Catalytic pyrolysis using UZM-44 aluminosilicate zeolite
A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula. Na n M m k+ T t Al 1-x E x Si y O z where “n” is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, “m” is the mole ratio of M to (Al+E), “k” is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 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. a microporous crystalline zeolite, UZM-44, having a three-dimensional framework of at least AlO 2 and SiO 2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
Na n M m k+ T t Al 1-x E x Si y O z
where “n” is the mole ratio of Na to (Al+E) and has a value from approximately 0.05 to 0.5, M represents a metal or metals selected from the group consisting of zinc, Group 1 (IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3), the lanthanide series of the periodic table, and any combination thereof, “m” is the mole ratio of M to (Al+E) and has a value from 0 to 0.5, “k” is the average charge of the metal or metals M, T is the organic structure directing agent or agents derived from reactants R and Q where R is an A,Ω-dihalogen substituted alkane having 5 carbon atoms and Q is at least one neutral monoamine having 6 or fewer carbon atoms, “t” is the mole ratio of N from the organic structure directing agent or agents to (Al+E) and has a value of from 0.5 to 1.5, E is an element selected from the group consisting of gallium, iron, boron and combinations thereof, “x” is the mole fraction of E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than 9 to about 25 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z =( n+k·m+ 3+4 ·y )/2
b.
and
wherein the microporous crystalline zeolite, UZM-44, is further characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A:
TABLE A
2-Theta
d(†)
I/Io %
7.72
11.45
m
8.88
9.95
m
9.33
9.47
m
12.47
7.09
w-m
12.85
6.88
vw
14.62
6.05
vw-w
15.27
5.80
w
15.57
5.68
w
16.60
5.34
w
17.70
5.01
vw-w
18.71
4.74
w-m
19.30
4.59
w
22.55
3.94
m
23.03
3.86
vs
23.39
3.80
s
24.17
3.68
m
25.01
3.56
m
26.19
3.40
vw-w
26.68
3.34
w-m
28.76
3.10
w-m
30.07
2.97
w
35.72
2.51
vw-w
45.08
2.01
w
45.83
1.98
vw-w
46.77
1.94
vw-w.
2. The process of claim 1 wherein the microporous crystalline zeolitic catalyst is thermally stable up to a temperature of greater than 600° C.
3. The process of claim 1 wherein the microporous crystalline zeolitic catalyst has a micropore volume as a percentage of total pore volume of less than 60%.
4. The process of claim 1 wherein the microporous crystalline zeolitic catalyst has a micropore volume of less than 0.155 mL/g.
5. The process of claim 1 wherein the microporous crystalline zeolitic catalyst has micropore volume of less than 0.150 mL/g.
6. The process of claim 1 wherein the microporous crystalline zeolitic catalyst exhibits no feature at 200-300 Å on a dV/dlog D versus pore diameter plot of differential volume of nitrogen adsorbed as a function of pore diameter.
7. The process of claim 1 wherein the microporous crystalline zeolitic catalyst exhibits an adsorption feature occurring at greater than 450 Å on a dV/dlog D versus pore diameter plot of differential volume of nitrogen adsorbed as a function of pore diameter.
8. The process of claim 1 wherein the differential volume of nitrogen adsorbed by the microporous crystalline zeolitic catalyst at a pore diameter of 475 Å is greater than 00.1 mL N 2 /gÅ on a dV/dlog D versus pore diameter plot of differential volume of nitrogen adsorbed as a function of pore diameter.
9. The process of claim 1 wherein the differential volume of nitrogen adsorbed by the microporous crystalline zeolitic catalyst at pore diameters greater than 475 Å is greater than 0.1 mL N 2 /gÅ on a dV/dlog D versus pore diameter plot of differential volume of nitrogen adsorbed as a function of pore diameter.
10. 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.
11. 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 50% by weight.
12. 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.
13. 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.
14. The process of claim 1 wherein the pyrolysis conditions include a temperature from about 300° C. to about 800° C.
15. The process of claim 1 wherein the catalyst is in a fluidized state.
16. The process of claim 1 wherein the step of contacting the carbonaceous biomass feedstock with a microporous crystalline zeolitic catalyst at pyrolysis conditions is carried out at a catalyst-to-carbonaceous biomass feedstock ratio of about 0.1 to about 200.
17. The process of claim 1 wherein the microporous crystalline zeolitic catalyst comprises the heat transfer medium for a fast pyrolysis process.
18. A process for producing low oxygen biomass-derived pyrolysis oil comprising pyrolyzing a carbonaceous biomass feedstock by contacting the 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. a microporous crystalline zeolite, UZM-44, having a three-dimensional framework of at least AlO 2 and SiO 2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
Na n M m k+ T t Al 1-x E x Si y O z
where “n” is the mole ratio of Na to (Al+E) and has a value from approximately 0.05 to 0.5, M represents a metal or metals selected from the group consisting of zinc, Group 1 (IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3), the lanthanide series of the periodic table, and any combination thereof, “m” is the mole ratio of M to (Al+E) and has a value from 0 to 0.5, “k” is the average charge of the metal or metals M, T is the organic structure directing agent or agents derived from reactants R and Q where R is an A,Ω-dihalogen substituted alkane having 5 carbon atoms and Q is at least one neutral monoamine having 6 or fewer carbon atoms, “t” is the mole ratio of N from the organic structure directing agent or agents to (Al+E) and has a value of from 0.5 to 1.5, E is an element selected from the group consisting of gallium, iron, boron and combinations thereof, “x” is the mole fraction of E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than 9 to about 25 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z =( n+k·m+ 3+4 ·y )/2
and
wherein the macroporous crystalline zeolite, UZM-44, is further characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A:
TABLE A
2-Theta
d(†)
I/Io %
7.72
11.45
m
8.88
9.95
m
9.33
9.47
m
12.47
7.09
w-m
12.85
6.88
vw
14.62
6.05
vw-w
15.27
5.80
w
15.57
5.68
w
16.60
5.34
w
17.70
5.01
vw-w
18.71
4.74
w-m
19.30
4.59
w
22.55
3.94
m
23.03
3.86
vs
23.39
3.80
s
24.17
3.68
m
25.01
3.56
m
26.19
3.40
vw-w
26.68
3.34
w-m
28.76
3.10
w-m
30.07
2.97
w
35.72
2.51
vw-w
45.08
2.01
w
45.83
1.98
vw-w
46.77
1.94
vw-w.