Process for the production of phenylalkanes that use a zeolitic catalyst that is based on silica-alumina

• US 20060224030A1
• Filed: 04/05/2005
• Published: 10/05/2006
• Est. Priority Date: 04/05/2004
• Status: Active Grant

• Current Assignee: Institut Francais Du Petrole (IFP Energies Nouvelles)
• Original Assignee: Institut Francais Du Petrole (IFP Energies Nouvelles)
• Inventors: Guillon, Emmanuelle, Euzen, Patrick
• Granted Patent: US 7,297,828 B2
• Time in Patent Office: Days
• US Class Current: 585/467
• CPC Class Codes: B01J 21/12 Silica and alumina
• CPC Class Codes: B01J 2229/16 to increase the Si/Al ratio; Dealumination
• CPC Class Codes: B01J 2229/26 to stabilize the total catalyst structure
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/06 Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• CPC Class Codes: B01J 29/084 Y-type faujasite
• CPC Class Codes: B01J 35/10 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/1019 100-500 m2/g
• CPC Class Codes: B01J 35/1023 500-1000 m2/g
• CPC Class Codes: B01J 35/1038 less than 0.5 ml/g
• CPC Class Codes: B01J 35/1061 2-50 nm
• CPC Class Codes: B01J 35/108 Pore distribution
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/617 500-1000 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 35/66 Pore distribution
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/10 in the presence of water, e.g. steam
• CPC Class Codes: C07C 15/107 : having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
• CPC Class Codes: C07C 15/113 : having at least two saturated side-chains, each containing at least six carbon atoms
• CPC Class Codes: C07C 2/66 : Catalytic processes
• CPC Class Codes: C07C 2/68 : with halides
• CPC Class Codes: C07C 2521/12 : Silica and alumina
• CPC Class Codes: C07C 2523/42 : Platinum
• CPC Class Codes: C07C 2523/44 : Palladium
• CPC Class Codes: C07C 2523/46 : Ruthenium, rhodium, osmium or iridium
• CPC Class Codes: C07C 2527/12 : Fluorides
• CPC Class Codes: C07C 2529/08 : of the faujasite type, e.g. type X or Y
• CPC Class Codes: C07C 2529/18 : of the mordenite type
• CPC Class Codes: C07C 2529/70 : of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
• CPC Class Codes: C07C 6/126 : of more than one hydrocarbon

Abstract

An alkylating process for the production of at least one of 2-, 3-, 4-, 5-, and 6-phenylalkanes by alkylation of an aromatic compound with a feedstock containing at least one olefin comprising at least 9 carbon atoms per molecule, in the presence of a catalyst comprising at least one substrate based on at least a zeolite and a non-zeolitic silica-alumina matrix with a low content of macropores, whereby said matrix contains an amount of more than 5% by weight and less than or equal to 95% by weight of silica (SiO₂), whereby said process is carried out at a temperature of between 30 and 400° C., a pressure of between 0.1 and 10 MPa, an hourly volumetric flow rate of 0.50 to 200 h⁻¹, and an aromatic compound/olefin molar ratio of between 1:1 and 50:1.

Claims

1. A catalytic process for the production of at least one compound selected from the group consisting of 2-, 3-, 4-, 5-, and 6-phenylalkanes, said process comprising alkylation of an aromatic compound with a feedstock containing at least one olefin having at least 9 carbon atoms per molecule, wherein the process is conducted in the presence of a catalyst that comprises at least one substrate comprising an intimate mixture of (A) at least one zeolite or a mixture of zeolites and (B) a non-zeolitic silica-alumina matrix, said matrix containing an amount of more than 5% by weight and less than or equal to 95% by weight of silica (SiO₂), said catalyst exhibiting the following characteristics:

a mean pore diameter, measured by mercury porosimetry, encompassed between 20 and 140 Å

,

a total pore volume, measured by mercury porosimetry, encompassed between 0.1 ml/g and 0.6 ml/g,

a total pore volume, measured by nitrogen porosimetry, encompassed between 0.1 ml/g and 0.6 ml/g,

a BET specific surface area encompassed between 100 and 850 m²/g,

a packing density after calcination of more than 0.65 g/cm³,

a pore volume, measured by mercury porosimetry, encompassed in the pores with diameters of more than 140 Å

, of less than 0.1 ml/g,

a pore volume, measured by mercury porosimetry, encompassed in the pores with diameters of more than 160 Å

, of less than 0.1 ml/g,

a pore volume, measured by mercury porosimetry, encompassed in the pores with diameters of more than 200 Å

, of less than 0.1 ml/g,

a pore volume, measured by mercury porosimetry, encompassed in the pores with diameters of more than 500 Å

, of less than 0.1 ml/g,

an X-ray diffraction diagram that contains at least the main lines that are characteristic of at least one of the transition aluminas contained in the group of alpha-, rho-, chi-, eta-, gamma-, kappa-, theta- and delta-aluminas,

a pore distribution such that the ratio between volume V2, measured by mercury porosimetry, encompassed between D_mean−

30 Å and

D_mean+30 Å

, to the total mercury volume is more than 0.6, such that volume V3, measured by mercury porosimetry, encompassed in the pores with diameters of more than D_mean+30 Å

, is less than 0.1 ml/g, and such that volume V6, measured by mercury porosimetry, encompassed in the pores with diameters of more than D_mean+15 Å

, is less than 0.2 ml/g, and

wherein said process is conducted at a temperature of between 30 and 400°

C., a pressure of between 0.1 and 10 MPa, an hourly volumetric flow rate of 0.05 to 200 h<sup>−

1</sup>, and an aromatic compound/olefin molar ratio of between 1;

1 and 50;

1.

2. A process according to claim 1, wherein the aromatic compound is benzene.

3. A process according to claim 1, wherein the pore volume, measured by mercury porosimetry, encompassed in the pores with diameters of more than 500 Å

is less than 0.05 ml/g.

4. A process according to claim 1, wherein at least one zeolite is selected from the FAU-structural-type zeolites.

5. A process according to claim 4, wherein at least one zeolite is selected from the group consisting of Y zeolite and Y zeolites that have undergone a secondary treatment.

6. A process according to claim 1, wherein at least one zeolite is selected from the group consisting of mordenite, beta, NU-87 and EU-1.

7. A process according to claim 1, wherein the catalyst contains at least one hydro-dehydrogenating element that is selected from the group consisting of the noble elements of group vm and the elements of group VIB of the periodic table.

8. A process according to claim 7, wherein the catalyst comprises at least one noble element of group VIII that is selected from the group consisting of platinum, palladium and ruthenium.

9. A process according to claim 8, wherein the catalyst comprises platinum and palladium.

10. A process according to claim 7, wherein the content by mass of metals of group VIII or group VIB in metallic form or in oxide form is encompassed between 0.005 and 5% by weight.

11. A process according to claim 1, wherein the catalyst comprises at least one halogen.

12. A process according to claim 11, wherein the halogen is chlorine or fluorine.

13. A process according to claim 12, wherein the halogen is fluorine.

14. A process according to claim 11, wherein the content by mass of the halogen is encompassed between 0.5 and 10% by weight.

15. A process according to claim 1, wherein the catalyst exhibits a bed crushing value of more than 0.5 MPa.

16. A process according to claim 1, wherein the catalyst substrate exhibits an acidity that is measured by infrared tracking of the thermodesorption of the pyridine such that the B/L ratio (number of Bronsted sites/number of Lewis sites) of the silica-alumina matrix is encompassed between 0.05 and 1.

17. A process according to claim 1, wherein the non-zeolitic silica-alumina matrix comprises a single silico-aluminum zone that has an Si/Al ratio that is equal to the overall Si/Al ratio that is determined by X-ray fluorescence and is less than 2.3.

18. A process according to claim 1, wherein the non-zeolitic silica-alumina matrix comprises at least two silico-aluminum zones that have Si/Al ratios that are less than or more than the overall Si/Al ratio determined by X-ray fluorescence.

19. A process according to claim 1, wherein the reactions of alkylation and transalkylation take place in a combined reaction zone.

20. A process according to claim 19 comprising the following successive stages in the combined alkylation and transalkylation zone:

Reaction of the aromatic compound with a feedstock that contains at least one olefin (olefinic feedstock) upon contact with the catalyst that is based on silica-alumina (alkylation reaction),

Fractionation of the resultant product so as to collect separately a first fraction containing unconverted aromatic compound, a second fraction containing at least one olefin that is initially present in the feedstock (unconverted), a third fraction that contains 2-, 3-, 4-, 5- and 6-phenylalkanes, and a fourth fraction that contains at least one poly-alkylaromatic compound (or poly-alkylaromatic fraction), whereby the latter is then at least partially recycled to said reaction zone where it reacts with the aromatic compound upon contact with the catalyst, so as to be at least partially transalkylated (transalkylation reaction), and

Collection of a mixture of 2-, 3-, 4-, 5- and 6-phenylalkanes.

21. A process according to claim 20, wherein the first fraction that contains the unconverted aromatic compound is at least partially recycled to the joint reaction zone.

22. A process according to claim 20, wherein the second fraction that contains at least one unconverted olefin is at least partially recycled in the reaction zone.

23. A process according to claim 20, wherein heavy alkylaromatic compounds are removed from the recycled portion of the fourth fraction by fractionation.

24. A process according to claim 1, wherein the alkylation reaction is carried out in the presence of hydrogen.

25. A process according to claim 1, wherein the feedstock that contains at least one olefin for comprises the most part of paraffins.