# US 9,433,935 B2 · Synthesis of framework modified ZSM-48 crystals

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- Number: US 9,433,935 B2
- Document ID: US9433935B2
- Status: Granted
- Kind: B2
- Application number: 14/228,568
- Filed: 2014-03-28
- Published: 2015-10-01
- Granted: 2016-09-06
- Earliest claimed: 2014-03-28
- Assignees: ExxonMobil Research and Engineering Company
- Applicants: Wenyih Frank Lai; Lei Zhang
- Inventors: Wenyih Frank Lai; Lei Zhang
- Web page: https://patentgrep.com/patent/US9433935B2

## CPC

- B01J 29/703: {MRE-type, e.g. ZSM-48}
- B01J 29/048: {Zincosilicates, Aluminozincosilicates (B01J29/005 takes precedence)}
- B01J 29/89: Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium {(B01J29/005 takes precedence)}
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- C01B 39/48: using at least one organic template directing agent
- C10G 45/62: containing platinum group metals or compounds thereof
- C10G 45/64: containing crystalline alumino-silicates, e.g. molecular sieves
- B01J 29/7461: {MRE-type, e.g. ZSM-48}
- B01J 29/7861: {MRE-type, e.g. ZSM-48}
- B01J 2229/183: in framework positions
- B01J 2229/186: not in framework positions
- B01J 2229/36: Steaming
- B01J 2229/40: Special temperature treatment, i.e. other than just for template removal
- B01J 2229/42: Addition of matrix or binder particles
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- 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

Methods are provided for synthesis ZSM-48 crystals (or other MRE framework crystals) having heteroatoms different from silicon and aluminum incorporated into the framework structure, and use of such crystals for applications such as catalytic processing of hydrocarbonaceous feeds. Examples of heteroatoms can include titanium, zirconium, and zinc.

## Claims

### Claim 1

A method of dewaxing a hydrocarbonaceous feedstock, comprising:
exposing a feedstock under effective dewaxing conditions to a catalyst comprising ZSM-48 crystals containing at least one of titania, zirconia, or zinc oxide as a framework metal oxide in a ZSM-48 structural framework, a molar ratio of SiO2 to the framework metal oxide in the ZSM-48 structural framework being 70 to 200, a molar ratio of SiO2 to Al7O3 in the ZSM-48 structural framework of 120 to 225.

### Claim 2 (depends on 1)

The method of claim 1, wherein the ZSM-48 crystals are substantially free of intentionally added alumina.

### Claim 3 (depends on 1)

The method of claim 1, wherein the framework metal oxide is titania.

### Claim 4 (depends on 1)

The method of claim 1, wherein the effective dewaxing conditions comprise a temperature from 200° C. to 450° C., a pressure from 0 psig to 1000 psig 6.9 MPag), a WHSV from 0.2 hr−1 to 10 hr−1, and a hydrogen/hydrocarbon mole ratio from 0.5 to 10.

### Claim 5 (depends on 1)

The method of claim 1, wherein the catalyst further comprises a metal oxide binder.

### Claim 6 (depends on 1)

The method of claim 1, wherein the catalyst further comprises a metal hydrogenation component.

### Claim 7 (depends on 6)

The method of claim 6, wherein the metal hydrogenation component comprises a group VIII metal, a Group VIB metal, or a combination thereof.

### Claim 8 (depends on 6)

The method of claim 6, wherein the metal hydrogenation component comprises 0.1 wt % to 1.5 wt % of Pt, Pd, or a combination thereof.

### Claim 9

A method of synthesizing ZSM-48 crystals containing at least one of titania, zirconia, or zinc oxide as a framework metal oxide in a zeolite structural framework, the method comprising crystallizing a reaction mixture comprising a source of water, a source of SiO2, a source of the framework metal oxide, a source of an alkali metal M, and a source of a structure directing agent in the form of an organic cation, Q,
the reaction mixture having a molar ratio of structure directing agent cation, Q, to SiO2 in said reaction mixture of 0.01 to 0.2; a molar ratio of SiO2 to framework metal oxide in said reaction mixture of 50 to 225; a molar ratio of water to SiO2 in said reaction mixture of 1 to 500; a molar ratio of hydroxyl group concentration to SiO2 in said reaction mixture of from 0.1 to 0.5; a molar ratio of alkali metal, M, to SiO2 in said reaction mixture of from 0.05 to 0.5; and a molar ratio of SiO2 to Al2O3 in said reaction mixture of 120 to 225.

### Claim 10 (depends on 9)

The method of claim 9, wherein the structure directing agent cation Q is a hexamethonium cation.

### Claim 11 (depends on 9)

The method of claim 9, wherein the reaction mixture is substantially free of a source of intentionally added Al2O3.

### Claim 12 (depends on 9)

The method of claim 9, wherein the reaction mixture further comprises seeds of ZSM-48 in an amount such that a weight percent of seeds relative to total weight of SiO2 in said reaction mixture is between 0.1 wt % and 20 wt %.

### Claim 13 (depends on 9)

The method of claim 9, wherein the framework metal oxide is titania.