new zeolites for methanol tonew zeolites ......• tridirectional large pore zeolite • micropore...
TRANSCRIPT
NEW ZEOLITES FOR METHANOL TONEW ZEOLITES FOR METHANOL TO OLEFINS AND GAS SEPARATION
PROCESSESPROCESSES.
Main researchers: Prof. Takashi Tatsumi and Prof. Fernando Reyy
Tokyo Institute of Technology, Yokohama, Japan (TITECH)Instituto de Tecnología Química (CSIC-UPV) Valencia Spain (ITQ)Instituto de Tecnología Química (CSIC-UPV) Valencia, Spain (ITQ)
MOTIVATION OF THE PROJECTMOTIVATION OF THE PROJECT
PORES OF MOLECULAR DIMENSIONSM l l iMolecular sieves
FaujasiteChabazite ZSM-510 TO 12 TO2
7.4 x 7.4 Å8 TO2
3.8 x 3.8 Å10 TO2
5.5 x 5.1 Å
MOTIVATION OF THE PROJECTMOTIVATION OF THE PROJECT
Zeolites can select moleculesZeolites can select moleculesZeolites can select molecules Zeolites can select molecules accessing or leaving their voids.accessing or leaving their voids.
MOLECULAR SIEVESMOLECULAR SIEVESMOLECULAR SIEVESMOLECULAR SIEVES
MOTIVATION OF THE PROJECTMOTIVATION OF THE PROJECT
Zeolites can select moleculesZeolites can select moleculesZeolites can select molecules Zeolites can select molecules accessing or leaving their voids. accessing or leaving their voids.
SeparationSeparation CatalysisCatalysisyy
SHAPE SELECTIVITY OF ZEOLITES
Toluene alkylation with ethanol to ethyl-tolueneToluene alkylation with ethanol to ethyl toluene
o-ethyl-toluene
+Zeolita
m-ethyl-toluene+
p-ethyl-toluenetoluene ethanol
PORES OF MOLECULAR DIMENSIONSM l l iMolecular sieves
Zeolite Beta ZSM-5
Para 2 01 6 36Para 2.01 6.36
Meta 2.36 0.83Yiel
dY
Ortho 2.29 0.20
p/o ratio 0 87 32 13ZSM-510 TO
p/o ratio 0.87 32.13
10 TO25.5 x 5.1 Å
GAS SEPARATION USING ZEOLITES
8 MRZeolite A 8 MRITQ-29
Isobutene 1-butene
GAS SEPARATION USING ZEOLITES
GAS SEPARATION USING ZEOLITES
Hideki OnoNippon Oil
Number of Zeolitic Structures
206 structures
SYNTHESIS OF ZEOLITES
Silica Structure directingSilica Structure directingWater agents
Zeolite
Temperature, time
SYNTHESIS OF ZEOLITES
Silica Structure directing
Zeolite
Silica Structure directingWater agents
Temperature, time
STRUCTURE DIRECTING AGENTS
S bili i ff f hStabilizing effect of thestructure directing agent.
Van der Waals
Filling of the empty space
M i d ki
ZSM-5 – TPA+Maximum docking.
CALCINATION PROCESS OF AS-MADE ZEOLITES
C l i tiCalcination
CALCINATION PROCESS OF AS-MADE ZEOLITES
C l i tiCalcination
CO2
H2O
NOx
Calcination
x
WHAT CAN WE DO ABOUT THE STRUCTURE DIRECTING AGENTS?STRUCTURE DIRECTING AGENTS?
• We can avoid its use. This is the most preferred choicep
• The SDA could introduce new functionalities in the final zeoliteThe SDA could introduce new functionalities in the final zeolite
WHAT CAN WE DO ABOUT THE STRUCTURE DIRECTING AGENTS?STRUCTURE DIRECTING AGENTS?
• We can avoid its use. This is the most preferred choicepTITECH (JAPAN)
• The SDA could introduce new functionalities in the final zeoliteThe SDA could introduce new functionalities in the final zeoliteITQ (SPAIN)
Arranged during our kick-off meeting in April 2010 at TITECHg g g p
WHAT CAN WE DO ABOUT THE STRUCTURE DIRECTING AGENTS?STRUCTURE DIRECTING AGENTS?
• We can avoid its use. This is the most preferred choicepTITECH (JAPAN)
• The SDA could introduce new functionalities in the final zeoliteThe SDA could introduce new functionalities in the final zeoliteITQ (SPAIN)
Arranged during our kick-off meeting in April 2010 at TITECHg g g p
CAN WE TAKE ANY PROFIT FROM THE SDA?
C l i ti
CO2
H OCalcination H2O
NOx
CAN WE TAKE ANY PROFIT FROM THE SDA?
CO2
H2OC l i ti
MOx
Calcination
CAN WE TAKE ANY PROFIT FROM THE SDA?
COCO2
H2OCalcination
MOx
Calcination
Calcination
CAN WE TAKE ANY PROFIT FROM THE SDA?
CO2
H2OC l i ti
MOx
Calcination
MOXX….
P2O5
SiO2
2 5
CAN WE TAKE PROFIT FROM THE SDA?
CO2
H2OC l i ti
MOx
Calcination
MOX….
P OSiO2
P2O5
P-CONTAINING STRUCTURE DIRECTING AGENTS
CO2
H2OC l i ti
MOx
Calcination
MOX….[P(i-Pr)4]+
P OSiO2
P2O5
P-CONTAINING STRUCTURE DIRECTING AGENTS
TETRAALKYLPHOSPHONIUM TETRAALKYLPHOSPHONIUM CATIONS:CATIONS:
•• PhosphinesPhosphines are more reactive than amines.are more reactive than amines.•• Tetraalkylphosphonium cations Tetraalkylphosphonium cations interact to silica interact to silica
i t li t l th lth lspecies more strongly species more strongly than analogous than analogous tetraalkylammoniumtetraalkylammonium cationscations..
This work was partially done in collaboration with EXXONThis work was partially done in collaboration with EXXON--MOBILMOBIL
P-CONTAINING STRUCTURE DIRECTING AGENTS
TETRAALKYLPHOSPHONIUM CATIONSTETRAALKYLPHOSPHONIUM CATIONSTETRAALKYLPHOSPHONIUM CATIONS:TETRAALKYLPHOSPHONIUM CATIONS:
ITQ-27ITQ 27
• Bidirectional large pore zeolite• Bidirectional large pore zeolite• Micropore volume: 0.21 cc/g• Pore openning: 12MR = 6.2 x 6.9 A
Projection along [1 0 0]p g
14MR = 8.5 x 7.2 AStrohmaier, Dorset, Kennedy, Corma, Diaz-Cabañas, Rey; in WO2006/055305 and J. Am. Chem. Soc., 128, 8862 (2006)
P-CONTAINING STRUCTURE DIRECTING AGENTS
TETRAALKYLPHOSPHONIUM CATIONS:TETRAALKYLPHOSPHONIUM CATIONS:
ITQ-26
PP PP
• Tridirectional large pore zeolite• Micropore volume: 0.20 cc/g• Pore openning: 12MR = 7.8 x 6.8 A
12MR sinusoidal = 7 1 x 6 6 A
Projection along [1 0 0]
12MR sinusoidal = 7.1 x 6.6 AStrohmaier, Dorset, Kliewer, Corma, Diaz-Cabañas, Rey; in WO2007/075382 A1Dorset,. Strohmaier, Kliewer, Corma, Diaz-Cabanas, Rey, Gilmore, Chem. Mater., 20, 5323 (2008)
P-CONTAINING STRUCTURE DIRECTING AGENTS
ITQ-34
T idi ti l di lit
ITQ-34Projection along [1 0 0]• Tridirectional medium pore zeolite
• Micropore volume: 0.15 cc/g• Pore openning: 10MR = 6 0 x 4 9 A
Projection along [1 0 0]
• Pore openning: 10MR = 6.0 x 4.9 A10MR sinusoidal = 5.3 x 4.7 A9MR sinusoidal = 4.9 x 4.1 A
Corma, Rey, Díaz, Jordá, PCT WO 2008/073237 A2Corma, Diaz-Cabanas, Jorda, Rey, Sastre, Strohmaier, J. Am. Chem. Soc. 130, 16482 (2008)Corma,.Diaz Cabañas, Jorda, Rey, Boulahya, Gonzalez-Calbet, J. Phys. Chem. C, 113, 9305 (2009)
P-CONTAINING STRUCTURE DIRECTING AGENTS
Shape Porous structureSpherical Cages (Clathrasils or 8R zeolites)Lineal/cylindrical Unidirectional h l tLineal/cylindrical Unidirectional channel systemsBranched Tridirectional channel systems
P-CONTAINING STRUCTURE DIRECTING AGENTS
Shape Porous structureSpherical Cages (Clathrasils or 8R zeolites)Lineal/cylindrical Unidirectional h l tLineal/cylindrical Unidirectional channel systemsBranched Tridirectional channel systems
P-CONTAINING STRUCTURE DIRECTING AGENTS
Shape Porous structureSpherical Cages (Clathrasils or 8R zeolites)Lineal/cylindrical Unidirectional h l tLineal/cylindrical Unidirectional channel systemsBranched Tridirectional channel systems
Zeolitic materials as catalysts for MTO process
Commercial catalystsSAPO-34 for olefin production
Commercial catalystsZSM-5 for C4+ production
P-CONTAINING STRUCTURE DIRECTING AGENTS
Shape Porous structureSpherical Cages (Clathrasils or 8R zeolites)Lineal/cylindrical Unidirectional h l tLineal/cylindrical Unidirectional channel systemsBranched Tridirectional channel systems
Zeolitic materials as catalysts for MTO process
Commercial catalystsSAPO-34 for olefin production
Commercial catalysts
8R ZEOLITES SPECIALLY WELL SUITED FOR MTOZSM-5 for C4+ production
8R-ZEOLITES SPECIALLY WELL SUITED FOR MTO
P-CONTAINING STRUCTURE DIRECTING AGENTS
Shape Porous structureSpherical Cages (Clathrasils or 8R zeolites)Lineal/cylindrical Unidirectional h l tLineal/cylindrical Unidirectional channel systemsBranched Tridirectional channel systems
P
P-CONTAINING STRUCTURE DIRECTING AGENTS
RUB-13
• Bidirectional small pore zeolite Cavity of RUB-13
p• Micropore volume: 0.19 cc/g• Pore openning: 8MR = 41. x 3.8 A
8MR = 5.6 x 2.5 ARelatively large cavities
P-CONTAINING STRUCTURE DIRECTING AGENTS
Si/Al Al/P P(wt%)Inf. 0 2.7Inf. 0 2.7
23 0.33 2.6
18 0 80 2 718 0.80 2.7
13 1.01 2.95 10 15 20 25 30 35 40
2 (degrees)
P-CONTAINING STRUCTURE DIRECTING AGENTS
31P MAS NMRAs-made RUB-13 Calcined RUB-13
* Spinning sidebands
* *p g
Si/Al=13
* *Si/Al=18
* *
Si/Al 18
100 80 60 40 20 0 100 60 20 20 60 100
*Si/Al=23
100 80 60 40 20 031P (ppm)
100 60 20 -20 -60 -10031P (ppm)
P-CONTAINING STRUCTURE DIRECTING AGENTS
27Al MAS NMRAs-made RUB-13 Calcined RUB-13
Si/Al=13
Si/Al=18
120 80 40 0 40 120 80 40 0 -40 -80
Si/Al=23120 80 40 0 -40
27Al (ppm)120 80 40 0 -40 -80
27Al (ppm)
P-CONTAINING STRUCTURE DIRECTING AGENTS
Calcination of P-SDA-RUB-13 zeolites
P-CONTAINING STRUCTURE DIRECTING AGENTS
IR spectroscopy(OH region)
calcined
3900 3750 3600 3450 3300
calcined
3900 3750 3600 3450 3300Wavenumber (cm-1)
P-CONTAINING STRUCTURE DIRECTING AGENTS
IR spectroscopy(OH region)
No acid Si-OH-Al sites
calcined
3900 3750 3600 3450 3300
calcined
3900 3750 3600 3450 3300Wavenumber (cm-1)
P-CONTAINING STRUCTURE DIRECTING AGENTS
Calcination of P-SDA-RUB-13 zeolitesCalcination of P SDA RUB 13 zeolites
HH2
P-CONTAINING STRUCTURE DIRECTING AGENTS
IR spectroscopy(OH region)
HSi-O-Al
H
reduced
calcinedcalcined
3900 3750 3600 3450 33003900 3750 3600 3450 3300Wavenumber (cm-1)
P-CONTAINING STRUCTURE DIRECTING AGENTS
27Al MAS NMR
reducedreduced
calcined
120 80 40 0 40
as- made
120 80 40 0 -40 (ppm)
P-CONTAINING STRUCTURE DIRECTING AGENTS
Recovering of the PH3Recovering of the PH3
HH2
P-CONTAINING STRUCTURE DIRECTING AGENTS
Recovering of the PH3Recovering of the PH3
HH2
I-iPrI iPr
P-CONTAINING STRUCTURE DIRECTING AGENTS
Recovering of the PH3Recovering of the PH3
HH2
I-iPrI iPr
P-CONTAINING STRUCTURE DIRECTING AGENTS
Application of P-containing RUB-13Application of P containing RUB 13
Methanol to olefins reactionCommercial catalysts: ZSM-5 (10R) and SAPO-34 (8R)
P-CONTAINING STRUCTURE DIRECTING AGENTS
MTO PROCESSMTO PROCESS
P-CONTAINING STRUCTURE DIRECTING AGENTS
Prof. Tatsumi
P-CONTAINING STRUCTURE DIRECTING AGENTS
Methanol to olefins reaction on P RUB 13
Olefin Distribution (Conversion level: 90 100%)
Methanol to olefins reaction on P-RUB-13
60
Olefin Distribution (Conversion level: 90-100%)
Reaction conditions
40
50
ity
Catalyst: 100mg, WHSV = 0.5h-1, Temperature: 400ºC
20
30
wt%
selectivi
RUB‐13
CHA
SAPO‐34
10
20w
ZSM‐5
0
C1 C2 C3 C4 C5+
P-CONTAINING STRUCTURE DIRECTING AGENTS
Methanol to olefins reaction on P RUB 13Catalyst stability
Methanol to olefins reaction on P-RUB-13y y
P-CONTAINING STRUCTURE DIRECTING AGENTS
Methanol to olefins reaction on P RUB 13Catalyst stability
Methanol to olefins reaction on P-RUB-13y y
Catalyst stability increasesy ywith the Al content
Si/Al %P P/Al10.54 3.09 0.7917 20 3 02 1 2117.20 3.02 1.2144.22 3.02 3.00
P-CONTAINING STRUCTURE DIRECTING AGENTS
Methanol to olefins reaction on P RUB 13Catalyst stability
Methanol to olefins reaction on P-RUB-13y y
Catalyst stability increasesy ywith the Al content
Si/Al %P P/Al10.54 3.09 0.7917 20 3 02 1 2117.20 3.02 1.2144.22 3.02 3.00
P-CONTAINING STRUCTURE DIRECTING AGENTS
Methanol to olefins reaction on P RUB 13Catalyst stability
Methanol to olefins reaction on P-RUB-13y y
Catalyst stability increasesy ywith the Al content
Si/Al %P P/Al10.54 3.09 0.7917 20 3 02 1 2117.20 3.02 1.2144.22 3.02 3.00
P-CONTAINING STRUCTURE DIRECTING AGENTS
Application of P-containing RUB-13Application of P containing RUB 13
Methanol to olefins reaction
P-CONTAINING STRUCTURE DIRECTING AGENTS
Application of P-containing RUB-13Application of P containing RUB 13
Methanol to olefins reaction
P-CONTAINING STRUCTURE DIRECTING AGENTS
Methanol to olefins reaction on P RUB 13Methanol to olefins reaction on P-RUB-13
P-CONTAINING STRUCTURE DIRECTING AGENTS
50Calcined Reduced
40
50
40
50
30
40
ity (%
)
30ity (%
)
20
Sele
ctiv
i
20
Sele
ctiv
10 10
Si/Al = 17 Si/Al = 450
Si/Al = 17 Si/Al = 450
C2= C3
= C4= C2-C3 paraffins C4 paraffins C5+
P-CONTAINING STRUCTURE DIRECTING AGENTS
Calcined P-SDA-RUB-13 zeolitesCa c ed S U 3 eo tes
Phosphate species are entrapped inside the inner cavities of RUB 13 Phosphate species are entrapped inside the inner cavities of RUB-13
Aluminium sites interact to phosphate anions
Thi i t ti d lit idit i Al ZSM 5 h This interaction decreases zeolite acidity as occurs in Al-ZSM-5 when treated with phosphate solutions.
Reduction allows to develop the full acidity of the Al-RUB-13 catalysts. p y y
CH4 separation from Natural GasCH4 separation from Natural Gas
NATURAL GAS UPGRADINGNATURAL GAS UPGRADING
CH4 separation from Natural GasCH4 separation from Natural Gas
CO2 adsorption CH4 adsorption
CH4 separation from Natural GasCH4 separation from Natural Gas
CO2 /CH4 selectivity
CH4 separation from Natural GasCH4 separation from Natural Gas
CO2 /CH4 selectivity
3
CH4 separation from Natural GasCH4 separation from Natural Gas
CO2 /CH4 selectivity
CH4 separation from Natural GasCH4 separation from Natural Gas
Silica Structure directing
Zeolite
Silica Structure directingWater agents
Temperature, time
CH4 separation from Natural GasCH4 separation from Natural Gas
NaOHSilica Structure directing
NaOH
Zeolite
Silica Structure directingWater agents
Temperature, time
CH4 separation from Natural GasCH4 separation from Natural Gas
CO2 /CH4 selectivity
CO2 /CH4 SEPARATION CAN BE DONE USING A COST EFFECTIVE
ZEOLITIC ADSORBENTZEOLITIC ADSORBENT
CH4 Purification from Natural GasCH4 Purification from Natural Gas
Zeolite RHO
P di t 3 6 3 6 ÅPore diameter = 3.6 3.6 ÅSi/Al ~ 5
CH4 Purification from Natural GasCH4 Purification from Natural Gas
Zeolite RHO6
7
CO
g)
4
5
6 CO2
ed (m
mol
/g2
3
4
unt a
dsor
be
SelCO2/CH4 > 10
P di t 3 6 3 6 Å 0 100 200 300 400 5000
1 CH4amou
Zeolite RHO gives the highest selectivity large CO
Pore diameter = 3.6 3.6 ÅSi/Al ~ 5
0 100 200 300 400 500
P (kPa)
Zeolite RHO gives the highest selectivity, large CO2
adsorption capacity and reasonable regenerability
Possible scheme for CH4 purificationf N t l Gfrom Natural Gas
TEC
H
CO B-1
3-TI
T
CO2
Al-R
UB
A
Possible scheme for CH4 purificationf N t l Gfrom Natural Gas
ITQ
TEC
H
RH
O-I
B-1
3-TI
TA
l-RU
BA
SOME OTHER RESULTSSOME OTHER RESULTS
P-OSDA: New zeolite ITQ-49
Cavidades (18.3 Å x 5.8 Å) con entradas 7R (3.7 Å x2.2 Å) y 8R (5.0 Å x3.6 Å). Interior con 10R (5.8 Å x5.5 Å).
P-OSDA: New zeolite ITQ-45
¿OH?
10R along c (6.0Å x 5.1Å), coneccting cavities, also conected through 8R (4.4 Å x 3.6 Å) along ab.
P-OSDA: New zeolite ITQ-52
10R along b (6.0Å x 5.1Å), crossed by 8R (4.4 Å x 3.6 Å) along ac.
SYNTHESIS OF BOGGSITE
BoggsiteBoggsiteoggs teoggs te
SYNTHESIS OF BOGGSITE
Simancas, et al., Science 330, 1219 (2010)
Thi d d ith th P iThis paper was awarded with the Prize:
‘La La VanguardiaVanguardia de la de la CienciaCiencia 20102010’
to the best Spanish Scientific Publication along 2010.
There are benefits in using PThere are benefits in using P--containingcontainingstructure directing agents that deserve to bestructure directing agents that deserve to be
studied.studied.
It could allow to obtain new zeolites withIt could allow to obtain new zeolites withIt could allow to obtain new zeolites withIt could allow to obtain new zeolites withunseen adsorption and catalytic propertiesunseen adsorption and catalytic properties