# US 11,027,271 B2 · Methods for producing multifunctional catalysts for upgrading pyrolysis oil

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- Number: US 11,027,271 B2
- Document ID: US11027271B2
- Status: Granted
- Kind: B2
- Application number: 16/916,234
- Filed: 2020-06-30
- Published: 2021-01-07
- Granted: 2021-06-08
- Earliest claimed: 2019-07-03
- Assignees: Saudi Arabian Oil Company
- Applicants: Saudi Arabian Oil Company
- Inventors: Miao Sun
- Web page: https://patentgrep.com/patent/US11027271B2

## CPC

- B01J 27/199: with chromium, molybdenum, tungsten or polonium
- B01J 37/082: {Decomposition and pyrolysis}
- B01J 27/19: Molybdenum
- B01J 27/24: Nitrogen compounds
- B01J 29/045: {containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium}
- B01J 29/061: {containing metallic elements added to the zeolite}
- B01J 29/076: containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J 29/7007: {Zeolite Beta}
- B01J 29/7815: {Zeolite Beta}
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 35/615: {100-500 m2/g}
- B01J 35/643: {less than 2 nm}
- B01J 35/67: monomodal
- B01J 37/0201: {Impregnation}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/088: {Decomposition of a metal salt}
- B01J 37/28: Phosphorising
- C07C 4/06: Catalytic processes {(C07C4/025 takes precedence)}
- C07C 4/26: by splitting polyaryl compounds at a bond between uncondensed six-membered aromatic rings, e.g. biphenyl to benzene
- C10G 1/086: {Characterised by the catalyst used}
- C10G 11/05: Crystalline alumino-silicates, e.g. molecular sieves
- C10G 35/065: {containing crystalline zeolitic molecular sieves, other than aluminosilicates}
- C10G 45/54: containing crystalline alumino-silicates, e.g. molecular sieves
- C10G 45/64: containing crystalline alumino-silicates, e.g. molecular sieves
- C10G 47/20: the catalyst containing other metals or compounds thereof
- C10G 65/12: including cracking steps and other hydrotreatment steps
- C10G 65/14: plural parallel stages only
- C10G 65/18: including only cracking steps
- C10G 67/00: Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G 69/04: including at least one step of catalytic cracking in the absence of hydrogen
- C10G 69/06: including at least one step of thermal cracking in the absence of hydrogen
- C10G 69/14: plural parallel stages only
- B01J 37/0213: {Preparation of the impregnating solution}
- B01J 2229/186: not in framework positions
- B01J 2229/22: to destroy the molecular sieve structure or part thereof
- B01J 2229/32: Reaction with silicon compounds, e.g. TEOS, siliconfluoride
- B01J 2229/38: Base treatment
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- C07C 2529/70: of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C 2529/78: containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C10G 2300/1033: Oil well production fluids
- C10G 2300/4006: Temperature
- C10G 2300/4012: Pressure
- C10G 2300/708: Coking aspect, coke content and composition of deposits
- C10G 2400/30: Aromatics
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A method of making a multifunctional catalyst for upgrading pyrolysis oil includes contacting a zeolite support with a solution including at least a first metal catalyst precursor and a second metal catalyst precursor, the first metal catalyst precursor, the second metal catalyst precursor, or both, including a heteropolyacid. Contacting the zeolite support with the solution deposits or adsorbs the first metal catalyst precursor and the second catalyst precursor onto outer surfaces and pore surfaces of the zeolite support to produce a multifunctional catalyst precursor. The method further includes removing excess solution from the multifunctional catalyst precursor and calcining the multifunctional catalyst precursor to produce the multifunctional catalyst comprising at least a first metal catalyst and a second metal catalyst deposited on the outer surfaces and pore surfaces of the zeolite support.

## Claims

### Claim 1

A multifunctional catalyst produced by a method of making a multifunctional catalyst for upgrading pyrolysis oil, the method comprising:
contacting a zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor, the first metal catalyst precursor, the second metal catalyst precursor, or both, comprising a heteropolyacid and the zeolite support comprising a molar ratio of silica to alumina of from 10 to 70, where the contacting deposits the first metal catalyst precursor and the second metal catalyst precursor onto outer surfaces and pore surfaces of the zeolite support to produce a multifunctional catalyst precursor;
removing excess solution from the multifunctional catalyst precursor; and
calcining the multifunctional catalyst precursor at a temperature of at least 500 degrees Celsius to produce the multifunctional catalyst comprising at least a first metal catalyst and a second metal catalyst deposited on the outer surfaces and pore surfaces of the zeolite support, and
where the multifunctional catalyst has an acidity of less than 10,000 micromoles of ammonia per gram (μmol(NH3)/g).

### Claim 2 (depends on 1)

The multifunctional catalyst of claim 1, in which the first metal catalyst comprises molybdenum and the second metal catalyst comprises cobalt.

### Claim 3 (depends on 1)

The multifunctional catalyst of either of claim 1, further comprising phosphorous deposited on the outer surfaces and pore surfaces of the zeolite support.

### Claim 4 (depends on 1)

The multifunctional catalyst of claim 1, in which the multifunction catalyst has a BET surface area of less than or equal to 400 meters squared per gram (m2/g).

### Claim 5 (depends on 1)

The multifunctional catalyst of claim 1, in which the heteropolyacid comprises phosphormolybdic heteropolyacid having formula H3PMo12O40.

### Claim 6 (depends on 1)

The multifunctional catalyst of claim 1, in which the heteropolyacid comprises decamolybdodicobaltate heteropolyacid.

### Claim 7 (depends on 1)

The multifunctional catalyst of claim 1, in which the zeolite support comprises a nano beta zeolite having an average pore size of less than or equal to 2 micrometers.

### Claim 8 (depends on 1)

The multifunctional catalyst of claim 1, in which the solution includes from 1 weight percent (wt. %) to 20 wt. % of the first metal catalyst precursor.

### Claim 9 (depends on 1)

The multifunctional catalyst of claim 1, in which the solution includes from 1 wt. % to 20 wt. % of the second metal catalyst precursor.

### Claim 10 (depends on 1)

The multifunctional catalyst of claim 1, in which the solution does not include an organic compound.

### Claim 11 (depends on 1)

The multifunctional catalyst of claim 1, in which the first metal of the first metal precursor consists of molybdenum.

### Claim 12 (depends on 1)

The multifunctional catalyst of claim 1, in which the second metal of the second metal precursor consists of cobalt.

### Claim 13 (depends on 1)

The multifunctional catalyst of claim 1, in which the multifunctional catalyst has an acidity of from 1000 μmol(NH3)/g to 5000 μmol(NH3)/g.

### Claim 14 (depends on 1)

The multifunctional catalyst of claim 1, in which the multifunctional catalyst does not include a binder or a matrix.

### Claim 15 (depends on 1)

The multifunctional catalyst of claim 1, in which the heteropolyacid comprises at least one heteroatom selected from the group consisting of phosphorous, silicon, germanium, arsenic, and combinations of these.