US 12,460,140 B2
Two stage fixed-bed catalytic process for upgrading pyrolysis oil to BTX
Miao Sun, Dhahran (SA); Lianhui Ding, Dhahran (SA); Noor Al-Mana, Al Khobar (SA); Mohammed I. AlAmer, Dammam (SA); and Sameer A. Ghamdi, Dhahran (SA)
Assigned to Saudi Arabian Oil Company, Dhahran (SA)
Filed by Saudi Arabian Oil Company, Dhahran (SA)
Filed on Jul. 20, 2023, as Appl. No. 18/355,789.
Prior Publication US 2025/0026995 A1, Jan. 23, 2025
Int. Cl. C10G 65/10 (2006.01); B01J 21/04 (2006.01); B01J 21/06 (2006.01); B01J 23/00 (2006.01); B01J 23/745 (2006.01); B01J 23/83 (2006.01); B01J 29/04 (2006.01); B01J 29/16 (2006.01); B01J 29/78 (2006.01); B01J 35/40 (2024.01); B01J 35/50 (2024.01); B01J 37/00 (2006.01); B01J 37/02 (2006.01); C10G 47/04 (2006.01); C10G 47/20 (2006.01)
CPC C10G 65/10 (2013.01) [B01J 21/04 (2013.01); B01J 21/066 (2013.01); B01J 23/002 (2013.01); B01J 23/745 (2013.01); B01J 23/83 (2013.01); B01J 29/045 (2013.01); B01J 29/166 (2013.01); B01J 29/7815 (2013.01); B01J 35/40 (2024.01); B01J 35/50 (2024.01); B01J 37/0009 (2013.01); B01J 37/0201 (2013.01); C10G 2300/1096 (2013.01); C10G 2300/4006 (2013.01); C10G 2300/4012 (2013.01); C10G 2300/70 (2013.01); C10G 2400/30 (2013.01)] 18 Claims
OG exemplary drawing
 
1. A method for upgrading pyrolysis oil, the method comprising:
contacting a pyrolysis oil feed with hydrogen in the presence of a mixed metal oxide catalyst and a secondary catalyst in a first fixed-bed reactor, where:
the pyrolysis oil feed comprises multi-ring aromatic compounds comprising greater than or equal to sixteen carbon atoms;
the first fixed-bed reactor comprises a first catalyst bed and a second catalyst bed downstream from the first catalyst bed;
the first catalyst bed comprises the mixed metal oxide catalyst;
the mixed metal oxide catalyst comprises a plurality of MMO particles and each of the plurality of MMO particles comprises Fe2O3, ZrO2, CeO2, and Al2O3;
the second catalyst bed comprises the secondary catalyst, where the secondary catalyst has a different composition from the mixed metal oxide catalyst;
the method comprises contacting the pyrolysis oil feed and the hydrogen with the mixed metal oxide catalyst in the first catalyst bed and then with the secondary catalyst downstream of the mixed metal oxide catalyst in the second catalyst bed in the first fixed-bed reactor; and
contacting the pyrolysis oil feed with hydrogen in the presence of the mixed metal oxide catalyst in the first catalyst bed and the secondary catalyst in the secondary catalyst bed in the first fixed-bed reactor causes at least a portion of the multi-ring aromatic compounds in the pyrolysis oil feed to react to produce an intermediate stream comprising di-aromatic compounds, tri-aromatic compounds, or combinations thereof;
contacting the intermediate stream with hydrogen in the presence of a mesoporous supported metal catalyst in a second fixed-bed reactor, where the mesoporous supported metal catalyst has a different composition from the secondary catalyst, where:
the mesoporous supported metal catalyst comprises nickel and tungsten impregnated onto a mesoporous support comprising a large pore alumina, a binder, and at least one zeolite;
contacting the intermediate stream with the hydrogen in the presence of the mesoporous supported metal catalyst causes at least a portion of the di-aromatic compounds and/or tri-aromatic compounds in the intermediate stream to react to produce a second reactor effluent comprising aromatic compounds having six to eight carbon atoms.