# US 9,518,229 B2 · Catalysts for thermo-catalytic conversion of biomass, and methods of making and using

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- Number: US 9,518,229 B2
- Document ID: US9518229B2
- Status: Granted
- Kind: B2
- Application number: 13/838,706
- Filed: 2013-03-15
- Published: 2014-01-23
- Granted: 2016-12-13
- Earliest claimed: 2012-07-20
- Assignees: Inaeris Technologies, LLC
- Applicants: Inaeris Technologies, LLC
- Inventors: Jerry Jon Springs; Bruce ADkins; Stephen Schuyten; Gopal Juttu; Christine M. Henry; Kelsey Shogren
- Web page: https://patentgrep.com/patent/US9518229B2

## CPC

- C10G 1/086: {Characterised by the catalyst used}
- B01J 29/084: {Y-type faujasite}
- B01J 29/18: of the mordenite type
- B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J 29/65: of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J 29/7007: {Zeolite Beta}
- B01J 35/32: Bulk density
- B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)}
- B01J 37/28: Phosphorising
- C10G 1/08: with moving catalysts
- B01J 35/615: {100-500 m2/g}
- B01J 35/63: Pore volume
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 35/66: Pore distribution
- B01J 35/67: monomodal
- B01J 37/0045: {Drying a slurry, e.g. spray drying}
- B01J 2229/42: Addition of matrix or binder particles
- C10G 2300/1011: Biomass
- C10G 2300/1014: of vegetal origin
- Y02P 30/20: using bio-feedstock
- 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
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Disclosed are catalyst compositions including zeolite and silica components, methods of making, and processes of using in the thermo-catalytic conversion of biomass. Such disclosed methods of making include: i) spray drying of the catalyst precursor slurry at a pH below 1, or ii) the removal of ions such as sodium from the binder material prior to spray drying the catalyst precursor slurry at a pH below 2.7, or iii) spray drying the catalyst precursor including a pore regulating agent followed by steam treating, or iv) some combination of i), ii) and iii).

## Claims

### Claim 1

A method of making a biomass conversion catalyst comprising:
a) preparing an aqueous slurry comprising a phosphorous-promoted zeolite and a silica precursor, wherein the zeolite is selected from the group consisting of ZSM-5, mordenite, beta, ferrierite, zeolite-Y, and combinations thereof;
b) spray drying said aqueous slurry at a pH equal to or less than about 2.7, thereby gelling said silica precursor and forming a biomass conversion catalyst in the form of particles;
c) wet impregnating the biomass conversion catalyst with phosphorous; and
d) drying the wet impregnated biomass conversion catalyst, forming a phosphorous-promoted biomass conversion catalyst.

### Claim 2 (depends on 1)

The method of claim 1 wherein said aqueous slurry further comprises a clay; said zeolite is ZSM-5; and said silica precursor is at least one of silicic acid and polysilicic acid.

### Claim 3 (depends on 2)

The method of claim 2 wherein said clay is kaolin, and said biomass conversion catalyst is free of or substantially free of amorphous alumina.

### Claim 4 (depends on 2)

The method of claim 2 wherein said particles have: i) an average pore volume of pores ranging in diameter from about 80 to about 600 Å of at least about 0.025 cm3/g, and ii) an average pore volume of pores ranging in diameter from about 20 to about 80 Å of no more than about 0.08 cm3/g; wherein each of said average pore volumes in i) and ii) are obtained from the adsorption branch of the nitrogen isotherm, when measured per ASTM method D4222 at about 77° K, and discretized according to the BJH pore size distribution model.

### Claim 5

A method of making a biomass conversion catalyst comprising:
a) preparing an aqueous slurry comprising: (i) a phosphorous-promoted zeolite, wherein the zeolite is selected from the group consisting of ZSM-5, mordenite, beta, ferrierite, zeolite-Y, and combinations thereof, (ii) a silica precursor which is substantially sodium free, and (iii) a pore regulating agent selected from the group consisting of ionic pore regulating agents, nonionic pore regulating agents, and combinations thereof;
b) spray drying said aqueous slurry at a pH equal to or less than about 2.7, thereby gelling said silica precursor and forming said biomass conversion catalyst into particles; wherein said particles have an average mesopore surface area (average MSA) less than or equal to about 50 m2/g, and wherein said biomass conversion catalyst has a salt concentration less than about 0.1 times the mass of said silica; and
c) promoting the biomass conversion catalyst with phosphorous.

### Claim 6 (depends on 5)

The method of claim 5 wherein said aqueous slurry further comprises a clay; said zeolite is ZSM-5; said silica precursor is at least one of silicic acid and polysilicic acid; and wherein said biomass conversion catalyst is free of or substantially free of amorphous alumina.

### Claim 7 (depends on 5)

The method of claim 5 wherein, prior to step a), a ZSM-5 material is treated with a phosphorous-containing compound to form a phosphorous promoted ZSM-5 which is used as said zeolite in said aqueous slurry.

### Claim 8 (depends on 5)

The method of claim 5 wherein said particles have: i) an average pore volume of pores ranging in diameter from about 80 to about 600 Å of no more than about 0.020 cm3/g, and ii) an average pore volume of pores ranging in diameter from about 20 to about 80 Å of no more than about 0.010 cm3/g; wherein each of said average pore volumes in i) and ii) are obtained from the adsorption branch of the nitrogen isotherm, when measured per ASTM method D4222 at about 77° K, and discretized according to the BJH pore size distribution model.

### Claim 9 (depends on 5)

The method of claim 5 wherein said aqueous slurry is spray dried in step b) at a pH equal to or less than about 1, thereby gelling said silica precursor and forming said biomass conversion catalyst into particles.

### Claim 10 (depends on 9)

The method of claim 9 wherein said particles have: i) an average pore volume of pores ranging in diameter from about 80 to about 600 Å of at least about 0.01 cm3/g, and ii) an average pore volume of pores ranging in diameter from about 20 to about 80 Å of no more than about 0.03 cm3/g; wherein each of said average pore volumes in i) and ii) are obtained from the adsorption branch of the nitrogen isotherm, when measured per ASTM method D4222 at about 77° K, and discretized according to the BJH pore size distribution model.

### Claim 11 (depends on 9)

The method of claim 9 wherein said aqueous slurry further comprises a clay; said zeolite is ZSM-5; and said silica precursor is at least one of silicic acid and polysilicic acid.

### Claim 12 (depends on 9)

The method of claim 9 wherein, prior to step a), a ZSM-5 material is treated with a phosphorous-containing compound to form a phosphorous promoted ZSM-5 which is used as said zeolite in said aqueous slurry.

### Claim 13 (depends on 9)

The method of claim 9 wherein following said spray drying step said biomass conversion catalyst is promoted with phosphorous.