Methods for producing mesoporous zeolite multifunctional catalysts for upgrading pyrolysis oil
A method of making a multifunctional catalyst for upgrading pyrolysis oil includes contacting a hierarchical mesoporous zeolite support with a solution including at least a first metal catalyst precursor and a second metal catalyst precursor, each or both of which may include a heteropolyacid. The hierarchical mesoporous zeolite support may have an average pore size of from 2 nm to 40 nm. Contacting the hierarchical mesoporous 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 hierarchical mesoporous zeolite support to produce a multifunctional catalyst precursor. The method further includes removing excess solution 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 hierarchical mesoporous zeolite support.
1. A multifunctional catalyst for upgrading pyrolysis oil produced by a method comprising:
contacting a hierarchical mesoporous zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor, where:
the hierarchical mesoporous zeolite support has an average pore size of from 2 nanometers to 40 nanometers as determined by Barrett-Joyner-Halenda (BJH) analysis;
the first metal catalyst precursor, the second metal catalyst precursor, or both, comprises a heteropolyacid having at least one heteroatom selected from the group consisting of phosphorous, silicon, germanium, arsenic, or combinations of these; and
the contacting deposits the first metal catalyst precursor and the second metal catalyst precursor onto outer surfaces and pore surfaces of the hierarchical mesoporous 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 comprising at least a first metal catalyst and a second metal catalyst deposited on the outer surfaces and pore surfaces of the hierarchical mesoporous zeolite support.
2. The multifunctional catalyst of claim 1 , in which the first metal catalyst is the heteropolyacid and comprises molybdenum and the second metal catalyst comprises cobalt.
3. The multifunctional catalyst of claim 1 , where the multifunctional catalyst has an acidity of less than 15,000 micromoles of ammonia per gram (μmol(NH 3 )/g).
4. The multifunctional catalyst of claim 1 , where the multifunctional catalyst has an acidity of less than 15,000 micromoles of ammonia per gram (μmol(NH 3 )/g).
5. The multifunctional catalyst of claim 1 , in which the hierarchical mesoporous zeolite support comprises a hierarchical mesoporous beta zeolite support.
6. The multifunctional catalyst of claim 1 , in which the hierarchical mesoporous zeolite support has a total pore volume of greater than or equal to 0.35 cubic centimeters per gram.
7. The multifunctional catalyst of claim 1 , in which the hierarchical mesoporous zeolite support comprises a molar ratio of silica to alumina of from 20 to 100.
8. The multifunctional catalyst of claim 1 , in which the hierarchical mesoporous zeolite support has an average pore size of from 5 nanometers to 25 nanometers as determined by BJH analysis.
9. The multifunctional catalyst of claim 1 , in which the first heteropolyacid or the second heteropolyacid is H 3 PMo 12 O 40 .
10. The multifunctional catalyst of claim 1 , in which removing the excess solution from the multifunctional catalyst precursor comprises filtering or decanting the excess solution from the multifunctional catalyst precursor and drying the multifunctional catalyst precursor to remove solvent.
11. The multifunctional catalyst of claim 1 , in which the multifunctional catalyst comprises phosphorous deposited on the outer surfaces and pore surfaces of the hierarchical mesoporous zeolite support.