Catalytic pyrolysis using UZM-39 aluminosilicate zeolite
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. Na n M m n+ R r Q q Al 1-x E x Si y O z 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.
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 AlO 2 and SiO 2 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
M1 a N+ Al (1-x) E x Si y′ O z″
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 ′)/2
and 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 C 2/m and orthorhombic C mcm 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 B1
2θ
d (Å)
I/Io %
7.11-7.16
12.42-12.25
vw-m
7.5-8.1*
11.78-10.91
m-s
8.84
10.00
m-s
9.06-9.08
9.75-9.73
w-m
9.24
9.56
vw-m
12.46-12.53
7.10-7.06
w-m
22.56
3.94
vw-m
22.75-23.2
3.90-3.83
vs
23.40
3.80
m-s
24.12-24.23
3.69-3.67
w-m
24.92-25.37
3.57-3.51
m
28.71-29.27
3.11-3.05
w-m
45.32-45.36
2.00
w
*composite peak consisting of multiple overlapping reflections
2. The process of claim 1 wherein the hydrocarbons produced include aromatic compounds and the selectivity to aromatic compounds within the condensable portion of the pyrolysis gases is greater than 33% by weight.
3. The process of claim 1 wherein the hydrocarbons produced include aromatic compounds and the selectivity to aromatic compounds within the condensable portion of the pyrolysis gases is greater 50% by weight.
4. The process of claim 1 wherein the hydrocarbons produced include aromatic compounds and the yield of aromatic compounds is greater than 2% by weight based upon the biomass.
5. The process of claim 1 wherein the hydrocarbons produced include aromatic compounds and the yield of aromatic compounds is greater than 3% by weight based upon biomass.
6. The process of claim 1 wherein the pyrolysis conditions include a temperature from about 300° C. to about 800° C.
7. The process of claim 1 wherein the catalyst is in a fluidized state.
8. The process of claim 1 wherein the contacting a carbonaceous biomass feedstock with a microporous crystalline zeolitic catalyst is carried out using a catalyst-to-carbonaceous biomass feedstock ratio of about 0.1 to about 200.
9. The process of claim 1 wherein the coherently grown composite of TUN and IMF zeotypes is thermally stable up to a temperature of greater than 600° C.
10. The process of claim 1 wherein the coherently grown composite of TUN and IMF zeotypes has a micropore volume as a percentage of total pore volume of greater than 60%.
11. The process of claim 1 wherein the microporous crystalline zeolitic catalyst comprises the heat transfer medium of a fast pyrolysis process.
12. The process of claim 1 further comprising regenerating the catalyst after contacting with the feedstock to form a regenerated catalyst and recycling the regenerated catalyst to the contacting step.
13. 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 AlO 2 and SiO 2 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
M1 a N+ Al (1-x) E x Si y′ O z″
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 O to (Al+E) and has a value determined by the equation:
z ″=( a·N+ 3+4 ·y′ )/2
and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table B1:
TABLE B1
2θ
d (Å)
I/Io %
7.11-7.16
12.42-12.25
vw-m
7.5-8.1*
11.78-10.91
m-s
8.84
10.00
m-s
9.06-9.08
9.75-9.73
w-m
9.24
9.56
vw-m
12.46-12.53
7.10-7.06
w-m
22.56
3.94
vw-m
22.75-23.2
3.90-3.83
vs
23.40
3.80
m-s
24.12-24.23
3.69-3.67
w-m
24.92-25.37
3.57-3.51
m
28.71-29.27
3.11-3.05
w-m
45.32-45.36
2.00
w
*composite peak consisting of multiple overlapping reflections
14. The process of claim 13 wherein the catalyst is further 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 C 2/m and orthorhombic C mcm unit cells for TUN and IMF respectively.
15. A process for producing low oxygen biomass-derived pyrolysis oil comprising pyrolyzing 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 AlO 2 and SiO 2 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
M1 a N+ Al (1-x) E x Si y′ O z″
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 ′)/2
and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table B1:
TABLE B1
2θ
d (Å)
I/Io %
7.11-7.16
12.42-12.25
vw-m
7.5-8.1*
11.78-10.91
m-s
8.84
10.00
m-s
9.06-9.08
9.75-9.73
w-m
9.24
9.56
vw-m
12.46-12.53
7.10-7.06
w-m
22.56
3.94
vw-m
22.75-23.2
3.90-3.83
vs
23.40
3.80
m-s
24.12-24.23
3.69-3.67
w-m
24.92-25.37
3.57-3.51
m
28.71-29.27
3.11-3.05
w-m
45.32-45.36
2.00
w
*composite peak consisting of multiple overlapping reflections
16. The process of claim 15 wherein the catalyst is further 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 C 2/m and orthorhombic C mcm unit cells for TUN and IMF respectively.
17. The process of claim 15 wherein the coherently grown composite of TUN and IMF zeotypes has a micropore volume as a percentage of total pore volume of greater than 60%.
18. The process of claim 15 wherein the microporous crystalline zeolitic catalyst comprises the heat transfer medium of a fast pyrolysis process.
19. The process of claim 15 further comprising regenerating the catalyst after contacting with the feedstock to form a regenerated catalyst and recycling the regenerated catalyst to the contacting step.