Nanoscience and New Materials Ordered Porous Materials as - - PowerPoint PPT Presentation
1 st Spain-Japan Joint Workshop on Nanoscience and New Materials Ordered Porous Materials as heterogenous catalysts and adsorbents Fernando Rey Institute of Chemical Technology ITQ - Valencia Spanish Groups Working on Ordered Porous
Ordered Porous Materials as heterogenous catalysts and adsorbents Fernando Rey
Institute of Chemical Technology ITQ - Valencia
1st Spain-Japan Joint Workshop on
“Nanoscience and New Materials”
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Spanish Groups Working on Ordered Porous Materials
Zeolites Zeolites Natural Gas Natural Gas Upgrading Upgrading Olefin Olefin Production Production
Outline of the Presentation
Zeolites Zeolites Natural Gas Natural Gas Upgrading Upgrading Olefin Olefin Production Production
Outline of the Presentation
Zeolites Zeolites are are the the aluminosilicate aluminosilicate members members of
the family family of
microporous solids solids known known as "molecular as "molecular sieves sieves." ." The The term term molecular molecular sieve sieve refers refers to to a particular a particular property property of
these materials materials, , i.e i.e., ., the the ability ability to to selectively selectively sort sort molecules molecules based based primarily primarily on
a size size exclusion exclusion process process. . This This is is due due to to a a very very regular regular pore pore structure structure of
molecular molecular dimensions dimensions. . The The maximum maximum size size of
the molecular molecular or
ionic species species that that can can enter enter, , formed formed or
get out
the pores pores of
a zeolite zeolite is is controlled controlled by by the the dimensions dimensions of
the channels channels
Zeolites
Structure of Zeolite EU-1 Structure of Zeolite EU-1
Zeolites
Chabazite 8 TO2 3.8 x 3.8 Å Chabazite 8 TO2 3.8 x 3.8 Å ZSM-5 10 TO2 5.5 x 5.1 Å ZSM-5 10 TO2 5.5 x 5.1 Å Faujasite 12 TO2 7.4 x 7.4 Å Faujasite 12 TO2 7.4 x 7.4 Å
Zeolites
UTD-1 14 TO2 8.2 x 8.1 Å UTD-1 14 TO2 8.2 x 8.1 Å ECR-34 18 TO2 10.1 x 10.1 Å ECR-34 18 TO2 10.1 x 10.1 Å Cloverite 20 TO2 13.2 x 6.0 x 3.5 Å Cloverite 20 TO2 13.2 x 6.0 x 3.5 Å
0.2 0.4 0.6 0.8 1
h e l i u m n e
a r g
k r y p t
x e n
m e t h a n e e t h a n e p r
a n e b u t a n e e t h y n e e t h e n e p r
e n e 1
u t e n e i s
u t a n e n e
e n t a n e i s
t a n e c y c l
r
a n e c y c l
e x a n e b e n z e n e p
y l e n e
y l e n e a m m
i a ( C 4 H 9 ) 3 N ( C 4 F 9 ) 3 N w a t e r h y d r
e n c a r b
m
i d e c a r b
d i
i d e
y g e n n i t r
e n
Kinetic diameter [nm]
Zeolites
0.2 0.4 0.6 0.8 1
h e l i u m n e
a r g
k r y p t
x e n
m e t h a n e e t h a n e p r
a n e b u t a n e e t h y n e e t h e n e p r
e n e 1
u t e n e i s
u t a n e n e
e n t a n e i s
t a n e c y c l
r
a n e c y c l
e x a n e b e n z e n e p
y l e n e
y l e n e a m m
i a ( C 4 H 9 ) 3 N ( C 4 F 9 ) 3 N w a t e r h y d r
e n c a r b
m
i d e c a r b
d i
i d e
y g e n n i t r
e n
Kinetic diameter [nm]
3.8 Å 5.5 Å 7.4 Å 8.1 Å
Zeolites
0.2 0.4 0.6 0.8 1
h e l i u m n e
a r g
k r y p t
x e n
m e t h a n e e t h a n e p r
a n e b u t a n e e t h y n e e t h e n e p r
e n e 1
u t e n e i s
u t a n e n e
e n t a n e i s
t a n e c y c l
r
a n e c y c l
e x a n e b e n z e n e p
y l e n e
y l e n e a m m
i a ( C 4 H 9 ) 3 N ( C 4 F 9 ) 3 N w a t e r h y d r
e n c a r b
m
i d e c a r b
d i
i d e
y g e n n i t r
e n
Kinetic diameter [nm]
3.8 Å 5.5 Å 7.4 Å 8.1 Å
Natural Gas Upgrading
Gas separation of CO2/ N2 / CH4
To To understand understand the the aiming aiming
the Natural Gas Natural Gas Upgrading Upgrading, , it it is is needed needed to to spend spend some some time time looking looking at at the the energy energy landscape landscape for for the the near near future future
World Oil reserves World Oil reserves
Natural Gas Upgrading
World Oil reserves World Oil reserves 1.200 1.200 billion billion bbl bbl
Natural Gas Upgrading
World Oil World Oil depletion depletion
Natural Gas Upgrading
About 80% of the proven About 80% of the proven reserves are small and/or far reserves are small and/or far from final markets. from final markets.
World Natural Gas Reserves World Natural Gas Reserves 6.180 6.180 trillion trillion cubic cubic feet feet
Natural Gas Upgrading Their exploitation is not Their exploitation is not economically profitable economically profitable
Profiteable Profiteable Reserves Reserves 1.236 1.236 trillion trillion cubic cubic feet feet
World Natural Gas Reserves World Natural Gas Reserves 6.180 6.180 trillion trillion cubic cubic feet feet
Proved Proved Reserves Reserves 6.180 6.180 trillion trillion cubic cubic feet feet
Natural Gas Upgrading
Natural Gas Upgrading
Natural Gas is transported Natural Gas is transported through pipelines or as cryogen through pipelines or as cryogen liquid to final markets liquid to final markets
Contaminat Level (vol %) Problem CO2 0.5 – 10.0 , peak 70 Corrosion, no heating value, SH2 0 – 1, peak 10 Corrosion, toxicity N2 0.5 – 5.0, peak 25 No heating value Water 0.5 – 1.0 plugging of transmission lines C2+ 1 – 5 % Pipeline blocking, heating value
Natural Gas Upgrading
Natural Gas is transported Natural Gas is transported through pipelines needs a huge through pipelines needs a huge investment, only affordable in investment, only affordable in large landfills. large landfills.
Impurity Initial value Pipeline Gas CO2 0.5 vol% 3 – 4 vol.% H2S 10 vol% 5.7 – 22.9 mg/m3 N2 3 vol% 3 vol.% H2O 0.5 vol% 150 ppmv C2+ 4 vol% 4 vol%
Natural Gas Upgrading
The optimum situation is the in The optimum situation is the in-
situ production of liquefied Natural Gas. Natural Gas.
Impurity Initial value Pipeline Gas Feed to LNG Plant CO2 0.5 vol% 3 – 4 vol.% < 50 ppmv H2S 10 vol% 5.7 – 22.9 mg/m3 < 4 ppmv N2 3 vol% 3 vol.% < 1 vol.% H2O 0.5 vol% 150 ppmv < 0.1 ppmv C2+ 4 vol% 4 vol% < 2 vol.%
Natural Gas Upgrading
The actual technologies do not The actual technologies do not allow their easy installation and allow their easy installation and maintenance in remote places. maintenance in remote places.
Impurity Initial value Pipeline Gas Feed to LNG Plant CO2 0.5 vol% 3 – 4 vol.% < 50 ppmv H2S 10 vol% 5.7 – 22.9 mg/m3 < 4 ppmv N2 3 vol% 3 vol.% < 1 vol.% H2O 0.5 vol% 150 ppmv < 0.1 ppmv C2+ 4 vol% 4 vol% < 2 vol.%
Particularly difficult is the Particularly difficult is the removal of CO removal of CO2
2 and N
and N2
2 from
from raw Natural Gas streams. raw Natural Gas streams.
Natural Gas + CO2 Natural Gas Lean Amine Rich Amine CO2 Gas
Natural Gas Upgrading Aqueous amine or organic solvent scrubbing
Natural Gas Upgrading
Can Can help help zeolites zeolites in in upgrading upgrading CO CO2
2?
?
Natural Gas Upgrading
CO2 CH4
Adsorbed gas (mg/g) Temperature (ºC)
10 20 30 40 50 60 70
40 80 120 160 200 240
Pressure (bars)
P=0.025 P=0.050 P=0.100 P=0.200 P=0.400 P=0.600 P=1.00 P=1.50 P=2.0 P=3.0 P=4.0 P=5.0
New zeolite 8 TO2 3.7 x 3.7 Å New zeolite 8 TO2 3.7 x 3.7 Å
Molecular Sieve Technology for CO Molecular Sieve Technology for CO2
2 capture
capture
10 psi pressure drop PRODUCT C1, C2 5 psia TAIL GAS CO2, H2O, C3+, Lost HCs Enriched CH4 30 psia FEED High Pressure C1, C2, C3, C4+ CO2, H2O Feed Compressor Vacuum Compressor Pressure Swing Absorption
Filter Exchanger Booster Pump Flash Tank Sour Gas Sweet Gas Fuel Rich Amine Stripper (Steel) Condenser Acid Gas Reflux Pump Reboiler Heating Medium Lean Amine
Typical amine Process Natural Gas Upgrading
ACHIEVEMENTS ACHIEVEMENTS Raw Natural Gas con be upgraded to Methane of quality enough to Raw Natural Gas con be upgraded to Methane of quality enough to be transported as Liquid Methane with a simpler technology. be transported as Liquid Methane with a simpler technology. The use and transportation of amines is overcome by using this The use and transportation of amines is overcome by using this new sequestration model. new sequestration model. OBJECTIVES OBJECTIVES To increase the selectivity for the elective adsorption of N To increase the selectivity for the elective adsorption of N2
2 versus
versus CO CO2
2.
. To tailor the hydrophobic properties of the zeolite in order to To tailor the hydrophobic properties of the zeolite in order to increase the increase the regenerability regenerability of the adsorbent.
Natural Gas Upgrading
ACHIEVEMENTS ACHIEVEMENTS Raw Natural Gas con be upgraded to Methane of quality enough to Raw Natural Gas con be upgraded to Methane of quality enough to be transported as Liquid Methane with a simpler technology. be transported as Liquid Methane with a simpler technology. The use and transportation of amines is overcome by using this The use and transportation of amines is overcome by using this new sequestration model. new sequestration model. OBJECTIVES OBJECTIVES To increase the selectivity for the elective adsorption of N To increase the selectivity for the elective adsorption of N2
2 versus
versus CO CO2
2.
. To tailor the hydrophobic properties of the zeolite in order to To tailor the hydrophobic properties of the zeolite in order to increase the increase the regenerability regenerability of the adsorbent.
Natural Gas Upgrading
Profiteable Profiteable Reserves Reserves < 4.000 < 4.000 trillion trillion cubic cubic feet feet. . ZEOLITE TECHNOLOGY ZEOLITE TECHNOLOGY Profiteable Profiteable reserves reserves 1.236 1.236 trillion trillion cubic cubic feet feet Amine Amine technology technology
ETHYLENE AND PROPYLENE PRODUCTION ETHYLENE AND PROPYLENE PRODUCTION
Olefin production
Olefins are employed as very primary chemical building blocks of most of the goods we found in our life: plastics, fibers, lubricants, films, textiles, pharmaceuticals, etc. ---even chewing gum!
North America North America 2006 Ethylene Supply/Demand 2006 Ethylene Supply/Demand
Production by Feedstock Demand by End-Use Domestic Demand = 31 Million Metric Tons Domestic Demand = 31 Million Metric Tons
EDC 13% Ethylene Oxide 13% PE 58% Others 11% EBZ 5% Propane 15% Ethane 49% Others 5% Gas Oil 5% Naphtha 22% Butane 4%
North America North America 2006 Ethylene Supply/Demand 2006 Ethylene Supply/Demand
North America North America 2006 Ethylene Supply/Demand 2006 Ethylene Supply/Demand
North America North America 2006 Ethylene Supply/Demand 2006 Ethylene Supply/Demand
Total ethylene worldwide production is over 120 Million Metric Tons.
North America North America 2006 PG/CG Propylene Supply/Demand 2006 PG/CG Propylene Supply/Demand
49% Others 3% FCC/Splitters 48% Others 6% Acrylo- nitrile 10% Cumene 1% Acrylic Acid 6% Oxo Alc. 6% Propylene Oxide 12% PP 59%
Production by Source Demand by End-Use Domestic Demand = 16 Million Metric Tons Domestic Demand = 16 Million Metric Tons
Olefin production
Steam Cracking
BASF 2000
Naphta Ethane
Steam cracking process : Steam cracking process :
Operates at very high temperature (800 -
900 º ºC) C)
High water content in the stream (H2
2O /C = 1
O /C = 1 -
3)
Very short contact time
Selectivity towards valuable olefins is approx. 85%
The reaction is highly endothermic
Huge needing of energy Huge needing of energy
Olefin production
Steam cracking is the single Steam cracking is the single most energy most energy consuming process consuming process in the chemical industry in the chemical industry
and ca. 180 millions tons of CO2 in 2004
Another reason for innovation:
Olefin production
Olefin production
An attractive alternative to steam cracking is the selective oxidative dehydrogenation of low value paraffins (ODH). Paraffin + O2 CnH(2n+2) + O2 Olefin + Water CnH2n + H2O
Exothermic process Exothermic process Low temperature reaction (approx. 400 Low temperature reaction (approx. 400º ºC) C) Profesor Ueda is leadering this field
Olefin production
An attractive alternative to steam cracking is the selective oxidative dehydrogenation of low value paraffins (ODH). Paraffin + O2 CnH(2n+2) + O2 Olefin + Water CnH2n + H2O CO2 + Water
Combustion must be minimized!! Combustion must be minimized!!
Olefin production
Ethane to ethylene by ODH process Ethane + O2 C2H6 + O2 Ethene + Water C2H4 + H2O
20 40 60 80 100 20 40 60 80 100 Selectivity, % Ethane conversion, %
C2H4 COx
Reaction temperature = 400ºC
20 40 60 80 100 20 40 60 80 100 Selectivity, % Ethane conversion, %
C2H4 COx
Reaction temperature = 400ºC
Porous mixed oxide MoVTeNbO
Olefin production
Ethane + O2 C2H6 + O2 Ethene + Water C2H4 + H2O
Olefin production
Combustion is minimized!! Combustion is minimized!!
Ethane + O2 C2H6 + O2 Ethene + Water C2H4 + H2O
J.M. López Nieto et al Chem.l Comm. (2002) 1906-1907.
Olefin production Propane + O2 C3H8 + O2 Propene + Water C3H6 + H2O
Propane to propylene by ODH process
10 20 30 40 50 20 40 60 80 100 Selectivity, % Propane converison, % Propene CO CO2
Reaction temperature = 500ºC
10 20 30 40 50 20 40 60 80 100 Selectivity, % Propane converison, % Propene CO CO2
Reaction temperature = 500ºC
Olefin production Propane + O2 C3H8 + O2 Propene + Water C3H6 + H2O
Propane to propylene by ODH process
Vanadium-AlPO-5
Olefin production
Propane + O2 C3H8 + O2 Propene + Water C3H6 + H2O Propane to propylene by ODH process
10 20 30 40 50 20 40 60 80 100 Selectivity, % Propane converison, % Propene CO CO2
Reaction temperature = 500ºC
10 20 30 40 50 20 40 60 80 100 Selectivity, % Propane converison, % Propene CO CO2
Reaction temperature = 500ºC
Olefin production Propane + O2 C3H8 + O2 Propene + Water C3H6 + H2O
Propane to propylene by ODH process At At low low conversion conversion the the propylene propylene selectivity selectivity is is very very high high. .
COMBINED PROCESS COMBINED PROCESS REACTION REACTION-
ADSORPTION
Olefin production
Pressure Swing Absorption Feed Compressor
Propane + O2 C3H8 + O2
Propane Propane/Propene
Propene
ODH Reactor
Propane to propylene by ODH/separation process
Olefin production
Pressure Swing Absorption Feed Compressor
Propane + O2 C3H8 + O2
Propane Propane/Propene separation
Propene
ODH Reactor
Propane to propylene by ODH/separation process
100 200 300 400 500 600 0,0000 0,0002 0,0004 0,0006 0,0008
Propane Q (mol/g)
t (min)
Propene
Propane/propylene separation process Kinetic separation
I TQ-32 8 TO2 3.8 x 3.6 Å I TQ-32 8 TO2 3.8 x 3.6 Å
Olefin production
Promising results on
10 20 30 40 50 20 40 60 80 100 Selectivity, % Propane converison, % Propene CO CO2
Reaction temperature = 500ºC
10 20 30 40 50 20 40 60 80 100 Selectivity, % Propane converison, % Propene CO CO2
Reaction temperature = 500ºC
100 200 300 400 500 600 0,0000 0,0002 0,0004 0,0006 0,0008
Propane Q (mol/g)
t (min)
Propene
Propane ODH reaction
Propane/propene separation
Propane to propylene by ODH/separation process
Olefin production
ACHIEVEMENTS ACHIEVEMENTS Very selective catalyst for Ethylene production by ODH of ethane Very selective catalyst for Ethylene production by ODH of ethane. . Modest Modest selectivities selectivities in propane ODH reaction, but promising in propane ODH reaction, but promising expectatives expectatives in combined ODH/separation processes. in combined ODH/separation processes. OBJECTIVES OBJECTIVES Increase the selectivity of current propane ODH catalysts. Increase the selectivity of current propane ODH catalysts. To increase the selectivity for the selective adsorption of prop To increase the selectivity for the selective adsorption of propylene ylene versus propane (THERMODYNAMIC SEPARATION) versus propane (THERMODYNAMIC SEPARATION) To tailor the To tailor the hydrophillicity hydrophillicity properties of the properties of the zeolite zeolite in order to in order to increase the water retention capacity, without penalty of the increase the water retention capacity, without penalty of the propene propene adsorption. adsorption.
Olefin production
Fischer Fischer-
Tropsch process process to to Diesel Diesel Modified Modified Fischer Fischer-
Tropsch to to gasoline gasoline Modified Modified Fischer Fischer-
Tropsch to to olefins
Biomass Biomass to to fuels fuels and and/ /or
Biomass Biomass to to chemicals chemicals
Many application of zeolites in energy related processes