1st spain-japan joint workshop on “nanoscience and new
TRANSCRIPT
Ordered Porous Materials as heterogenous catalystsand adsorbents
Fernando ReyInstitute of Chemical Technology ITQ - Valencia
1st Spain-Japan Joint Workshop on“Nanoscience and New Materials”
ZeolitesZeolites
Natural Gas Natural Gas UpgradingUpgrading
OlefinOlefin ProductionProduction
Outline of the Presentation
ZeolitesZeolites
Natural Gas Natural Gas UpgradingUpgrading
OlefinOlefin ProductionProduction
Outline of the Presentation
ZeolitesZeolites are are thethe aluminosilicatealuminosilicatemembersmembers ofof thethe familyfamily ofof microporousmicroporoussolidssolids knownknown as "molecular as "molecular sievessieves." ."
TheThe termterm molecular molecular sievesieve refersrefers totoa particular a particular propertyproperty ofof thesethesematerialsmaterials, , i.ei.e., ., thethe abilityability toto selectivelyselectivelysortsort moleculesmolecules basedbased primarilyprimarily onon aasizesize exclusionexclusion processprocess. . ThisThis isis duedue totoa a veryvery regular regular porepore structurestructure ofofmolecular molecular dimensionsdimensions. . TheThe maximummaximumsizesize ofof thethe molecular molecular oror ionicionic speciesspeciesthatthat can can enterenter, , formedformed oror getget out out ofof thetheporespores ofof a a zeolitezeolite isis controlledcontrolled by by thethedimensionsdimensions ofof thethe channelschannels
Zeolites
Structure of Zeolite EU-1Structure of Zeolite EU-1
Zeolites
Chabazite8 TO2
3.8 x 3.8 Å
Chabazite8 TO2
3.8 x 3.8 Å
ZSM-510 TO2
5.5 x 5.1 Å
ZSM-510 TO2
5.5 x 5.1 Å
Faujasite12 TO2
7.4 x 7.4 Å
Faujasite12 TO2
7.4 x 7.4 Å
Zeolites
UTD-114 TO2
8.2 x 8.1 Å
UTD-114 TO2
8.2 x 8.1 Å
ECR-3418 TO2
10.1 x 10.1 Å
ECR-3418 TO2
10.1 x 10.1 Å
Cloverite20 TO2
13.2 x 6.0 x 3.5 Å
Cloverite20 TO2
13.2 x 6.0 x 3.5 Å
0
0.2
0.4
0.6
0.8
1
heliu
mne
onarg
onkry
pton
xeno
nmeth
ane
ethan
epro
pane
butan
eeth
yne
ethen
epro
pene
1-bute
neiso
-butan
ene
open
tane
iso-oc
tane
cyclo
propa
necy
clohe
xane
benz
ene
p-xyle
neo-x
ylene
ammon
ia(C
4H9)3
N(C
4F9)3
Nwate
rhy
droge
n
carbo
n monox
ide
carbo
n dioxid
eox
ygen
nitrog
en
Kin
etic
diam
eter
[nm
]
Zeolites
0
0.2
0.4
0.6
0.8
1
heliu
mne
onarg
onkry
pton
xeno
nmeth
ane
ethan
epro
pane
butan
eeth
yne
ethen
epro
pene
1-bute
neiso
-butan
ene
open
tane
iso-oc
tane
cyclo
propa
necy
clohe
xane
benz
ene
p-xyle
neo-x
ylene
ammon
ia(C
4H9)3
N(C
4F9)3
Nwate
rhy
droge
n
carbo
n monox
ide
carbo
n dioxid
eox
ygen
nitrog
enK
inet
icdi
amet
er[n
m]
3.8 Å
5.5 Å
7.4 Å
8.1 Å
Zeolites
0
0.2
0.4
0.6
0.8
1
heliu
mne
onarg
onkry
pton
xeno
nmeth
ane
ethan
epro
pane
butan
eeth
yne
ethen
epro
pene
1-bute
neiso
-butan
ene
open
tane
iso-oc
tane
cyclo
propa
necy
clohe
xane
benz
ene
p-xyle
neo-x
ylene
ammon
ia(C
4H9)3
N(C
4F9)3
Nwate
rhy
droge
n
carbo
n monox
ide
carb
on dioxide
oxyg
ennitr
ogenK
inet
icdi
amet
er[n
m]
3.8 Å
5.5 Å
7.4 Å
8.1 Å
Natural Gas Upgrading
Gas separation of CO2/ N2 / CH4
ToTo understandunderstand thethe aimingaimingofof thethe Natural Gas Natural Gas UpgradingUpgrading, , itit isis neededneeded totospendspend somesome time time lookinglookingat at thethe energyenergy landscapelandscapeforfor thethe nearnear futurefuture
World Oil reservesWorld Oil reserves
Natural Gas Upgrading
World Oil reservesWorld Oil reserves1.200 1.200 billionbillion bblbbl
Natural Gas Upgrading
World Oil World Oil depletiondepletion
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 ReservesWorld Natural Gas Reserves6.180 6.180 trilliontrillion cubiccubic feetfeet
Natural Gas Upgrading
Their exploitation is not Their exploitation is not economically profitableeconomically profitable
ProfiteableProfiteable ReservesReserves1.236 1.236 trilliontrillion cubiccubic feetfeet
World Natural Gas ReservesWorld Natural Gas Reserves6.180 6.180 trilliontrillion cubiccubic feetfeet
ProvedProved ReservesReserves6.180 6.180 trilliontrillion cubiccubic feetfeet
Natural Gas Upgrading
Natural Gas is transported Natural Gas is transported
through pipelines or as cryogen through pipelines or as cryogen
liquid to final marketsliquid 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 inThe optimum situation is the in--
situ production of liquefied 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 theParticularly difficult is theremoval of COremoval of CO22 and Nand N22 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
CO2
CH4
Ads
orbe
d ga
s (m
g/g)
Temperature (ºC)10 20 30 40 50 60 70
0
40
80
120
160
200
240Pressure (bars)
P=0.025P=0.050P=0.100P=0.200P=0.400P=0.600P=1.00P=1.50P=2.0P=3.0P=4.0P=5.0
New zeolite8 TO2
3.7 x 3.7 Å
New zeolite8 TO2
3.7 x 3.7 Å
Molecular Sieve Technology for COMolecular Sieve Technology for CO22 capturecapture
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
PressureSwing
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
ACHIEVEMENTSACHIEVEMENTSRaw 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.
OBJECTIVESOBJECTIVESTo increase the selectivity for the elective adsorption of NTo increase the selectivity for the elective adsorption of N22 versus versus COCO22..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 regenerabilityregenerability of the adsorbent. of the adsorbent.
Natural Gas Upgrading
ACHIEVEMENTSACHIEVEMENTSRaw 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.
OBJECTIVESOBJECTIVESTo increase the selectivity for the elective adsorption of NTo increase the selectivity for the elective adsorption of N22 versus versus COCO22..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 regenerabilityregenerability of the adsorbent. of the adsorbent.
Natural Gas Upgrading
ProfiteableProfiteable ReservesReserves< 4.000 < 4.000 trilliontrillion cubiccubic feetfeet..ZEOLITE TECHNOLOGYZEOLITE TECHNOLOGY
ProfiteableProfiteable reservesreserves1.236 1.236 trilliontrillion cubiccubic feetfeet
AmineAmine technologytechnology
Olefin production
Olefins are employed as very primary chemical building blocks ofmost of the goods we found in our life: plastics, fibers,lubricants, films, textiles, pharmaceuticals, etc. ---even chewinggum!
North AmericaNorth America2006 Ethylene Supply/Demand2006 Ethylene Supply/Demand
Production by Feedstock Demand by End-Use
Domestic Demand = 31 Million Metric TonsDomestic Demand = 31 Million Metric Tons
EDC13%
EthyleneOxide13%
PE58%
Others11%
EBZ5%
Propane15%
Ethane49%
Others5%Gas Oil
5% Naphtha22%
Butane4%
North AmericaNorth America2006 Ethylene Supply/Demand2006 Ethylene Supply/Demand
Total ethylene worldwide production
is over 120 Million Metric Tons.
North AmericaNorth America2006 PG/CG Propylene Supply/Demand2006 PG/CG Propylene Supply/Demand
Stm. Crackers49%
Others3%
FCC/Splitters48%
Others6%
Acrylo-nitrile10%
Cumene1%
Acrylic Acid6%
Oxo Alc.6%
Propylene Oxide12%
PP59%
Production by Source Demand by End-Use
Domestic Demand = 16 Million Metric TonsDomestic Demand = 16 Million Metric Tons
Steam cracking process :Steam cracking process :Operates at very high temperature (800 Operates at very high temperature (800 --900 900 ººC)C)High water content in the stream (HHigh water content in the stream (H22O /C = 1 O /C = 1 -- 3)3)Very short contact timeVery short contact timeSelectivity towards valuable olefins is approx. 85%Selectivity towards valuable olefins is approx. 85%The reaction is highly endothermicThe reaction is highly endothermic
Huge needing of energyHuge needing of energy
Olefin production
Steam cracking is the single Steam cracking is the single most energymost energyconsuming processconsuming process in the chemical industryin the chemical industry
ca. 30% of the sector’s total final energy useand ca. 180 millions tons of CO2 in 2004
Another reason for innovation: over 35% of European crackers are over 25 years old
Olefin production
Olefin production
An attractive alternative to steam cracking is the selective oxidative dehydrogenation of low value paraffins (ODH).
Paraffin + O2CnH(2n+2) + O2
Olefin + WaterCnH2n + H2O
Exothermic processExothermic processLow temperature reaction (approx. 400Low temperature reaction (approx. 400ººC)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 + O2CnH(2n+2) + O2
Olefin + WaterCnH2n + H2O
CO2 + Water
Combustion must be minimized!!Combustion must be minimized!!
Olefin production
Ethane to ethylene by ODH processEthane + O2
C2H6 + O2
Ethene + WaterC2H4 + H2O
20 40 60 80 1000
20
40
60
80
100
Sele
ctiv
ity, %
Ethane conversion, %
C2H4
COx
Reaction temperature = 400ºC
20 40 60 80 1000
20
40
60
80
100
Sele
ctiv
ity, %
Ethane conversion, %
C2H4
COx
Reaction temperature = 400ºC
Porous mixed oxideMoVTeNbO
Olefin production
•CO2 + Water
Combustion is minimized!!Combustion is minimized!!
Ethane + O2C2H6 + O2
Ethene + WaterC2H4 + H2O
J.M. López Nieto et alChem.l Comm. (2002) 1906-1907.
Olefin production
Propane + O2C3H8 + O2
Propene + WaterC3H6 + H2O
Propane to propylene by ODH process
0 10 20 30 40 500
20
40
60
80
100
Sel
ectiv
ity, %
Propane converison, %
Propene
CO
CO2
Reaction temperature = 500ºC
0 10 20 30 40 500
20
40
60
80
100
Sel
ectiv
ity, %
Propane converison, %
Propene
CO
CO2
Reaction temperature = 500ºC
Olefin production
Propane + O2C3H8 + O2
Propene + WaterC3H6 + H2O
T. Blasco; J.M. Lopez-Nieto et alJ. Catal., 152 (1995) 1-17.
Propane to propylene by ODH process
Vanadium-AlPO-5
Olefin production
• CO2 + Water
Propane + O2C3H8 + O2
Propene + WaterC3H6 + H2O
Propane to propylene by ODH process
0 10 20 30 40 500
20
40
60
80
100
Sel
ectiv
ity, %
Propane converison, %
Propene
CO
CO2
Reaction temperature = 500ºC
0 10 20 30 40 500
20
40
60
80
100
Sel
ectiv
ity, %
Propane converison, %
Propene
CO
CO2
Reaction temperature = 500ºC
Olefin production
Propane + O2C3H8 + O2
Propene + WaterC3H6 + H2O
T. Blasco; J.M. Lopez-Nieto et alJ. Catal., 152 (1995) 1-17.
Propane to propylene by ODH process
At At lowlow conversionconversion thethepropylenepropylene selectivityselectivityisis veryvery highhigh..
COMBINED PROCESSCOMBINED PROCESSREACTIONREACTION--ADSORPTIONADSORPTION
Olefin production
PressureSwing
Absorption
Feed Compressor
Propane + O2C3H8 + O2
Propane
Propane/Propene
PropeneO
DH
Rea
ctor
Propane to propylene by ODH/separation process
Olefin production
PressureSwing
Absorption
Feed Compressor
Propane + O2C3H8 + O2
Propane
Propane/Propeneseparation
PropeneO
DH
Rea
ctor
Propane to propylene by ODH/separation process
0 100 200 300 400 500 6000,0000
0,0002
0,0004
0,0006
0,0008
Propane
Q (m
ol/g
)
t (min)
Propene
Propane/propylene separation process
Kinetic separation
ITQ-328 TO2
3.8 x 3.6 Å
ITQ-328 TO2
3.8 x 3.6 Å
Olefin production
Promising results on
0 10 20 30 40 500
20
40
60
80
100
Sel
ectiv
ity, %
Propane converison, %
Propene
CO
CO2
Reaction temperature = 500ºC
0 10 20 30 40 500
20
40
60
80
100
Sel
ectiv
ity, %
Propane converison, %
Propene
CO
CO2
Reaction temperature = 500ºC
0 100 200 300 400 500 6000,0000
0,0002
0,0004
0,0006
0,0008
PropaneQ
(mol
/g)
t (min)
Propene
Propane ODH reactionon vanadium-AlPO-5
Propane/propene separationon ITQ-12 or ITQ-32
Propane to propylene by ODH/separation process
Olefin production
ACHIEVEMENTSACHIEVEMENTS
Very selective catalyst for Ethylene production by ODH of ethaneVery selective catalyst for Ethylene production by ODH of ethane..
Modest Modest selectivitiesselectivities in propane ODH reaction, but promising in propane ODH reaction, but promising expectativesexpectatives in combined ODH/separation processes. in combined ODH/separation processes.
OBJECTIVESOBJECTIVES
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 propTo increase the selectivity for the selective adsorption of propylene ylene versus propane (THERMODYNAMIC SEPARATION)versus propane (THERMODYNAMIC SEPARATION)
To tailor the To tailor the hydrophillicityhydrophillicity properties of the properties of the zeolitezeolite in order to in order to increase the water retention capacity, without penalty of the increase the water retention capacity, without penalty of the propenepropene
adsorption.adsorption.
Olefin production
FischerFischer--TropschTropsch processprocess toto DieselDiesel
ModifiedModified FischerFischer--TropschTropsch toto gasolinegasoline
ModifiedModified FischerFischer--TropschTropsch toto olefinsolefins
BiomassBiomass toto fuelsfuels andand//oror olefinsolefins
BiomassBiomass toto chemicalschemicals
Many application of zeolites in energy related processes