1st spain-japan joint workshop on “nanoscience and new

Ordered Porous Materials as heterogenous catalystsand adsorbents

Fernando ReyInstitute of Chemical Technology ITQ - Valencia

1st Spain-Japan Joint Workshop on“Nanoscience and New Materials”

Spanish Groups Working on Ordered Porous Materials

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


World Oil reservesWorld Oil reserves1.200 1.200 billionbillion bblbbl


World Oil World Oil depletiondepletion


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


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


Why ?


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 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%


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.%


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


Aqueous amine or organic solvent scrubbing


Can Can helphelp zeoliteszeolites in in upgradingupgrading COCO22??


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


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.


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.


ProfiteableProfiteable ReservesReserves< 4.000 < 4.000 trilliontrillion cubiccubic feetfeet..ZEOLITE TECHNOLOGYZEOLITE TECHNOLOGY

ProfiteableProfiteable reservesreserves1.236 1.236 trilliontrillion cubiccubic feetfeet

AmineAmine technologytechnology

ETHYLENE AND PROPYLENE PRODUCTIONETHYLENE AND PROPYLENE PRODUCTION

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%


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

Olefin production

Steam Cracking

BASF 2000

NaphtaEthane

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


Porous mixed oxideMoVTeNbO

Olefin production

•CO2 + Water

Ethane + O2C2H6 + O2


Olefin production

•CO2 + Water

Combustion is minimized!!Combustion is minimized!!

Ethane + O2C2H6 + O2


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


0 10 20 30 40 500

20

40

60

80

100

Sel

ectiv

ity, %


Propene

CO

CO2


Olefin production



T. Blasco; J.M. Lopez-Nieto et alJ. Catal., 152 (1995) 1-17.


Vanadium-AlPO-5

Olefin production

• CO2 + Water




0 10 20 30 40 500

20

40

60

80

100

Sel

ectiv

ity, %


Propene

CO

CO2


0 10 20 30 40 500

20

40

60

80

100

Sel

ectiv

ity, %


Propene

CO

CO2


Olefin production



T. Blasco; J.M. Lopez-Nieto et alJ. Catal., 152 (1995) 1-17.


At At lowlow conversionconversion thethepropylenepropylene selectivityselectivityisis veryvery highhigh..

COMBINED PROCESSCOMBINED PROCESSREACTIONREACTION--ADSORPTIONADSORPTION

Olefin production

PressureSwing

Absorption

Feed Compressor


Propane

Propane/Propene

PropeneO

DH

Rea

ctor

Propane to propylene by ODH/separation process

Olefin production

PressureSwing

Absorption

Feed Compressor


Propane

Propane/Propeneseparation

PropeneO

DH

Rea

ctor


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, %


Propene

CO

CO2


0 10 20 30 40 500

20

40

60

80

100

Sel

ectiv

ity, %


Propene

CO

CO2


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


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

1st spain-japan joint workshop on “nanoscience and new

Documents