Two stage catalytic process for pyrolysis oil upgrading to BTX
A method for upgrading pyrolysis oil includes contacting a pyrolysis oil feed with hydrogen in the presence of a mixed metal oxide catalyst in a first slurry reactor, where: the pyrolysis oil feed comprises multi-ring aromatic compounds comprising greater than or equal to sixteen carbon atoms, and contacting the pyrolysis oil feed with hydrogen in the presence of the mixed metal oxide catalyst in the first slurry reactor to convert at least a portion of the multi-ring aromatic compounds in the pyrolysis oil feed to light aromatic compounds comprising di-aromatic compounds, tri-aromatic compounds, or both, passing an intermediate stream comprising the light aromatic compounds to a second slurry reactor downstream of the first slurry reactor; and contacting the intermediate stream with hydrogen in the presence of a mesoporous zeolite supported metal catalyst in a second slurry reactor.
1 . A system for upgrading pyrolysis oil, the system comprising:
a mixed metal oxide catalyst comprising a plurality of catalyst particles, where each of the plurality of catalyst particles comprises a plurality of different metal oxides;
a first slurry reactor configured to contact a pyrolysis oil feed with hydrogen in the presence of the mixed metal oxide catalyst to produce a first reactor effluent comprising light aromatic compounds that include di-aromatic compounds, tri-aromatic compounds, or both;
a first separator disposed downstream of the first slurry reactor and configured to separate the first reactor effluent to produce a used mixed metal oxide catalyst and an intermediate stream comprising the light aromatic compounds;
a mesoporous zeolite supported metal catalyst;
a second slurry reactor downstream of the first separator and configured to contact the intermediate stream with hydrogen in the presence of the mesoporous zeolite supported metal catalyst to produce a second reactor effluent comprising aromatic compounds having six to eight carbon atoms; and
a second separator disposed downstream of the second slurry reactor and configured to separate the second reactor effluent to produce a used mesoporous zeolite supported metal catalyst and at least one product effluent comprising aromatic compounds having six to eight carbon atoms.
2 . The system of claim 1 , in which the first separator is directly downstream of the first slurry reactor.
3 . The system of claim 1 , in which the second slurry reactor is directly downstream of the first separator.
4 . The system of claim 1 , in which the used mixed metal oxide catalyst is recycled back to the first slurry reactor.
5 . The system of claim 1 , in which the used mesoporous zeolite supported metal catalyst is recycled back to the second slurry reactor.
6 . The system of claim 1 , wherein plurality of metal oxides of the mixed metal oxide catalyst comprise oxides of metals in groups 3-13 of the International Union of Pure and Applied Chemistry (IUPAC) periodic table.
7 . The system of claim 1 , wherein the plurality of metal oxides in the mixed metal oxide catalyst are selected from the group consisting of iron oxide (Fe 2 O 3 ), zirconium oxide (ZrO 2 ), cerium oxide (CeO 2 ), aluminum oxide (alumina) (Al 2 O 3 ), silica (SiO 2 ), tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), titanium oxide (TiO 2 ), and combinations of these.
8 . The system of claim 1 , wherein the mixed metal oxide catalyst comprises from 60 wt. % to 95 wt. % iron oxide, based on the total weight of the mixed metal oxide catalyst.
9 . The system of claim 1 , wherein the mixed metal oxide catalyst comprises from 1 wt. % to 20 wt. % zirconium oxide, based on the total weight of the mixed metal oxide catalyst.
10 . The system of claim 1 , wherein the mixed metal oxide catalyst comprises from 0.1 wt. % to 10 wt. % cerium oxide, based on the total weight of the mixed metal oxide catalyst.
11 . The system of claim 1 , wherein the mixed metal oxide catalyst comprises from 1 wt. % to 20 wt. % aluminum oxide (Al 2 O 3 ), based on the total weight of the mixed metal oxide catalyst.
12 . The system of claim 1 , wherein the mixed metal oxide catalyst comprises from 60 wt. % to 95 wt. % iron oxide, from 1 wt. % to 20 wt. % zirconium oxide, from 0.1 wt. % to 10 wt. % cerium oxide, and from 1 wt. % to 20 wt. % aluminum oxide (Al 2 O 3 ), based on the total weight of the mixed metal oxide catalyst.
13 . The system of claim 1 , wherein the mixed metal oxide catalyst comprises 83 wt. % iron oxide, 7.5 wt. % zirconium oxide, 2.5 wt. % cerium oxide, and 7.0 wt. % aluminum oxide (Al 2 O 3 ).
14 . The system of claim 1 , wherein the first slurry reactor is configured to contact the pyrolysis oil feed with hydrogen in the presence of the mixed metal oxide catalyst at a temperature of from 300° C. to 500° C. and a pressure of from 1 MPa to 20 MPa.
15 . The system of claim 1 , wherein the mesoporous zeolite supported metal catalyst comprises a first metal catalyst and a second metal catalyst supported on a mesoporous zeolite support.
16 . The system of claim 15 , wherein the first metal catalyst, the second metal catalyst, or both comprises a heteropolyacid.
17 . The system of claim 16 , wherein the heteropolyacid comprises:
at least one metal selected from cobalt, molybdenum, vanadium, or combinations of these; and
at least one heteroatom selected from phosphorous, silicon, arsenic, germanium, or combinations of these.
18 . The system of claim 16 , wherein the heteropolyacid comprises phosphormolybdic heteropolyacid having formula H 3 PMo 12 O 40 , decamolybdodicobaltate heteropolyacid having chemical formula H 6 [Co 2 Mo 10 O 38 H 4 ], or silicomolybdic heterpolyacid having chemical formula H 4 [SiMo 12 O 40 ].
19 . The system of claim 15 , wherein the first metal catalyst comprises a first heteropolyacid and the second metal catalyst comprises a second heteropolyacid that is different from the first heteropolyacid.
20 . The system of claim 1 , wherein the second slurry reactor is configured to contact the light aromatic compounds with hydrogen in the presence of the mesoporous zeolite supported metal catalyst at a temperature of from 300° C. to 500° C. and a pressure of from 1 MPa to 20 MPa.