Dra.

Sibele Pergher
UFRN

31demaroe01deabrilde2016
CETEM RiodeJaneiro
Topics
p
Introduction
PillaredClays
Pill dCl Synthesis
S h i
PillaringAgents MixedAl/CoPillar
OthersPillaredLamelarMaterials
Moreaccessiblepillaredmaterials
Conclusion
 Introduction

Clay minerals
Clayminerals

http://www.soils4teachers.org/mineralogy
 Introduction

Clay mineral Structure

ClaymineralStructure
SiO 4 Tetrahedral
TETRAEDRO DE SiO4 AlO 6 Octahedral
OCTAEDRO DE AlO6

SiO4

OxygenAtoms
TOMOS DE OXIGNIO OxygenAtoms
TOMOS DE OXIGNIO
SiliconAtoms
TOMOS DE SLICIO TOMOS DE ALUMNIO
AluminumAtoms AlO6

SiO4
SheetofSiTetrahedrals
FOLHA DE TETRAEDROS DE Si SheetofAlOctahedrals
FOLHA DE OCTAEDROS DE Al

SiO4

Montmorillonite
 Introduction

PillaredClay

Handbook of Clays Bergaya

 Introduction

PillaredLayered Materials

d1 P d2 P P

Clays
1)RobustPillars d1 LayeredDoubledHydroxides
2)Pillarsseparation d2 Phosphatesofmetalsin
3)Rigidlayers oxidationstateIV
OthersLayersMaterials
Highsurfaceareas:100a1000m2/g
Interlayersurfaceisaccessibleonlytowaterorslightlypolarmolecules
whichcansolvatethecompensatingions.
Hightemperaturesleadtostructurecollapse.
Pinnavaia,T.J.;ACSAdv.Chem.Ser.1995,245,283.
 Introduction
Properties
d001(16,4a28,4
( ,4 ,4 ))
Methodemployed Specificarea(200a500m2/g)
PillaringAgent
PillaringAgent Thermalstability
y
Acidity
Clayused
15,5
9,7
Pillarization

18,5

ExchangebleCations
AluminiunPillars

FewPillars
ManyPillars ManyPillars
Baddispersed Welldispersed
 PILC Synthesis

Pill d Cl
PillaredClayssynthesis:
h i

Smectite
Layer
Cationic
Exchanged Calcination
Pillar
Interlayer
cations

Acessibility:
y d001 Porosity Properties

Scaleuppillaring:Astudyoftheparametersthatinfluencetheprocess FrancineBertella,Sibele B.C.

Pergher.Inpress
eg e. p
Reuseofpillaringagentinsequentialbentonite claypillarization process FrancineBertella,Sibele B.C.
Pergher.Inpress
PatentPI1100547-5 2011 (NovoprocedimentoparasntesedeArgilasPilarizadas emGrandeEscala)
 PILC Synthesis

TraditionalMethodforPillarization:

250 mL 500 mL
6 days under stirring at
AlCl3.6H2O NaOH
room temperature
0.2 mol/L 0.2 mol/L

3g clay 300 mL H2O 2h under stirring at

room temperature

2h under stirring at
Suspension Pillaring Agent
room temperature

Filtration
C l i ti
Calcination d i
drying and
washing
 PILC Synthesis

Natural Clay Pillared Clay

d001 = 15.12
15 12 d001 = 17.80
17 80

SBET = 58 m/g SBET = 234 m/g

1000

900

800

700
u.a.)

600
(u
)
(a.u.)

Poo A
ntensidade

500
ntensity

400

300
In

PooAP02
In

200

100 PooAP02c
0
10 20 30 40 50 60
2
 PILC Synthesis

Pillarizationsforscaleupprocess:
Group 1: Pre-expansion effect

Solution Amount of Amount of

Ratio
Concentra Pillared water in clay d001 S BET
Method Clay/water
tion Clay suspension () (m/g)
(g/mL)
(mol/L) (g) (mL)
Traditional 0.2 1/100 3 300 17.86 234.4
1 0.6 1/10 10 100 16.84 142.4
4 0.6 1/50 10 500 17.54 217.0
5 0.6 1/100 10 1000 17.90 216.3
9* 0.6 1/100 10 1000 17.83 149.7
10* 0.6 1/100 10 1000 17.34 149.5
*remove500mL;900mL
 PILC Synthesis

Pillarizationsforscaleupprocess:
Group 1: Pre-expansion effect

Solution Amount of Amount of

Ratio
Concentra Pillared water in clay d001 S BET
Method Clay/water
tion Clay suspension () (m/g)
(g/mL)
(mol/L) (g) (mL)
Traditional 0.2 1/100 3 300 17.86 234.4
1 0.6 1/10 10 100 16.84 142.4
4 0.6 1/50 10 500 17.54 217.0
5 0.6 1/100 10 1000 17.90 216.3
9* 0.6 1/100 10 1000 17.83 149.7
10* 0.6 1/100 10 1000 17.34 149.5
*remove500mL;900mL
 PILC Synthesis

Group 2: Method effect

Mass
Solution Ratio of Ratio of
of d001 S BET
Method Conc. meqAl/g of Clay/water Observations
Clay () (m/g)
(mol/L) clay (g/mL)
(g)
Trad. 0.2 15 1/100 3 17.86 234.4 ---
6 0.6 15 --- 3 13.75 85.1 Reflux
7 0.6 15 1/100 10 17.20 226.9 1 month
11 0.6 15 ---- 10 17.10 71.4 In Situ
In Situ c/
12 0.2 16,6 1/100 3 12.96 73.8
expan.
13 06
0.6 35 Acetone 50% 5 16 74
16.74 221 9
221.9 Ca Acetone
15 0.6 30 Acetone 50% 5 17.27 207.9 Acetone
16 0.2 16 1/50 3 17.79 225.1 PILC 1 dia
20 0.6 15 1/100 10 17.58 237.3 PILC. 1 dia
 PILC Synthesis

Method 20:

Dropping at 60C and

250 mL 500 mL
aging overnight at room
AlCl3.6H
6H2O N OH
NaOH
temperature
0.6 mol/L 0.6 mol/L

10g Clay 1 L H2O 2h under stirring at room

temperature

Suspension Pillaring Agent 2h under stirring at

room temperature

Filtration
Calcination drying and
washing
 PILC Synthesis

Group 3: increasing the amount of clay

Solution Ratio Mass

d001 S BET
Method Conc. clay/water of Clay Observations
() ( / )
(m/g)
(mol/L) (g/mL) (g)
Trad. 0.2 1/100 3 17.86 234.4 6 dias
5 0.6 1/100 10 17.90 216.3 6 dias
20 0.6 1/100 10 17.58 237.3 60C, 24h
17 1.2 1/100 20 17.68 191.4 6 dias
22 1.2 1/100 20 17.54 251.2 60C, 24h
21 1.5 1/100 50 16.62 179.1 6 dias
23 1.2 1/100 50 17.58 197.0 6 dias
24 12
1.2 1/100 50 17 58
17.58 233 0
233.0 60C 24h
60C,
 PILC Synthesis

Grupo 4: Reuse of Pillaring Solution

Solutions Ratio Mass

d001 S BET
Method Conc. clay/water of clay Observations
() (m/g)
(mol/L) (g/mL) (g)
Trad. 0.2 mol/L 1/100 3g 17.86 234.44 ---
19 (1) 0.2 mol/L 1/100 3g 17.86 237.47 1 time
19 (2) 0.2 mol/L 1/100 3g 17.83 248.23 2 time
19 (3) 0.2 mol/L 1/100 3g 17.54 239.73 3 time
 PILC Synthesis

The pre
preexpansion
expansion of clay in water is one of the most
important steps of the process.

The temperature influences

Th i fl the
h formation
f i off
pillaring agent.

50g of clay could be pillared with high basal spacing

(17.58 ) and with high specific surface area (233 m/g)
by the method using heating in the synthesis of
pillaring agent (01 day).
The pillaring agent can be reused and stored.
 Pillaring Agents

Pillaring Agents
Polynuclear Cations
Aluminium oxides
Zirconium oxides
Chromium Oxides
Keggin Ion (Fe3O(OCOCH3)6.3H2O)+
Iron Oxides
Titanium Oxides
Silicon oxides
Mixed and other

[Zr(OH)2.4H2O]8+
Titanium Oxides
 PillaringAgents

PillaringAgents
PolynuclearCations
Aluminiumoxides
Parameters
Zirconiumoxides
ChromiumOxides Theconcentrationofthemetalion
IronOxides Thebasicityordegreeofhydrolysis(R=OH/M)

TitaniumOxides Temperature
TimeandTemperatureaging
Siliconoxides
Methodofpreparation
Mixedandother
 Pillaring Agents

Kegging
egg g Ion
o ((Al13)) 100
All
mono
80

Al
poly

Al
60

%A
40

Al
13
20

0
0,0 0,5 1,0 1,5 2,0 2,5 3,0
r

60
Al
poly
50

40
% Al
30 Al
13

20 Al
mono

10

H2O]+7
[Al13O4(OH)24.12H 0
50 60 70 80 90 100
T (oC)
 Al/CoMixedPillar

Al/Co PillaredClay

PillaringofBentonite ClaywithAlandCo F.Bertella andS.Pergher Microporous andMesoporous

MaterialsVol 201,1January2015,Pages116123.
PatentBR 10 2014 013725 4 (Argilapilarizada LPM1compilaresmistosdealumnioecobalto)
 Al/CoMixed Pillar

Mixed Pillars Al/Co:

PCo10Al90
3 g clay + 300 mL H2O
NaOH
500 mL
L 0,2
0 2 mol/L
l/L PC 25Al75
PCo25Al75

PCo50Al50
AlCl3.6H2O
and/or PCo75Al25
6H2O
CoCl2.6H
250 mL 0,2
PCo100
mol/L
c1 e c2
 Al/CoMixed Pillar

Mixed Pillars Al/Co Sample d001 ()

PooA 15,1
Low contents of Co:
PCo10Al90 18,4,
PCo25Al75 19,3 e 9,6
19,3
15,1 Mix 9,6
18,4 Al/Co
(u.a.)
(a.u.)

PooA
Intenntensidade
nsity
In

PC 10Al90
PCo10Al90

9,6
10 20 30 40 50 60
PCo25Al75
85,6 %
2

88,3 %
23
 Al/CoMixed Pillar

Mixed Pillars Al/Co

Sample d001 ()
High contents of Co:
PooA 15,1
14,7
PCo50Al50 14,7
15,1
PCo75Al25 14,7 e 7,9
14,7 7,9 PCo100 7,5
a.)
u.)

PooA

(u.a
Intensidade(a.u
Intensity

PCo50Al50

PC 75Al25
PCo75Al25
pH = 6
7,5
PCo100

10 20 30 40 50
0 60
2
 Al/CoMixed Pillar

Sample CoHDL PCo75Al25 PCo100

Mixed Pillars Al/Co Mols of Co 0.1 0.0375 0.05
M l off Al 0.05
Mols 0 05 0 0125
0.0125 ---
High contents of Co:
Mols NaOH 0.25 0.1 0.1
OH/metal 1.66 2 2
7,56
Co/Al 2 3 ---
a.u.)(u.a.)

1200
* * Co 3O 4
7,89
, PCo100
ade

Q = quartzo
1000
(a
Intensida
Intensity

dade (u.a.)
800

((a.u.)
HDL 600

Intensid
Intensity
PCo75Al25400
*
* *
*
Q *
PCo100
200
10 20 30 40 50 60

7,50 2 0
10 20 30 40 50 60
2
 Al/CoMixed Pillar

Mixed Pillars Al/Co

Porosity
140
PCo10Al90c2
Isotermas type IIb
PCo25Al75c2
120
PCo50Al50c2
PCo75Al25c2 Rouquerol, Rouquerol and Sing (1999).
100 PC 100 2
PCo100c2

80
Vads ((cm/g)

60

40

20

0
0,0 0,2 0,4 0,6 0,8 1,0
p/po
 Al/CoMixed Pillar

Mixed Pillars Al/Co

Porosity
Sample SBET (m/g) Smicro (m/g) Sext (m/g) Vmicro (cm/g) Vtotal (cm/g)
P A
PooA 58 19 39 0 010
0,010 00,070
070
PCo10Al90c1 209 17,6 188 21 0,076 0,128
PCo25Al75c1 304 18,6
18 6 281 23 0,114 0,165
PCo50Al50c1 69 45 24 0,019 0,087
PCo75Al25c1 30 4 26 0,003 0,095
PCo100c1 44 7 37 0,004 0,160
PCo10Al90c2 233 17,6 212 21 0,083 0,141
PCo25Al75c2 334 18,1 310 24 0,122 0,174
PCo50Al50c2 68 36 32 0,014 0,088
PCo75A25c2 75 43 32 0,017 0,112
PCo100c2 34 --- 34 --- 0,148
 Al/CoMixed Pillar

Mixed Pillars Al/Co

Co content incorporated

El
Element
t (%)
Sample
Si Al Ca Mg Co Na K
Natural 83,02 13,55 1,01 1,67 n.d. 0,25 0,50
PILC 64,02 34,52 n.d. 1,24 n.d. 0,17 0,05
PCo10Al90 77,03 21,57 n.d. 0,82 0,04 0,12 0,24
PCo25Al75 73 30
73,30 24 90
24,90 nd
n.d. 1 16
1,16 0 26
0,26 0 15
0,15 0 23
0,23
PCo50Al50 78,46 13,48 0,12 0,69 6,72 0,19 0,34
PCo75Al25 48,60 12,20 0,23 0,51 37,49 0,57 0,40
PCo100 15,81 3,83 0,12 0,24 79,28 0,57 0,15
 Al/CoMixed Pillar

Mixed Pillars Al/Co

Co content incorporated
PCo10Al90 PCo25Al75

Itisnotpossibletoobserve
agglomeratesofcobaltdepositedon
thelamellae!
 Al/CoMixed Pillar

Mixed Pillars Al/Co

Co
C content iincorporatedd

PCo25Al75 Co - PCo25Al75

PCo50Al50 Co - PCo50Al50
 Al/CoMixed Pillar

Mixed Pillars Al/Co

Co
C content iincorporatedd

PCo75Al25 Si Co

PCo100 Si Co
 Al/CoMixed Pillar

Mixed Pillars Al/Co

Evidence for the formation of mixed pillars

Oct
PILC Al
PCo25Al75 Sample AlVI/AlIV
PCo10Al90
PILC Al 8,11
PCo10Al90 7,98
Tet PCo25Al75 6,89
200 150 100 50 0 -50 -100 -150 -200
ppm Al3+ Co3+

AlVI/AlIV AlVI CoVI 67,5 pm 68,5 pm

 Al/CoMixed Pillar

Mixed Pillars Al/Co

/

Pillared clays were obtained and the results indicate the

formation of mixed pillars Al / Co
Best results with 25% Co.
Due to the high content of Co used,
used layered double
hydroxides have been generated.
Applications
Reao Argila Pilarizada Referncia
Craqueamento de gasleo Al - Montmorillonita (9) (10) (41) (69) (88)
Al - Laponita (89) (90) (91) (92) (93)
Al-,ZrAl
Al ZrAl-,Al
Al-Hectorita
Hectorita
Al - Rectorita
AlZrB - Bentonita
Craqueamento Al , Ce/Al - Montmorillonita (13) (23) (25) (34) (50)
Craqueamento
q de cumeno Ga,Ga/Al,Cr
, , - Montmotillonita ((84)) (92)
( ) (94)
( ) (95)
( ) (96)
( )
Craqueamento de n-parafinas Al - Beidellita (97) (98) (99)
Craqueamento de trimetilpentanos Ti , Al- Bentonita, Mont.
Al - Rectorita
Ni/Al, Al Saponita
Desproporcionao de 1,2,4 - Al , Zr - Montmorillonita (30) (84) (94) (100)
trimetilbenzeno Al - Saponita (101) (102) (103) (104)
Desproporcionao de m-xileno Al - Laponita (105) (106) (107) (108)
Desproporcionao de tolueno Al - Bentonita
Desproporcionao de alquilsilanos Al - Hectorita
Al - Beidellita
Dealquilao de p-isopropilnaftaleno Al - Montmorillonita (28)
Al - Laponita
IIsomerizao
i dde m-xileno
il Al , G
Ga - Montmorillonita
M t ill it (13) (23) (109) (110)
Isomerizao de 2,2,4 -trimetilpentano Al, Ga - Beidellita
Isomerizao de n-parafinas Al - Bentonita
Oligomerizao de propileno Al - Montmorillonita (84)
Converso de ciclohexano a benzeno Cr - Montmorillonita (39)
Sntese Fisher Tropsch Fe - Montmorillonita (31) (111)
 Hidroxilao de fenol e terfenol Al Bentonita (112) (113) (114)
Ti - Montmorillonita
Formao de eterglicol a partir do Al - Montmorillonita (115)
epxido e lcool
Alquilao de tolueno com metanol Al Montmorillonita (84) (93) (116) (117)
Alquilao de aromticos com olefinas Al Bentonita (118) (119) (120) (121)
Alquilao de bifenilo com propeno Fe Montmorillonita (126)
Alquilao de benzeno por dodec-1-eno
Al il d
Alquilao de b
benzeno com propeno
Converso de metanol La-, La/Ni - Montmorillonita (38) (41) (122) (123)
Decomposio de etanol Cr, Ti, - Montmorillonita (124) (125) (126) (127)
Decomposio de isopropanol Zr, Al - Montmorillonita
Desidratao de 1
1-butanol
butanol Si - Rectorita
Desidratao de 1-pentanol
Acilao de tio-butilo ou tio-fenilo ciclo Al - Montmorilonita (128)
alquenos
Reduo cataltica selectiva de NO com Cr, Fe, Ti, Zr, Al Bentonita (129) (130) (131) (132)
NH3 V/Ti - Montmorillonita
Oxidao de propeno a acetona Al ,Al/Fe, Al/Re - Bentonita (133) (134)
Oxidao de sulfutes a sulfxidos Ti - Montmorillonita
Desidratao de glucosa a cidos Fe ,Cr , Al - Montmorillonita (135) (136)
orgnicos
Mettese do propeno Mo/Al - Montmorillonita (137)

Pergher,S.B.C.;Detoni,C.;Mignoni,M.L. MateriaislaminaresPilarizados:preparao,
caracterizao,propriedadeseaplicaes Edifapes Erechim RS 2005.
 Pillarization

Othermaterialsthatcanbepillarized
p
Layereddoublehydroxides
PhosphatesofmetalsinoxidationstateIV
Layeredsilicates
Layeredtitanates
Layeredniobiates
Layeredzeolites
 Pilarization

Layered Double Hydroxide

LayeredDoubleHydroxide

XM12O40 n
[SiV3W9O40]7
[V10O28]6 [BVIVW11O40]7
[PV3W9O40]6
[H2W12O40]6

Pillarization

d001=12to23(h=7a18)ABET=30to160m2/g
Stability:at400oCoccurslayerdecomposition
 Pilarization

LayeredSilicates
Ilerita Na2Si8O17.nH
nH2O
Porous 20,7 to 36
Magadiita Na2Si14O29.9H2O
Kenyaita Na2Si20O41.10H2O
Areas 480 to 1150m2/g

Kanemita NaHSi2O5.3H2O
Makaita Na2Si4O9.5H2O

0,74nm
1nm 2,56nm

HIlerite pillarization process with octilamine and TEOS

Dailey,J.S.;Pinnavaia,T.J.;Chem.Mat. 1992,4,855.Kosuge,K.;TsunashimaA.;J.Chem.Soc.;Chem.Commun.
1995,2427.Landis,M.E. et al.J.Am.Chem.Soc.1991,113,3189.Inagaki,S.etal.Proc.ofthe9thInter.Zeolite
Conf.,Montreal1992,395.
 Pilarization
Layered Zeolites
Swelled Material
Precursor

Swelling

MCM36

HMI

CTMA OH
CTMA-OH
Calcination
TEOS 580C

Pillar of Si

Kresge,C.T.etal.Patente Mundial WO92/11934,1992.

Roth,W.J.etal.Catal.byMicrop.Mat. Stud.Surf.Sci.Catal. 1995,94 ,301.
Pergher,S.B.C.;Corma,A.;Forns,V.;Acta Scientiarum.Tecnology.2003,25,83.
 Moreaccessible materials?

PILC
Hexagonal
Arrangement
2.4 nm
m

Surfactant Micelle Silicate

Micelle Cylinder
Calcination

TSLS
TubularSilicateLayeredSilicate MCM41
 PHCs

PorousHeterostructuredClaysPHCs

Ionic SilicaSource Calcination

Exchange

AlkylammoniumCation Surfactant
NeutralAmine Cosurfactant

SmectiteClay Li+Fluorohectorite
SmectiteClay
 PHCs

Properties
TypeofClaymineral
f l l TypeandconcentrationofSurfactant
 PHCs

Characterization

XRD
 PHCs

TEM

N Ad
N2Adsorption
ti

PHC Saponite
PHC
 PHCs
Application
Aplicao Caractersticas do PCH Ano Ref.
Captura de metais pesados (Hg2+) PCH funcionalizado com 3- 1998 (MERCIER
mercaptopropyltrimethoxysilano. e PINNA-
Argila flfluorohectorita.
Argila: orohectorita VAIA, 1998)

Adsorventes de compostos orgnicos Adsoro com etanol, metil etil cetona, 2004 (PIRESet
volteis (VOCs) gua,
g dixido de carbono, etano, metano e al., 2004)
nitrognio em PCHs
Argila: bentonita
Oxidao cataltica seletiva de amnia PCHs modificados com espcies de cobre 2006 (CHMI-
para nitrognio e ferro
ferro. ELARZet
Argila: saponita sinttica al., 2006)
Epoxidao de alquenos PCH funcionalizado com complexos quirais 2010 (KUNI-
de metais transio mangans (III). ARSKA et
Argila: bentonita l 2011)
al.,

Reao de Fischer- Tropsch PCHs sem a adio de co-surfactante 2012 (HAO et al.,
impregnados com cobalto. 2012)
Argila: montmorillonita
Oxidao preferencial de CO em PCHs suportados com xidos de cobre e 2015 (CECIL-IA,
corrente rica em H2 crio et al., 2015)
Argila: montmorillonita
Encapsulao de 5-fluoroacil PCHs como suportes sistemas de liberao 2015 (GRE-A,
controlada de frmacos et al., 2015)
Argila: montmorillonita.
 Delaminated

Delaminated clays
Delaminatedclays
Microporosity
PillaredClay

Macroporoity

Method

Delaminated
PillaredClayy
Liofilization Air
Ai
 Delaminated

Delaminated Zeolites
DelaminatedZeolites
Layered Zeolitic MCM-22
precursor

C l i ti
Calcination

Delamination MCM-36

Q
ITQ-2
 Delaminated

C ki fG il
CrackingofGasoil
M 22-50
60
ITQ 2-50

Converrsin (%)
M 36-50
50

40

30

0,1 0,2 0,3 0,4 0,5 0,6 0,7

CA T/O IL
10
M 22-50
22 50 M 22-50
22 50
25
ITQ2-50 ITQ2-50

M 36-50 M 36-50

Gasolinaa (%)
Diesel (%)

8 20

15
6

10
30 35 40 45 50 55 60 30 35 40 45 50 55 60
Conversin (% ) Conversin (%)
 Delaminated

CrackingofGasoil

25
M 22-50 M 22-50
4
IT Q 2-50
2 50 ITQ 2-50
2 50
20 M 36-50 M 36-50

que (%)
Gasses (%)

Coq
15
2

10 1

30 35 40 45 50 55 60 30 35 40 45 50 55 60
C onversin (% ) C onversin (% )
 Last Advances inour group

Moleculardimensionsinfluenceofswellingagentsonlamellarmorphologyof
MWWtypezeolites activeforfructoseconversion.A.J.Schwanke,S.B.C.
P h U D A C
Pergher,U.Daz,A.Corma. J
Journal
l off Materials
M t i l submited.
b it d
Moleculardimensionsinfluenceofswellingagentsonlamellarmorphologyof
Molecular dimensions influence of swelling agents on lamellar morphology of
MWWtypezeolites activeforfructoseconversion.A.J.Schwanke,S.B.C.
Pergher,U.Daz,A.Corma. Journal of Materials submited.
C l i
Conclusions
Clay minerals
Cl i l materials
t i l are very interesting
i t ti and
d
versatile materials.
May be
M b employed
l d as catalysts
l i naturall form,
in f can beb
transformed into different structures, like as: pillared,
heterostructured and delaminated materials.
materials
These types of materials can have different properties
depending on composition of layer, layer composition of
pillars, structure organization and porosity.
These layers materials are very promising materials to
be employed as catalyst and in particular for the design of
catalysts.