NEW ZEOLITES FOR METHANOL TONEW ZEOLITES ......• Tridirectional large pore zeolite • Micropore...

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

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

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

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

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

Calcination

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

• 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

• 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

H OCalcination H2O

H2OC l i ti

Calcination

H2OCalcination

Calcination

H2OC l i ti

Calcination

MOXX….

CAN WE TAKE PROFIT FROM THE SDA?

H2OC l i ti

Calcination

MOX….

P OSiO2

P-CONTAINING STRUCTURE DIRECTING AGENTS

H2OC l i ti

Calcination

MOX….[P(i-Pr)4]+

P OSiO2

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

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)

TETRAALKYLPHOSPHONIUM CATIONS:TETRAALKYLPHOSPHONIUM CATIONS:

ITQ-26

• 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)

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)

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

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

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

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)

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)

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)

Calcination of P-SDA-RUB-13 zeolites

IR spectroscopy(OH region)

calcined

3900 3750 3600 3450 3300

calcined

3900 3750 3600 3450 3300Wavenumber (cm-1)

No acid Si-OH-Al sites

calcined

3900 3750 3600 3450 3300

calcined

3900 3750 3600 3450 3300Wavenumber (cm-1)

Calcination of P-SDA-RUB-13 zeolitesCalcination of P SDA RUB 13 zeolites

HSi-O-Al

reduced

calcinedcalcined

3900 3750 3600 3450 33003900 3750 3600 3450 3300Wavenumber (cm-1)

27Al MAS NMR

reducedreduced

calcined

120 80 40 0 40

as- made

120 80 40 0 -40 (ppm)

Recovering of the PH3Recovering of the PH3

I-iPrI iPr

Application of P-containing RUB-13Application of P containing RUB 13

Methanol to olefins reactionCommercial catalysts: ZSM-5 (10R) and SAPO-34 (8R)

MTO PROCESSMTO PROCESS

Prof. Tatsumi

Methanol to olefins reaction on P RUB 13

Olefin Distribution (Conversion level: 90 100%)

Methanol to olefins reaction on P-RUB-13

Olefin Distribution (Conversion level: 90-100%)

Reaction conditions

Catalyst: 100mg, WHSV = 0.5h-1, Temperature: 400ºC

selectivi

RUB‐13

SAPO‐34

ZSM‐5

C1 C2 C3 C4 C5+

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

Methanol to olefins reaction

Methanol to olefins reaction on P RUB 13Methanol to olefins reaction on P-RUB-13

50Calcined Reduced

ity (%

30ity (%

Si/Al = 17 Si/Al = 450

C2= C3

= C4= C2-C3 paraffins C4 paraffins C5+

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

CO2 adsorption CH4 adsorption

CO2 /CH4 selectivity

Silica Structure directing

Zeolite

Temperature, time

NaOHSilica Structure directing

Zeolite

Temperature, time

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

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

CO B-1

Possible scheme for CH4 purificationf N t l Gfrom Natural Gas

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).

10R along c (6.0Å x 5.1Å), coneccting cavities, also conected through 8R (4.4 Å x 3.6 Å) along ab.

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

NEW ZEOLITES FOR METHANOL TONEW ZEOLITES ......• Tridirectional large pore zeolite • Micropore...

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