# US 10,118,166 B2 · Zeolitic materials with modified surface composition, crystal structure, crystal size, and/or porosity, methods for making the same, and methods for converting oxygenates to olefins via reactions catalyzed by the same

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- Number: US 10,118,166 B2
- Document ID: US10118166B2
- Status: Granted
- Kind: B2
- Application number: 14/519,441
- Filed: 2014-10-21
- Published: 2015-12-10
- Granted: 2018-11-06
- Earliest claimed: 2014-06-06
- Assignees: Uop LLC
- Applicants: Uop LLC
- Inventors: Nick J. Schoenfeldt; David Stickley; Jaime G. Moscoso; Deng-Yang Jan; Benjamin Daniel Yuhas
- Web page: https://patentgrep.com/patent/US10118166B2

## CPC

- B01J 29/85: Silicoaluminophosphates [SAPO compounds]
- B01J 29/06: Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- C01B 37/08: Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO}
- C01B 39/026: {After-treatment}
- C01B 39/54: Phosphates, e.g. APO or SAPO compounds
- C07C 1/20: starting from organic compounds containing only oxygen atoms as heteroatoms
- B01J 2229/12: to alter the outside of the crystallites, e.g. selectivation
- B01J 2229/186: not in framework positions
- B01J 2229/34: Reaction with organic or organometallic compounds
- B01J 2229/38: Base treatment
- C07C 2529/85: Silicoaluminophosphates (SAPO compounds)
- Y02P 20/52: using catalysts, e.g. selective catalysts
- Y02P 30/20: using bio-feedstock
- Y02P 30/40: Ethylene production
- 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}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Zeolitic materials with modified surface composition, crystal structure, crystal or particle size, and/or porosity, methods for making the same, and methods for converting oxygenates to olefins using the same are provided herein. In an exemplary embodiment, a method for reducing a surface silicon content of a silicon-containing zeolitic material is provided that includes providing a silicon-containing zeolitic material; and contacting the silicon-containing zeolitic material with a modifying solution comprising one or more of an amine, an alcoholamine, and an amino acid. In this embodiment, the contacting occurs under conditions suitable for the modifying solution to reduce a surface silicon content, increase the porosity, and/or decrease an average crystal or particle size of the silicon-containing zeolitic material.

## Claims

### Claim 1

A method for reducing a surface silicon content of a silicon-containing zeolitic material, the method comprising the steps of: providing a zeolitic material comprising silicon at a surface of the zeolitic material; and
contacting the surface of the zeolitic material with a modifying solution comprising one or more of an amine, or an alcoholamine,
wherein contacting the surface of the zeolitic material with the modifying solution reduces an amount of silicon at the surface to generate a modified zeolitic material with a reduced surface silicon content and wherein contacting the surface of the zeolitic material with a modifying solution comprises contacting the surface of the zeolitic material with an alcoholamine with one, two or three alcohol functionalities, a C1 to C4 chain length on an alcohol substituent, or both, or contacting the surface of the zeolitic material with a modifying solution comprises contacting the surface of the zeolitic material with a diethanolamine, or a combination thereof.

### Claim 2 (depends on 1)

The method of claim 1, wherein providing a zeolitic material comprises providing a silicoaluminophosphate (SAPO), a metal-substituted silicoaluminumphosphate (MeAPSO), or a combination thereof.

### Claim 3 (depends on 1)

The method of claim 1, wherein providing a zeolitic material comprises providing a metal-substituted silicoaluminumphosphate (MeAPSO) comprising one or more metals from groups 2 through 13 of the periodic table of elements.

### Claim 4 (depends on 1)

The method of claim 1, wherein providing a zeolitic material comprises providing a metal-substituted silicoaluminumphosphate (MeAPSO) comprising magnesium (Mg), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), or a combination thereof.

### Claim 5 (depends on 1)

The method of claim 1, wherein contacting the surface of the zeolitic material with a modifying solution comprises contacting the surface of the zeolitic material with one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, phenylamine, and diphenyl amine.

### Claim 6 (depends on 1)

The method of claim 1, wherein providing a zeolitic material comprises providing a SAPO-34 material and wherein the method produces a modified SAPO-34 material with a bulk silicon content of about 0.4 wt. % and 2.7 wt. % Si.

### Claim 7 (depends on 1)

The method of claim 1, wherein providing the zeolitic material comprises providing a SAPO-18 material and wherein the method produces a modified SAPO-18 material with a bulk silicon content of about 0.3 wt. % and 2.7 wt. % Si.

### Claim 8 (depends on 1)

The method of claim 1, wherein the zeolitic material comprises a silicoaluminophosphate (SAPO), a metal-substituted silicoaluminumphosphate (MeAPSO), or a combination thereof; and
wherein reducing the surface silicon content of the zeolitic material comprises reducing the silicon:(aluminum+phosphorous) ratio at the surface of the silicon-containing zeolitic material.

### Claim 9 (depends on 1)

The method of claim 1, wherein contacting the surface of the zeolitic material with the modifying solution additionally increases the % porosity, decreases the average crystal or particle size, or both, to generate a modified zeolitic material with a reduced surface silicon content and elevated % porosity, decreased crystal size, or both.

### Claim 10 (depends on 1)

The method of claim 1, wherein the zeolitic material comprises SAPO-34, metal-substituted SAPO-34, SAPO-18, metal-substituted SAPO-18, SAPO-56, SAPO-RHO, SAPO-5, or mixtures or intergrowths thereof.

### Claim 11

A method for reducing a surface silicon content of a silicon-containing zeolitic material, the method comprising the steps of:
providing a zeolitic material comprising silicon at a surface of the zeolitic material, wherein the zeolitic material comprises a silico-alumino-phosphate (SAPO), a metal-substituted silicoaluminumphosphate (MeAPSO), or combinations thereof, wherein the zeolitic material comprises SAPO-34, metal-substituted SAPO-34, SAPO-18, metal-substituted SAPO-18, SAPO-56, SAPO-RHO, SAPO-5, or mixtures or intergrowths thereof; and
contacting the surface of the zeolitic material with a modifying solution comprising one or more of an amine, or an alcoholamine, an alcoholamine with one, two, or three alcohol functionalities, a C1 to C4 chain length on an alcohol substituent, or both or wherein contacting the surface of the zeolitic material with a modifying solution comprises contacting the surface of the zeolitic material with a diethanolamine, or a combination thereof. wherein contacting the surface of the zeolitic material with the modifying solution reduces an amount of silicon at the surface to generate a modified zeolitic material with a reduced surface silicon content.

### Claim 12 (depends on 11)

The method of claim 11, wherein providing a zeolitic material comprises providing a metal-substituted silicoaluminumphosphate (MeAPSO) comprising one or more metals from groups 2 through 13 of the periodic table of elements.

### Claim 13 (depends on 11)

The method of claim 11, wherein the modifying solution has a concentration of active constituents of from about 0.01 g/ml to about 1 g/ml, or wherein a ratio of the zeolitic material to the modifying solution is about 1 to about 50 g zeolitic material:100 ml of modifying solution, or both.