| 摘要 |
A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula.
NanMmn+RrQqAl1-xExSiyOz
where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,Ω-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil. |
| 主权项 |
1. A process for producing low oxygen biomass-derived pyrolysis oil comprising contacting a carbonaceous biomass feedstock with a microporous crystalline zeolitic catalyst at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons, the catalyst catalyzing a deoxygenation reaction converting at least a portion of the oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water; and condensing a condensable portion of the pyrolysis gases to produce low oxygen biomass-derived pyrolysis oil; wherein the catalyst comprises a coherently grown composite of TUN and IMF zeotypes having a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units and an empirical composition in the hydrogen form after calcination, ion-exchange and calcination and on an anhydrous basis expressed by an empirical formula of
M1aN+Al(1-x)ExSiy′Oz″and where M1 is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metals, rare earth metals, zinc, ammonium ion, hydrogen ion and combinations thereof, “a” is the mole ratio of M1 to (Al+E) and varies from about 0.05 to about 50, “N” is the weighted average valence of M1 and has a value of about +1 to about +3, E is an element selected from the group consisting of gallium, iron, boron, and combinations thereof, “x” is the mole fraction of E and varies from 0 to 1.0, y′ is the mole ratio of Si to (Al+E) and varies from greater than about 9 to virtually pure silica and z″ is the mole ratio of 0 to (Al+E) and has a value determined by the equation:
z″=(a·N+3+4·y′)/2and is characterized in that it has TUN regions and IMF regions that are coherently aligned so that the [010]TUN zone axis and the [001]IMF zone axis are parallel to each other and there is continuity of crystal planes of type (002)TUN and (060)IMF, where the indexing is referred to monoclinic C2/m and orthorhombic Cmcm unit cells for TUN and IMF respectively
wherein the catalyst is further characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table B1:TABLE B12θd (Å)I/Io %7.11-7.1612.42-12.25vw-m 7.5-8.1*11.78-10.91m-s 8.8410.00m-s9.06-9.089.75-9.73w-m 9.24 9.56vw-m12.46-12.537.10-7.06w-m22.56 3.94vw-m22.75-23.2 3.90-3.83vs23.40 3.80m-s24.12-24.233.69-3.67w-m24.92-25.373.57-3.51m28.71-29.273.11-3.05w-m45.32-45.36 2.00w*composite peak consisting of multiple overlapping reflections |
