# US 10,870,106 B1 · Methods for producing multifunctional catalysts for upgrading pyrolysis oil

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- Number: US 10,870,106 B1
- Document ID: US10870106B1
- Status: Granted
- Kind: B1
- Application number: 16/807,451
- Filed: 2020-03-03
- Published: 2021-01-07
- Granted: 2020-12-22
- Earliest claimed: 2019-07-03
- Assignees: Saudi Arabian Oil Company
- Applicants: Saudi Arabian Oil Company
- Inventors: Miao Sun
- Web page: https://patentgrep.com/patent/US10870106B1

## 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 method for upgrading pyrolysis oil, the method comprising:
contacting the pyrolysis oil with a multifunctional catalyst at mild reaction conditions comprising reaction temperatures of less than 500 degrees Celsius (° C.) and pressures less than 6 megapascals (MPa) where:
the pyrolysis oil is a bottom stream from a steam cracking process and comprises multi-ring aromatic compounds;
the multifunctional catalyst is produced by a process 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 that includes a heteroatom selected from the group consisting of phosphorous, silicon, germanium, arsenic, and combinations of these, where the contacting causes the first metal catalyst precursor and the second metal catalyst precursor to deposit 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 to produce the multifunctional catalyst;
where the multifunctional catalyst comprises at least a first metal catalyst and a second metal catalyst supported on the zeolite support
where contact of the pyrolysis oil with the multifunctional catalyst at the reaction conditions converts at least a portion of the multi-ring aromatic compounds in the pyrolysis oil to one or more C6-C8 aromatic compounds.

### Claim 2 (depends on 1)

The method of claim 1, in which the C6-C8 aromatic compounds include one or more of benzene, toluene, ethylbenzene, xylene, or combinations of these.

### Claim 3 (depends on 1)

The method of claim 1, in which contacting the pyrolysis oil with the multifunctional catalyst at the reaction conditions converts the portion of the multi-ring aromatic compounds in the pyrolysis oil to C6-C8 aromatic compounds in a single step, without conducting a subsequent chemical reaction step.

### Claim 4 (depends on 1)

The method of claim 1, in which the pyrolysis oil is contacted with the multifunctional catalyst at a temperature of from 300° C. to 450° C.

### Claim 5 (depends on 1)

The method of claim 1, in which the pyrolysis oil is contacted with the multifunctional catalyst at a pressure of from 0.1 MPa to 5 MPa.

### Claim 6 (depends on 1)

The method of claim 1, where the pyrolysis oil comprises greater than or equal to 50 weight percent multi-aromatic compounds.

### Claim 7 (depends on 1)

The method of claim 1, where the first metal catalyst precursor, the second metal catalyst precursor, or both have a Keggin structure having general formula XM12O40n− or a Dawson structure having the general formula XM18O82n−, in which X is the heteroatom; M is the molybdenum and optionally one or more of colbalt, vanadium, or a combination of these; and n− is an integer indicative of the charge of the anion of the heteropolyacid.

### Claim 8 (depends on 1)

The method of claim 1, where the solution includes from 1 wt. % to 20 wt. % of the first metal catalyst precursor and from 1 wt. % to 20 wt. % of the second metal catalyst precursor.

### Claim 9 (depends on 1)

The method of claim 1, where the first metal of the first metal precursor is a metal selected from the group consisting of molybdenum, vanadium, and cobalt and the first metal is different from the second metal of the second metal precursor.

### Claim 10 (depends on 1)

The method of claim 1, where the second metal of the second metal precursor is a metal selected from the group consisting of molybdenum, vanadium, and cobalt and wherein the second metal is different from the first metal of the first metal precursor.