# US 10,766,022 B2 · Hydrocarbon conversion catalyst composition

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- Number: US 10,766,022 B2
- Document ID: US10766022B2
- Status: Granted
- Kind: B2
- Application number: 16/561,914
- Filed: 2019-09-05
- Published: 2019-12-26
- Granted: 2020-09-08
- Earliest claimed: 2010-10-25
- Assignees: Shell Oil Company
- Applicants: Shell Oil Company
- Inventors: László Domokos; Laurent Georges Huve; Hermanus Jongkind; Aan Hendrik Klazinga; Marcello Stefano Rigutto
- Web page: https://patentgrep.com/patent/US10766022B2

## CPC

- B01J 29/7446: {EUO-type, e.g. EU-1, TPZ-3 or ZSM-50}
- B01J 23/42: Platinum
- B01J 23/44: Palladium
- B01J 23/755: Nickel
- B01J 29/70: of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J 29/703: {MRE-type, e.g. ZSM-48}
- B01J 29/7049: {containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead}
- B01J 29/708: {MRE-type, e.g. ZSM-48}
- B01J 29/7261: {MRE-type, e.g. ZSM-48}
- B01J 29/7461: {MRE-type, e.g. ZSM-48}
- B01J 29/7661: {MRE-type, e.g. ZSM-48}
- B01J 29/7861: {MRE-type, e.g. ZSM-48}
- B01J 29/80: Mixtures of different zeolites
- B01J 35/60: characterised by their surface properties or porosity
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/0201: {Impregnation}
- B01J 37/18: with gases containing free hydrogen
- B01J 37/30: Ion-exchange
- C10G 35/065: {containing crystalline zeolitic molecular sieves, other than aluminosilicates}
- C10G 45/62: containing platinum group metals or compounds thereof
- C10G 45/64: containing crystalline alumino-silicates, e.g. molecular sieves
- C10G 47/16: Crystalline alumino-silicate carriers
- C10G 47/18: the catalyst containing platinum group metals or compounds thereof
- C10G 47/20: the catalyst containing other metals or compounds thereof
- C10G 49/08: containing crystalline alumino-silicates, e.g. molecular sieves
- C10G 50/00: Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G 65/043: {at least one step being a change in the structural skeleton}
- C10G 65/12: including cracking steps and other hydrotreatment steps
- B01J 2229/16: to increase the Si/Al ratio; Dealumination
- B01J 2229/186: not in framework positions
- 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
- B01J 2229/32: Reaction with silicon compounds, e.g. TEOS, siliconfluoride
- B01J 2229/37: Acid treatment
- B01J 2229/42: Addition of matrix or binder particles
- C10G 2300/1022: Fischer-Tropsch products
- C10G 2300/1059: Gasoil having a boiling range of about 330 - 427 °C
- C10G 2300/1062: Lubricating oils
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- C10G 2300/1074: Vacuum distillates
- C10G 2300/1096: Aromatics or polyaromatics
- C10G 2300/301: Boiling range
- C10G 2300/304: Pour point, cloud point, cold flow properties
- C10G 2300/70: Catalyst aspects
- C10G 2400/30: Aromatics
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES

## 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

### Claim 1

A catalytic dewaxing process for reducing the pour point of a wax-containing feedstock, said catalytic dewaxing process comprises:
contacting under dewaxing conditions said wax-containing feedstock, having a 10% distillation point at 200° C. as measured by ASTM D-2887-93, with a dewaxing catalyst composition, wherein said dewaxing conditions include a contacting temperature in the range of from 250 to 400° C., a contacting pressure in the range of from 5×105 to 200×105 Pa, and a liquid hourly space velocity in the range of from 0.1 to 10 hr −1, and thereby providing a reduction of the pour point of said wax-containing feedstock by at least 10° C.;
wherein said dewaxing catalyst comprises a dealuminated dried and calcined extrudate, wherein said extrudate, before drying and calcination, comprises a binder that is essentially free of alumina and which comprises both a silica powder, wherein said silica powder comprises powder particles having a mean diameter between 10 μm and 200 μm, 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 catalyst composition is at least 15% wt. of said 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.

### Claim 2 (depends on 1)

The process as recited in claim 1, wherein the EU-2 zeolite content in said catalyst composition, on a dry basis, is in the range of from 20 to 70 wt. % as calculated on the total weight of said catalyst composition.

### Claim 3 (depends on 2)

The process as recited in claim 2, 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’.

### Claim 4 (depends on 3)

The process as recited in claim 3, wherein the plasticizing agent is selected from the group consisting of dextrose, gelatin, glucose, glues, gums, salts, waxes, starch and cellulose ethers.

### Claim 5 (depends on 4)

The process as recited in claim 4, wherein said binder contains at most 2% wt. alumina, based on dry weight of the binder.

### Claim 6 (depends on 5)

The process as recited in claim 5, wherein said binder contains at most 1.1% wt. alumina, based on dry weight of the binder.

### Claim 7 (depends on 6)

The process as recited in claim 6, wherein said extrudate further comprises zeolite ZSM-12 that is present therein in an amount of at most 50% wt., based on the weight of said EU-2 zeolite present in said catalyst composition.

### Claim 8 (depends on 7)

The process as recited in claim 7, wherein the amount of EU-2 zeolite is at least 25% wt. and at most 65% wt.

### Claim 9 (depends on 8)

The process as recited in claim 8, wherein said plasticizing agent is methylcellulose or a methylcellulose derivative.

### Claim 10 (depends on 9)

The process as recited in claim 9, wherein said binder contains at most 0.2% wt. alumina, based on dry weight of the binder.

### Claim 11 (depends on 10)

The process according to claim 10, wherein said contacting temperature is in the range of from 275 to 350° C. and said contacting pressure is in the range of from 15×105 to 170×105 Pa.

### Claim 12 (depends on 11)

The process according to claim 11, wherein said wax-containing feedstock has a wax content of at least 50% by weight as determined by ASTM method D3235.

### Claim 13 (depends on 12)

The process according to claim 12, wherein said reduction of the pour point of said wax-containing feedstock is at least 20° C.

### Claim 14 (depends on 13)

The process according to claim 13, wherein said wax-containing feedstock has a wax content of at least 80% by weight.