax is a paraffin having 4 to 10 carbon atoms.

14. The method according to p. 12, characterized in that it is carried out in the presence of hydrogen at a temperature in the range of 25 - 300°C, at a pressure in the range of 0.5 to 8 MPa (5 to 80 bar), flow rate (h-1), expressed in g of paraffin/g cat·h, in the range of 0.01 to 1 and a molar ratio of hydrogen:the paraffin in the range of 5 to 30.

15. The method according to p. 14, characterized in that the temperature is in the range of 50 to 130°C., and the pressure is in the range of 2 to 5 MPa (20 - 50 bar).

16. The method according to p. 12, characterized in that the n-paraffin contains 5 to 6 carbon atoms.

17. The method according to p. 12, characterized in that the n-paraffin contains 7 to 9 carbon atoms.

18. The method according to p. 12, characterized in that the n-paraffin is a wax.

 

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