US 8,912,378 B2Granted

Dehydrocyclodimerization using UZM-39 aluminosilicate zeolite

AssigneeUop LLC

InventorsChristopher P. Nicholas, Mark A. Miller

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Abstract

A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for dehydrocyclodimerization reactions. 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 at least one aliphatic hydrocarbon having from 2 to about 6 carbon atoms per molecule with the coherently grown composites of TUN and IMF zeotypes to produce at least one aromatic hydrocarbon.

Claims18

Dependent claims

A process for dehydrocyclodimerization comprising contacting a feed comprising at least one aliphatic hydrocarbon having from 2 to about 6 carbon atoms per molecule with a microporous crystalline zeolitic catalytic composite at dehydrocyclodimerization conditions to produce at least one aromatic hydrocarbon, the catalytic composite comprising at least 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 as synthesized and anhydrous basis expressed by an empirical formula of:

NanMmk+TtAl1-xExSiyOz
where “n” is the mole ratio of Na to (Al+E) and has a value from approximately 0.05 to 0.5, M represents at least one metal selected from the group consisting of zinc, Group 1 (IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3), and 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 from 3 to 6 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 about 0.5 to about 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 is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A1:
TABLE A1
2θ
d (Å)
I/Io %
7.17-7.21
12.25-12.31
vw-m
7.5-8.1*
11.78-10.91
w-m
8.88
9.95
m
9.17
9.63
w-m
12.47-12.62
7.09-7.00
w-m
17.7
5.01
vw-m
22.8-23.2
3.90-3.83
vs
23.39-23.49
3.80-3.78
m-s
25.01-25.31
3.56-3.52
m
28.74-29.25
3.10-3.05
w-m
45.08-45.29
2.01-2.00
w.
*composite peak consisting of multiple overlapping reflections

39 more elements

A process for dehydrocyclodimerization comprising contacting a feed comprising at least one aliphatic hydrocarbon having from 2 to about 6 carbon atoms per molecule with a microporous crystalline zeolitic catalytic composite at dehydrocyclodimerization conditions to produce at least one aromatic hydrocarbon, the catalytic composite comprising at least 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 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

45 more elements

Dependencies are inferred from the claim text.

Facts

Application: 14/102,523Filed 11 Dec 2013 · us provisional application
Priority: 12 Dec 2012
Published: US 2014/0163276 A112 Jun 2014
Granted: 16 Dec 2014
Term ends: Not estimatedThe source records don’t support an estimate.

Classification31 codes

B01J 29/80
Crystalline aluminosilicate zeolites; Isomorphous compounds thereof: mixtures of different zeolites
B01J 29/70
Crystalline aluminosilicate zeolites; Isomorphous compounds thereof: of types characterised by their specific structure not provided for in groups…
B01J 29/76
Containing iron group metals, noble metals or copper: iron group metals or copper
B01J 35/30
Catalysts, in general, characterised by their form or physical properties: characterised by their physical properties