Hydrocarbon conversion catalyst composition

• US 10,449,525 B2
• Filed: 10/20/2011
• Issued: 10/22/2019
• Est. Priority Date: 10/25/2010
• Status: Active Grant

• Current Assignee: Shell USA Incorporated (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Domokos, Laszlo, Huve, Laurent Georges, Jongkind, Hermanus, Klazinga, Aan Hendrik, Rigutto, Marcello Stefano
• Primary Examiner(s): Wood, Elizabeth D
• Application Number:
  US13/881,058
• Publication Number:
  US 20140209506A1
• Time in Patent Office: 2,924 Days
• Field of Search: 502 64, 502 66, 502 67, 208133, 208135, 208137, 208138, 585477, 585480, 585481, 585482
• CPC Class Codes: B01J 2229/16 to increase the Si/Al ratio; Dealumination
• CPC Class Codes: B01J 2229/186 not in framework positions
• CPC Class Codes: B01J 2229/20 to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
• CPC Class Codes: B01J 2229/32 Reaction with silicon compounds, e.g. TEOS, siliconfluoride
• CPC Class Codes: B01J 2229/37 Acid treatment
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 23/42 Platinum
• CPC Class Codes: B01J 23/44 Palladium
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 29/70 of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• CPC Class Codes: B01J 29/703 MRE-type, e.g. ZSM-48
• CPC Class Codes: B01J 29/7049 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
• CPC Class Codes: B01J 29/708 MRE-type, e.g. ZSM-48
• CPC Class Codes: B01J 29/7261 MRE-type, e.g. ZSM-48
• CPC Class Codes: B01J 29/7446 EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
• CPC Class Codes: B01J 29/7461 MRE-type, e.g. ZSM-48
• CPC Class Codes: B01J 29/7661 MRE-type, e.g. ZSM-48
• CPC Class Codes: B01J 29/7861 MRE-type, e.g. ZSM-48
• CPC Class Codes: B01J 29/80 Mixtures of different zeolites
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• 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 37/0201 : Impregnation
• CPC Class Codes: B01J 37/18 : with gases containing free hydrogen
• CPC Class Codes: B01J 37/30 : Ion-exchange
• CPC Class Codes: C10G 2300/1022 : Fischer-Tropsch products
• CPC Class Codes: C10G 2300/1059 : Gasoil having a boiling range of about 330 - 427 °C
• CPC Class Codes: C10G 2300/1062 : Lubricating oils
• CPC Class Codes: C10G 2300/107 : Atmospheric residues having a boiling point of at least about 538 °C
• CPC Class Codes: C10G 2300/1074 : Vacuum distillates
• CPC Class Codes: C10G 2300/1096 : Aromatics or polyaromatics
• CPC Class Codes: C10G 2300/301 : Boiling range
• CPC Class Codes: C10G 2300/304 : Pour point, cloud point, cold flow properties
• CPC Class Codes: C10G 2300/70 : Catalyst aspects
• CPC Class Codes: C10G 2400/30 : Aromatics
• CPC Class Codes: C10G 35/065 : containing crystalline zeolitic molecular sieves, other than aluminosilicates
• CPC Class Codes: C10G 45/62 : containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 45/64 : containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 47/16 : Crystalline alumino-silicate carriers
• CPC Class Codes: C10G 47/18 : the catalyst containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 47/20 : the catalyst containing other metals or compounds thereof
• CPC Class Codes: C10G 49/08 : containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 50/00 : Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• CPC Class Codes: C10G 65/043 : at least one step being a change in the structural skeleton
• CPC Class Codes: C10G 65/12 : including cracking steps and other hydrotreatment steps

Abstract

A hydrocarbon conversion catalyst composition which comprises dealuminated ZSM-48 and/or EU-2 zeolite and a refractory oxide binder essentially free of alumina, processes for preparing such composition and processes for converting hydrocarbon feedstock with the help of such compositions.

Claims

1. A dewaxing or alkylaromatics isomerization catalyst composition, which consists essentially of:

a dealuminated dried and calcined extrudate, obtained from a dried and calcined extrudate, wherein the extrudate, before drying and calcination, comprises a binder that is essentially free of alumina and which comprises both silica powder, wherein said silica powder comprises powder particles having a mean diameter between 10 μ

m and 200 μ

m, and a silica sol;

EU-2 zeolite, wherein said EU-2 zeolite has a silica-to-alumina molar bulk ratio before the dealumination of said dried and calcined extrudate in the range of from 100 to 210;

a plasticising agent; and

water in an amount of at least 35% and not exceeding 60% by weight of the extrudate before drying and calcination; and

a catalytic metal selected from the group consisting of platinum, palladium and nickel;

wherein the dealumination of said dried and calcined extrudate is done by contacting said dried and calcined extrudate with an aqueous solution of fluorosilicate salt having a concentration of at least 0.005 mole of fluorosilicate salt/liter and at most 0.5 mole of fluorosilicate salt/liter and at a temperature in the range of from 10°

C. to 120°

C., and

wherein the amount of said EU-2 zeolite present in said hydroconversion catalyst composition is at least 15% wt of said hydrocarbon conversion catalyst composition; and

wherein the EU-2 zeolite is in the form of EU-2 zeolite particles, where the average aluminum concentration of the EU-2 zeolite particles is at least two times the aluminum concentration at the surface of the particles.

2. The catalyst composition according to claim 1, wherein the zeolite content, on a dry basis, is of from 20 to 70 wt % as calculated on the total of said dewaxing or alkylaromatics isomerization catalyst composition.

3. The catalyst composition according to claim 1, wherein said fluorosilicate salt of said fluorosilicate salt solution is represented by the formula:

(A)_2/bSiF₆

wherein ‘

A’

is a metallic or non-metallic cation other than H+ having the valence ‘

b’

.

4. A process for converting a hydrocarbon feedstock which process comprises contacting the feedstock with a catalyst composition according to claim 1 at a temperature of from 100 to 600°

C. and a pressure of from 1 to 100 bara.

5. A process according to claim 4 in which process the feedstock has a 10% distillation point greater than 343°

C. measured by ASTM D-2887-93.

6. The catalyst composition according to claim 2, wherein the plasticizing agent is selected from the group consisting of dextrose, gelatin, glucose, glues, gums, salts, waxes, starch and cellulose ethers.

7. The catalyst composition according to claim 6, wherein said binder contains at most 2% wt alumina, based on dry weight of the binder per se.

8. The catalyst composition according to claim 7, wherein said binder contains at most 1.1% wt alumina, based on dry weight of the binder per se.

9. The catalyst composition according to claim 8, wherein said extrudate further comprises zeolite ZSM-12 that is present therein in an amount of at most 50% wt, based on the amount of EU-2 zeolite present.

10. The catalyst composition according to claim 9, wherein the amount of EU-2 zeolite is at least 25% wt and at most 65% wt.

11. The catalyst composition according to claim 10, wherein said plasticizing agent is methylcellulose or a methylcellulose derivative.

12. The catalyst composition according to claim 11, wherein said binder contains at most 0.2% wt alumina, based on dry weight of the binder per se.