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UM
R 5
253
-In
stitu
t de
Chi
mie
Mol
écul
aire
et d
es
Mat
éria
ux d
e M
ontp
ellie
rM
atér
iaux
Ava
ncés
pou
r la
Cat
alys
e et
la S
anté Advanced materials for catalysis
Francesco Di RenzoInstitut Charles Gerhardt Montpellier
Advanced Materials for Catalysis and Healthcare
1st SINCHEM School Bologna, 17-20 February 2014
Control of structure, porosity and size of zeolite catalysts for
refinery and petrochemistry
Anastas P. T. et Warner J. C Green Chemistry: Theory and Practice. Oxford University Press 1998
Green chemistry's twelve principles
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
what chemists think about the principles of green chemistry?
the application of a process engineering basic principle
whole-of-system approach to optimisation
increased accountability, complete cycle analysis, think globally
nothing newchemists always did it
Molière (1622-1673)“there are more than forty years that I speak prose and I didn’t know it”
a public relation need in a world of increasing public awareness
Coluche (1944-1986) “ça va sans dire, mais il vaut
mieux en le disant”
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
what a catalyst is for?
to make a reaction possibleobtain a product from cheaper or renewable reagents
to improve productivityreduce time-on-stream, plant volume, energy costs
to improve selectivityavoid side-reactions or consecutive reactionatom efficiency means no need for separation (hence energy efficiency, less capital investment)
better catalysts: the key for better processes
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Giuseppe Bellussi
1992 Breck Award for the Ti-silicalite
current president of the IZA
isomorphous substitution in zeolite networks
Ti-silicalite
a redox site in a hydrophobic environment
SzigmundCsicsery
the theoretician of the shape selctivity in
zeolites Zeolites, 4 (1984) 202
M. Taramasso, G. Perego, B. Notari, US 4,410,501, 1983.G. Bellussi, A. Carati, M.G. Clerici, G. Maddinelli, R.Millini, J. Catal. 133 (1992) 220.
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
environment-friendly propylene oxide synthesis
made possible by TS-1 catalyst
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
environment-friendly propylene oxide synthesis
made possible by TS-1 catalyst
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
M. Clerici, G. Bellussi, EP 526945A1 (1993).
HClHCl
anthraquinone to be reduced to hydroxyanthraquinone by H2
7.4 Å
network of aluminosilicate tetrahedra in zeolite Y (faujasite with Si/Al 2.5)
Control of structure, porosity and size of zeolite catalysts for refinery
and petrochemistry
active site (acid or redox) : where the reaction takes place
micropore: shape selectivity by
molecular sieving
mesopores and micropores improve the diffusion of reagents and products
the size of crystals controls the diffusion
time
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Distillation fractions of different crude oils
-46
boiling point
the hydrogen deficit crude oil has lower H/C than most oil products (except gasoline = light naphtha)
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
HC hydrocracking
purposes: decrease boiling range (molecular mass), increase H/C ratiodifferences with FCC: hydrogen prevents the formation of olefins (sources
of gumming and coke), less deep cracking, less gas formedbifunctional catalyst: metal for hydrogenation, acid site for crackingNi/silica-alumina or Pt/zeolite catalysts, 300-370 °C, 10-20 bar H 2
HDT hydrotreatments
purpose: remove undesirable heteroatoms (sulfur, nitrogen), secondary effect: reduction of alkenes (gumming), aromatics
HDN denitrogenation
analog to desulfurisation butrequires higher T and more H2, as N can be removed only by hydrogenation of the aromatic ring:
HDS desulfurisation
RSH + H2 → RH + H2S
CoMoS/alumina catalyst300-420 °C, 10-50 bar H 2
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
0
0,5
1
1,5
2
300 350 400 450 500 550
Re
lati
ve
fir
st o
rde
r h
yd
rocr
ack
ing
ra
te c
on
sta
nt
Final boiling point of the feed
NiW/ SiO2-Al2O3(395°C)
NiW/ Y(355°C)
I.E. Maxwell, Catal. Today 1(1987)385
Zeolites vs ASA:
-Higher activity (Strong acid sites)
-Diffusion limitations(Micropores) prevent treatment of heavy molecules
- Lower middle distillate selectivitiy(Secondary cracking due to high residence time)
Hydrocracking catalystszeolites vs. amorphous silica-alumina (ASA)
Adequate (meso)porosity
Adequate acidity
need for Micro-Mesoporous zeolites: hierarchical porosityFrancesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
P. O’Connor, A.P. HumphiesAccessibility of functional sites in FCCPrep. ACS Div. Petrol. Chem. 38 (1993) 598-603
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
15-45 %
10-60 %
silica-alumina 15-30 %
FCC catalyst
a hierarchical pore system
distribution of cracking products
J. Weitkamp, S. Ernst, in Guidelines for mastering the properties of molecular sieves(D. Barthomeuf, E.G. Derouane, W. Holderich Eds), Plenum Press, New York 1990, 343
n-hexadecane feed hydrogen stabilizes the products of primary crackin gless secondary cracking = less gas, more liquid
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Micro-Mesoporous zeolites: hierarchical porosity to retain activity and decrease secondary reactions
R. Chal, C. Gerardin, M. Bulut, S. Van Donk. Overview and Industrial Assessment of Synthesis Strategies towards Zeolites with Mesopores. ChemCatChem, 3, 2011, 67-8
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
TEM image of a hierarchical TS-1 zeolite sample prepared using Carbon Black Pearls as hard-template
I. Schmidt, A. Krogh, K. Wienberg, A. Carlsson, M. Brorson and C. J. H. Jacobsen, Chem. Commun., 2000, 2157–2158.
hard templating
solid porogens in the zeolte
synthesis
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
TEM image of a hierarchical TS-1 zeolite sample prepared using Carbon Black Pearls as hard-template
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
yield ratios between classical and mesoporous TS-1 in epoxidation of 1-octene and cyclohexene
I.I. Ivanova, E.E. Knyazeva, Chem. Soc. Rev. 2013, 42,.3671-3688
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
D. P. Serrano, J. M. Escola, P. Pizarro, Synthesis strategies in the search for hierarchical zeolites, Chem. Soc. Rev. 2013, 42, 4004-4035
C. Gerardin, J. Reboul, M. Bonne, B. Lebeau, Ecodesign of ordered mesoporous silica materials, Chem. Soc. Rev. 2013, 42, 4217-4255
the aluminium content of zeolites increases with the alkalinity of the synthesis system
S.P. Zhdanov, in Molecular Sieves, R.M. Barrer Ed.,
Society of Chemical Industry, London 1968
at high alkalinity, silicates have less tendency to oligomerize and the spacing among aluminates decreases
selective solubility of silicate and aluminate in acid ans basic conditions
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Creation of a zeolite Y material with crystals comprising Trimodal intra-crystalline porosity:
K.P. de Jong, J. Zecevic, H. Friedrich, P.E. de Jongh, M. Bulut,, S. van Donk, R. Kenmogne, A. Finiels, V. Hulea, F. Fajula,
Angew. Chem.49 (2010) 10074
SteamingAcid leaching
Micropores +”Large”mesopores
Micropores
Al-removal Base leaching
Si-removal
CBV 760 from Zeolyst
HY-30
Dealumination :a classical method to
increase the Si/Al ratio of zeolite network
Desilication :a method to decrease the
Si/Al ratio of zeolite networkR. Le Van Mao, S.T. Le, D. Ohayon, F. Caillebot, L. Gelebart, G. Denes.
Zeolites 19 (1997) 270
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Secondary porosity is formed by both destructive methods
bifunctional catalysisthe effect of temperature
J. Weitkamp, S. Ernst, in Guidelines for mastering the properties of molecular sieves(D. Barthomeuf, E.G. Derouane, W. Holderich Eds), Plenum Press, New York 1990, 343
shifts from isomerisation to cracking with the incr ease of temperature
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Catalysts with hierarchical porosity
to combine the high selectivity of shape-selective microporous zeolites with the high diffusivity in
mesoporous channels
Angew. Chemie Int. Ed. 49 (2010) 10074WO 2010/072976
Chem. Commun. 46 (2010) 7840
Electron tomography and pore size distribution of a zeolite Y with trimodal porosity obtained by consecutive dealumination and desilication treatments. A first acid leachingallows to connect the structural micropores (0.7 nm) by 3 nm mesopores. A consecutive basic leaching further improves the accessibility of reagents by opening 30 nm mesopores.
The addition of surfactants to the leaching solution allows to obtain monodispersed mesopores
Due to better accessibility of reagents, a zeolite Y with hierarchical porosity (green triangles) requires lower temperature than the parent dealuminated zeolite (black crosses) to reach high conversion in hexadecane hydrocracking.
catalysts with 0.3 % Pt, 20 bar H2
Hydroconversion of n-hexadecaneWHSV = 1-3 h-1, PH2 = 20 Atm., H2/hc = 4 (mol.), 220-280°C
Hydroisomerisation and hydrocracking yields vs total conversion
0
10
20
30
40
50
60
70
0 20 40 60 80 100
Rendem
ent en p
roduits
(%)
Conversion totale (%)
Pt/HY-30 ♦ HC ◊ HIPt/HY-30A ● HC ○ HIPt/HY-30B ▲ HC ∆ HI
Total conversion (%)
Yie
ld (
%)
cracking
Desilication Towards ideal hydroconversion behaviour
Isomerization
Cracking
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Pt/HY-30
Pt/HY30-A Pt/HY30-B
Pt/HY-30: Conv. : 68 %; Cracking yield. 25.2 %; C6/C10 = 1.79Pt/HY-30A: Conv. : 85,6 %; Cracking yield. 44.7 %; C6/C10 = 1.21Pt/HY-30B: Conv. : 72,6 cracking yield. 15.6 %; C6/C10 = 0.92
Hydroconversion of n-hexadecaneDistribution of hydrocracking products
Classical DealuminatedY zeolite
Dealuminated & Desilicated
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
better accessibilityno secondary crackingsymmetrical product distribution
Hydroconversion of n-hexadecane
Symmetry index (C 6/C10 ratio) of the distribution in cracking products as a function of conversion
Desilicated zeolites primary cracking
Dealuminated
Dealuminated & desilicated
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
@ 75% conversion
For hydrocracking of squalane (i-C30) the product s ymmetry is largely improved:
• Limit residence time of reactants in micropores
• Decrease in the contribution of secondary cracking (gas production)
• Enhanced selectivity and yield of middle distillate s.
gasolinejet fuel or diesel oil
Pt/Dealuminated Y zeolite
Pt/Dealuminated & Desilcated Y zeolite
hydrocracking of squalane
Pt/HY-30 Pt/HY30-A
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
why squalane?
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
bacteria-produced C15 sesquiterpene
squalenea triperpene extracted from some plants
(cosmetics) and actively studied for industrial production from microalgae (biofuel)
T.G. Tornabene, Formation of hydrocarbons by bacteria and algae, US Dpt Energy SER I /TP-621 -999 (1980)
Makazawa et al. Biores. Technol. 109 (2012) 287–291
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
can micelle-templated mesoporous silicas
find useful applications in catalysis?
Towards ideal hydrocracking catalysts
Mesoporous Silica (MCM-48)
Nitrogen sorption isotherms of parent and aluminated mesoporous silic a
0 100 200 300 400 500 6000,000
0,004
0,008
0,012
0,016
Vite
sse
de d
esor
ptio
n de
NH
3 (u
a)
Temperature oC
Pt/MCM-48B sites forts sites faibles
Acidity profile (Ammonia TPD) of MSA(Total : 0.7 mmol/g, Strong : 0.22 mmol/g)
Post-synthesis alumination of a mesoporous silica (MCM-48)
No microporesNo large mesopores
M. Bulut, R. Kenmogne-GatchuissiF. Fajula, J.P. Dath, S. van Donk, A. Finiels, V. Hulea WO 2012/085289
Mesoporous Silica Alumina (MCM-48, 13 wt% Al2O3)
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Towards ideal hydrocracking catalysts
Comparison of the activity of hydrocracking catalysts based on dealuminated Y (HY-30), dealuminated & desilicated Y
(Pt/HY-30A) and Mesoporous Silica Alumina (Pt/MSA)
Pt/MSA (MCM-48)
Hydroconversion of n-hexadecaneWHSV = 1-3 h-1, PH2 = 20 Atm., H2/hc = 4 (mol.)
Pt/MSA (MCM-48) same activity & higher selectivity than desilicated HY
0
20
40
60
80
100
0 20 40 60 80 100
Re
nd
em
en
t en
pro
du
its (%
)
Conversion totale (%)
Hydroisomerisation and hydrocracking yields vs total conversion
Pt/MSA(MCM-48)
(Pt/HY-30A)
M. Bulut, R. Kenmogne-GatchuissiF. Fajula, J.P. Dath,
S. van Donk, A. Finiels, V. Hulea WO 2012/085289
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Towards ideal hydrocracking catalysts
Comparison of the activity of hydrocracking catalysts based on dealuminated Y (HY-30), dealuminated & desilicated Y
(Pt/HY-30A) and Mesoporous Silica Alumina (Pt/MSA)
Pt/MSA (MCM-48)
Hydroconversion of n-hexadecaneWHSV = 1-3 h-1, PH2 = 20 Atm., H2/hc = 4 (mol.)
Pt/MSA (MCM-48) same activity & higher selectivity than desilicated HY
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
0
1
2
0 20 40 60 80 100
C6
/C1
0
Conversion totale (%)
Pt/HY-30
Pt/HY-30A
Pt/MCM-48Pt/MSA (MCM-48)
Symmetry (C6/C10 ratio) of the distribution of cracking products as a function of
conversion
a: Reaction rate slower than reagent diffusion (k i < kd), CS = C – Chemical controlb: Reaction faster than reagent diffusion (k i > kd), CS > C – Physical control
⇒ If (b): not worth looking for a more active catalys t!⇒ same rationale for thermal conduction as for reagen t diffusion
physical or chemical control?
catalyst particleC reagent concentrationK i reaction rateKd diffusion rate
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
E.A. Swabb, B.C. Gates, Ind. Eng. Chem. Fund. 11 (1972) 540
the effectiveness of a porous catalyst can be affected by diffusional constraints related to the length of the pores
size matters
mordenite : unidirectional pores
along the c axis
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
F. Hamidi, F. Boukli-Hacène, A. Bengueddach, F. Di Renzo, Microp. Mesop. Mater. 153 (2012) 59
1.E+14
1.E+15
1.E+16
1.E+17
1.E+18
0 1 2 3 4 5
OH- (moles L-1)
germ
s pe
r m
ole
Ag
The number of zeolite crystals nucleated by silver seeding does not depend on the type of zeolite formed (A, LSX, X, Y, L, Beta), nor on the Si/Al
ratio and decreases only at high alkalinity, due to partial Ag2O dissolution)
Nucleation promotion of zeolite crystals by in-situ formation of silver-based heterogeneous nuclei
The addition of silver nitrate to the synthesis gel of zeolites allows to form heterogeneous silver oxide seeds on which zeolite crystals can grow.
The enhanced nucleation brings to the formation of smaller zeolite crystals, with improved diffusional and kinetic properties.
2Ag+ + 2OH → 2AgOH↓→ Ag2O↓ + H2O
0 2 4 6grain size D (µm)
fre
que
ncy
M/(Σ
M*∆
D)
0 1 2 3grain size D (µm)
fre
que
ncy
M/(Σ
M*∆
D) LSX X
0 2 4 6grain size D (µm)
fre
que
ncy
M/(Σ
M*∆
D)
0 1 2 3grain size D (µm)
fre
que
ncy
M/(Σ
M*∆
D) LSX X
Size distribution of crystals of zeolites LSX and X formed in the absence (dashed lines) and in the presence (full line) of silver nucleation promoter
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
why pore geometry is important ?
SAPO-34 (CHA)SAPO-17 (ERI)SAPO-18 (AEI)
ZSM-5 (MFI)
UOP/Hydro LurgiExxonMobil
J.Q. Chen et al. Catal. Today 106 (2005) 103
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
methanol to olefinsMTO
SAPO-34:
light olefins highly favoured,
C2=/C3= higher than equilibrium distribution
C2=-C5= olefin equilibria
ZSM-5:
near to the equilibrium distribution
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
addition of Ethylene Glycol led to the formation of SAPO-18
instead than SAPO-34
not completely unexpected: the earliest synthesis of SAPO-18 were in the presence of EtOH
and isopropanol can also be used
SAPO-34 (CHA)
D6R in parallel rows
SAPO-18 (AEI)
D6R in alternate rows
very similar structures with 8R channels formed by connected D6R (hexagonal prisms)
[110]
Cmcm[001]
R3m
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
36-tetrahedra cages of SAPO-34 and SAPO-18 : same volume, different shapes
[001] windows of CHA (left) and AEI (right)
similar MTO behaviour of SAPO-18 and SAPO-34
J. Chen, J.M. Thomas, P.A. Wright, R.P. Townsend, Catal. Lett. 28 (1994) 241.
R. Wendelbo, D. Akporiaye, A. Andersen, I.M. Dahl, H.B. Mostad, Appl. Catal. A 142 (1996) L197
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
common morphologies of SAPO-34
common morphologies of SAPO-18
J. Chen et al., J. Phys. Chem. 98 (1994) 10216
R. Wendelbo et al., Appl. Catal. A 142 (1996) 197
1 µm 1 µm
1 µm1 µm
D. Chen et al., Microp. Mesop. Mater. 29 (1999) 191 commercial calcined SAPO-34
1 µm CHAR3m
AEICmcm
typical pseudocubic rombohedra of chabazite (Parrsboro, Nova Scotia)
rombohedra of trigonal crystals are formed by slow growth of apical faces
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Synthesis of EthGly SAPO-18
Synthesis formulation (molar basis)
1.0 TEAOH ⋅ xSiO2 ⋅ Al2O3 ⋅ P2O5 ⋅ zH2O ⋅ yEThGlyx = 0.025 ÷ 0.1 y = 1 ÷ 12 z = 0 ÷ 45 150 °C
possible to form SAPO-18 with Si/tet ratio in the range 0.01-0.08
peculiar morphology
50 nm-thick lamellae
orientation (h00)
EthGly/TEA ratio in crystals ≤ 0.05
1 µm
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
W. Vermeiren, N. Nesterenko, C. Petitto, F. Di Renzo, F. Fajula, WO 2008/110526
Catalytic testsTemperature: 450 °C MeOH WHSV: 2h -1
C2/C3 olefin ratio on thick SAPO-34 crystals (500 nm) and thin SAPO-18 crystals (50 nm)
0
0.5
1
1.5
2
0 1 2 3 4 5 6 7
lamellar EthGly SAPO-18
time on stream (Hours)
70% MeOH 30%H2O
100% MeOH
C2/
C3
olef
inra
tio
0
0.5
1
1.5
2
0 1 2 3 4 5 6
pseudocubic SAPO-34
time on stream (Hours)
70% MeOH 30%H2O
100% MeOH
C2/
C3
olef
inra
tio
the ethylene/propylene ratio does depend on the crystal size
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
TON = 340 TON = 317
0
10
20
30
40
50
60
0 1 2 3 4 5 6 7
SAPO-18 Si/(Si + Al + P) = 0.031
Time on stream (Hours)
C2H4
C3H6
C4 =
CH4C5=
MeOH
DME
wt
(%)
0
10
20
30
40
50
60
0 1 2 3 4 5 6 7Time on stream (Hours)
SAPO-34 Si/(Si + Al + P) = 0.041
DME
MeOH
C3H6
C2H4
C4 =
CH4C5=
wt
(%)
MTO test450 °C MeOH WHSV: 2h-1Feed : 70 % MeOH 30 % H2O
isometric morphology
C2=/C3= ratio 1.3 C2=/C3= ratio 1.3
the ethylene/propylene ratio does not depend on the structure difference between SAPO-18 and SAPO-34
MTO test450 °C MeOH WHSV: 2h -1
Feed : 100 % MeOH
EthGly SAPO-18 TON = 100
SAPO-34 TON = 60
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
1 µm
lamellar SAPO-18 crystals formed in the presence of 'EG
thickness ~ 50 nmorientation (h00) (postdoc Rossella Arletti)
control of the ratio Si/(Si+P+Al) in the range 0.01-0.08
a better dispersion of heat shifts the equilibria towards higher olefins
S.W. Kaiser, US 4,499,327 (1985), US 4,613,721 (1986), D.M. Ruthven, in Karge, Weitkamp, Molecular Sieves Adsorption and Diffusion, Springer 2008, 1
historical mechanism of MTO reaction ∆H° STP
-23.4 KJ/mol
5.4 KJ/mol
-66.5 KJ/mol
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
historique AIE, CCFA
40
90
140
190
240
290
1998 2000 2002 2004 2006 2008 2010 2012 2015
FOD
Gasoline
Diesel
Heavy Fuel
Jet/kero
Mto
n/y
Evolution of demand in Europe-27 dieselisation
In the coming years:
� GOM and JET demands are foreseen to increase in the next year
� Gasoline demand will continue to decrease
Traditionally, gasoline excesses are exported to th e USA; however, gasoline importation in the USA is decreasing due to:
� The use of cars with a better fuel-economy
� The generalization of bio ethanol use
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Olefins oligomerisationOverview of existing technologies
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Company Cuts Purpose Catalyst Process
UOP Olefins ex FT Gasoline SPA CATPOLY
IFP C3-C4 Gasoline IP501 (ASA) Polynaphta
IFP C3-C4 Gasoline Ion Liquid Dimersol
ExxonMobil Olefins ex MTO Gasoline/Jet/Diesel ZSM-5 or ZSM-22 MOGD
Shell C2-C6 Gasoline/Jet/Diesel Ni/MOR SPGK
Süd-Chemie/Lurgi Olefins ex MTO Gasoline/Jet/Diesel ZSM-5 MTS
Süd-Chemie FT naphtha Jet/Diesel CODZSM-5
Süd-Chemie Olefins ex FT Gasoline SPA
Gasoline
Jet/Diesel
valorisation of excess ethylene
formation of hydrocarbons in the jetfuel-diesel rangea double challenge
Ni-exchanged porous catalysts(~ 1.5 %Ni, Si/Al = 15-20, 150 °C, 35 bar, 1 h)
ethylene oligomerisation
120
140
Ni-MCM-48interconnected mesopores(3.5 nm)
Ni-SBA-15interconnected mesopores(8.5 nm)
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
M. Lallemand, A. Finiels, F. Fajula, V. Hulea, Chem. Eng. J. 172 (2011) 1078
Distillate-Range Products from Non-Oil-Based Sources by Catalytic Cascade ReactionsA. Lacarrière, J. Robin, D. Swierczynski, A. Finiels, F. Fajula, F. Luck, V. Hulea, ChemSusChem. 5 (2012) 1787
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Activity of Ni-MCM-41(3.5) catalysts in ethylene oligomerization as a function of nickel loading (150 8C, 3.5 MPa, reaction time 1 h).
TPR profiles of Ni-MCM-41(3.5) for various nickel loadings. a) Ni1.4-MCM-41(3.5), b) Ni2.0-MCM-41(3.5), and c) Ni7.5-MCM-41(3.5).
15.8 kmol ethylene /mol Ni/h 25 kmol ethylene /mol Ni/h
1 catalyst (Ni-MCM-41) 2 catalysts (Ni-MCM-41 + H-MCM- 41)
Single-site Ni catalystC4 olefins
Bifunctional catalystJetfuel
oligomerisation catalyst
condensation catalyst
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
A. Lacarrière et al. ChemSusChem. 5 (2012) 1787
Self-assembly of surfactant aggregates and inorganic precursors to form an orderedmesophase in which the micelles are separated by amorphous silica walls
+ silicates
∆T
An ordered pore system is formedby extraction or calcination of the micellar template
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Design of new mesostructure directing agents
Previously : Sacrificial porogens to be removed
Use smart micelles : responsive to stimuli in aqueous medium� Dissociable in water for recovery under soft conditions
� Able to confer functionalities to the mesoporous material
Double-hydrophilic block copolymers (DHBC)
Two hydrosoluble blocks : - different affinities for a substrate or a molecule- different sensitivities to a change of parameter- neutral or charged, with variable functions
stimuluspH, ionic strength,
T, radiationhydrophilichydrophilic
Reversible micellizationin waterDHBC
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
N. Anik, M. Airiau, M.P. Labeau, C.T. Vuong, J. Reboul, P. Lacroix-Desmazes, C. Gérardin, H. Cottet, Macromolecules 2009, 42, 2767
PolyIon electrostaticComplex (PIC) Micelle
pH-sensitive electrostatic complex micelles of DHBC
DHBC : weak acid – neutral
- - - - - - - - - - - - - -neutral
pKaacid
pH
DHBC micellization induced by complexation of an oppositely charged polymer :
+ + + + + + + + + + + + + + +
pKabase
Weak base : polyamine neutral
pH
AUXILIARY OF MICELLISATION
PAA-b-PEO(CH2-CH(COOH))m-b-(CH2-CH2-O)n
ChitosanFrancesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
N. Anik, M. Airiau, M.P. Labeau, C.T. Vuong, J. Reboul, P. Lacroix-Desmazes, C. Gérardin, H. Cottet, Macromolecules 2009, 42, 2767
Micelle dissociation Washing
Inorganicpolycondensation
Micelle arrangement
Hybrid material
PAA b PEO and chitosane in
solution, without TEOS.
+
+TEOS
TEOS hydrolysis
0
100
200
300
400
500
600
700
800
2 4 6 8 10 12pH
Inte
nsité
(Kcp
s/s)
Inte
nsity
(kc
ps/s
)
PAA b PEO and chitosane with
TEOS :
silica structuring
MATERIAL SYNTHESIS
Templating of mesoporous silica by pH-switchable mic ellar assemblies
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
N. Baccile, J. Reboul, B. Blanc, B. Coq, P. Lacroix-Desmazes, M. In, C. Gérardin, Angew. Chem. Int. Ed. 2008, 42, 3681
H20
Electrostatic complex
Environment-friendly process
Versatile/functional micelle system Controlled reversible micellization
Controlledmesostructures
lamellar, hexagonal…
Polymer- functionalized mesoporous silica
H20
PIC
pH=2
pH=5.5
pH=7.7
pH=5.5
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
N. Baccile, J. Reboul, B. Blanc, B. Coq, P. Lacroix-Desmazes, M. In, C. Gérardin, Angew. Chem. Int. Ed. 2008, 42, 3681
Elemental analyses :N/COO=1 in the solid
Silica based hybrid material templated with PEO5000-b-PAA1580/chitosan
100
1000
104
105
0 0,05 0,1 0,15 0,2
q en A -1
Inte
nsité
(K
cps/
s)
JRS4
d(100)=13.9 nm
SAXS
3 µµµµm3 µµµµm
Polyion electrostatic complex micelles can adopt a c ylindrical morphology in long-range ordered mesophases: lyotropic behaviour / silicates
2D hexagonal structure.
1 2 √7(100) (200) (210)
0
50
100
150
200
250
0 0,2 0,4 0,6 0,8 1p/p
0
Va
ds (
cm3 /
g)
TEM SEM
N2 adsorption
WO2009/081000
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
POE(113)-b-PAA(4)
100 nm100 nm100 nm
100 nm100 nm100 nm
POE(113)-b-PAA(15)
AA/OE = 0.03
AA/OE = 0.13
POE(113)-b-PAA(33)
AA/OE = 0.3
Non mesostructuredmaterial
2D hexagonal structure
Lamellarmesostructure
AA/OE
++
++
+-
--
--
-++
+
++
++
++
++
++
--
--
--+
++
Tuning mesostructures by varying the volume fraction of polymer blocks
--
--
-+
++
++
--
--
--
++
++
++
++
++
-
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
Micelle dissociation
Template removal
Inorganicpolycondensation
Micelle arrangement
+
+TEOS
TEOS hydrolysis
0
100
200
300
400
500
600
700
800
2 4 6 8 10pH
Inte
nsi
té(K
cps/
s)
Inte
nsi
ty (
kcp
s/s)
Micelle dissociation
Template removal
Micelle dissociation
Template removal
Micelle dissociation
Template removal
Inorganicpolycondensation
Micelle arrangement
Inorganicpolycondensation
Micelle arrangement
+
+TEOS
TEOS hydrolysis
+
+TEOS
TEOS hydrolysis
+
+TEOS
TEOS hydrolysis
0
100
200
300
400
500
600
700
800
2 4 6 8 10pH
Inte
nsi
té(K
cps/
s)
Inte
nsi
ty (
kcp
s/s)
0
100
200
300
400
500
600
700
800
2 4 6 8 10pH
Inte
nsi
té(K
cps/
s)
Inte
nsi
ty (
kcp
s/s)
Silica structuring and template removalAfter material washing in water at pH 7.7
100 nm
(100
)
(110
)(2
00)
(210
)
10
100
1000
104
105
106
0.04 0.08 0.12 0.16 0.2
matériau hybridematériau lavématériau calciné
Inte
nsité
(u
.a.)
q (A-1)
(100
)
(110
)(2
00)
(210
)
10
100
1000
104
105
106
0.04 0.08 0.12 0.16 0.2
matériau hybridematériau lavématériau calciné
Inte
nsité
(u
.a.)
q (A-1)
Calcined materialWashed materialHybrid material
0
100
200
300
400
0 0,2 0,4 0,6 0,8 1
Vad
s (cm
3 /g
)
p/p0
10
6,5
Pore diameter
(BJH) (nm)
15,513,5Washed
13,511,5Calcined
15,513,5Hybrid
dc-c (nm)
d100 (nm)
Matérial
Angewandte Chemie, 2008, 47, 8433.
Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014
thank you for your attention