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 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

Outline of the Presentation Zeolites Zeolites Natural Gas Upgrading Upgrading Natural Gas Olefin Production Production Olefin

Outline of the Presentation Zeolites Zeolites Natural Gas Upgrading Upgrading Natural Gas Olefin Production Production Olefin

Zeolites Zeolites are are the the aluminosilicate aluminosilicate Zeolites members of of the the family family of of microporous microporous members solids known known as "molecular as "molecular sieves sieves." ." solids The term term molecular molecular sieve sieve refers refers to to The a particular property property of of these these a particular materials, , i.e i.e., ., the the ability ability to to selectively selectively materials sort molecules molecules based based primarily primarily on on a a sort size exclusion exclusion process process. . This This is is due due to to size a very very regular regular pore pore structure structure of of a molecular dimensions dimensions. . The The maximum maximum molecular size of of the the molecular molecular or or ionic ionic species species size that can can enter enter, , formed formed or or get get out out of of the the that pores of of a a zeolite zeolite is is controlled controlled by by the the pores dimensions of of the the channels channels dimensions Structure of Zeolite EU-1 Structure of Zeolite EU-1

Zeolites Chabazite ZSM-5 Faujasite Chabazite ZSM-5 Faujasite 8 TO 2 10 TO 2 12 TO 2 8 TO 2 10 TO 2 12 TO 2 3.8 x 3.8 Å 5.5 x 5.1 Å 7.4 x 7.4 Å 3.8 x 3.8 Å 5.5 x 5.1 Å 7.4 x 7.4 Å

Zeolites UTD-1 ECR-34 Cloverite UTD-1 ECR-34 Cloverite 14 TO 2 18 TO 2 20 TO 2 14 TO 2 18 TO 2 20 TO 2 8.2 x 8.1 Å 10.1 x 10.1 Å 13.2 x 6.0 x 3.5 Å 8.2 x 8.1 Å 10.1 x 10.1 Å 13.2 x 6.0 x 3.5 Å

Zeolites 1 Kinetic diameter [nm] 0.8 0.6 0.4 0.2 0 e n e e e e e e e e e e e e e N N n e n n m n n n e e e a r n n n e d d o o o o n n n n n n n n n n n n n i e e e 3 3 u n t a y e e a a a a a e e e t g i i g g e g n a a a e ) ) a x x p o i t p x 9 9 l n r e h h p t h h p t t t z l l o o o y o e u n y y w a y u u c m o t o o e n H F r x r x t t t x x n i h r e e b e e b b e o d d h o t k r r r e m 4 o i p - - - 4 m p p - - p y n o o b p o C 1 o C m n o o a h l s s o e c ( l ( i i c y n b n y c o r c a b c r a c

Zeolites 1 8.1 Å Kinetic diameter [nm] 0.8 7.4 Å 5.5 Å 0.6 3.8 Å 0.4 0.2 0 e n e e e e e e e e e e e e e N N n e n n m n n n e e e a r n n n e d d o o o o n n n n n n n n n n n n n i e e e 3 3 u n t a y e e a a a a a e e e t g i i g g e g n a a a e ) ) a x x p o i t p x 9 9 l n r e h h p t h h p t t t z l l o o o y o e u n y y w a y u u c m o t o o e n H F r x x t t t x x n i r h r e e b e e b b e o d d h o t k r r r e m 4 4 o i p - - - m p p - - p y n o o b p o C 1 o C m n o o a h l s s o e c ( l ( i i c y n b n y c o r c a b c r a c

Natural Gas Upgrading Gas separation of CO 2 / N 2 / CH 4 1 8.1 Å Kinetic diameter [nm] 0.8 7.4 Å 5.5 Å 0.6 3.8 Å 0.4 0.2 0 e n e d e n e e e e e e e e e e e e N N n n e m n n n n e e e a r i n n n e d x o o o o n n n n n n n n n n n n i e e g a 3 3 u n t a y e e a a a a a e e e t g i o g e g n a a e ) ) a x o p h o i t p x 9 9 l n r e h p t h h p t t t z l l o o i y e u n y y w r a y t u u c m d o t o o e n H F r x t x e t t x x n h r e b e e b b e o d i h o k m r r r e m 4 4 o n n p - - - p p - - p y o o b p o C 1 o C m o o o a h l s s e c ( b l ( i i c y n n r y c o a c b c r a c

Natural Gas Upgrading World Oil reserves World Oil reserves To understand understand the the aiming aiming To of the the Natural Gas Natural Gas of Upgrading, , it it is is needed needed to to Upgrading spend some some time time looking looking spend at the the energy energy landscape landscape at for the the near near future future for

Natural Gas Upgrading World Oil depletion depletion World Oil World Oil reserves World Oil reserves 1.200 billion billion bbl bbl 1.200

Natural Gas Upgrading World Natural Gas Reserves World Natural Gas Reserves 6.180 trillion trillion cubic cubic feet feet 6.180 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.

Natural Gas Upgrading World Natural Gas Reserves World Natural Gas Reserves 6.180 trillion trillion cubic cubic feet feet 6.180 Their exploitation is not Their exploitation is not economically profitable economically profitable Proved Reserves Reserves Proved Profiteable Reserves Profiteable Reserves 6.180 trillion trillion cubic cubic feet feet 1.236 trillion trillion cubic cubic feet feet 6.180 1.236

Why ? 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 CO 2 0.5 – 10.0 , peak 70 Corrosion, no heating value, SH 2 0 – 1, peak 10 Corrosion, toxicity N 2 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 CO 2 0.5 vol% 3 – 4 vol.% 5.7 – 22.9 mg/m 3 H 2 S 10 vol% N 2 3 vol% 3 vol.% H 2 O 0.5 vol% 150 ppmv C 2+ 4 vol% 4 vol%

Natural Gas Upgrading The optimum situation is the in- - The 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 CO 2 0.5 vol% 3 – 4 vol.% < 50 ppmv 5.7 – 22.9 mg/m 3 H 2 S 10 vol% < 4 ppmv N 2 3 vol% 3 vol.% < 1 vol.% H 2 O 0.5 vol% 150 ppmv < 0.1 ppmv C 2+ 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. Particularly difficult is the Particularly difficult is the removal of CO 2 and N 2 from removal of CO 2 and N 2 from raw Natural Gas streams. raw Natural Gas streams. Impurity Initial value Pipeline Gas Feed to LNG Plant CO 2 0.5 vol% 3 – 4 vol.% < 50 ppmv 5.7 – 22.9 mg/m 3 H 2 S 10 vol% < 4 ppmv N 2 3 vol% 3 vol.% < 1 vol.% H 2 O 0.5 vol% 150 ppmv < 0.1 ppmv C 2+ 4 vol% 4 vol% < 2 vol.%

Natural Gas Upgrading Aqueous amine or organic solvent scrubbing CO 2 Gas Lean Amine Natural Gas Natural Gas + CO 2 Rich Amine

Natural Gas Upgrading Can help help zeolites zeolites in in upgrading upgrading CO CO 2 ? Can 2 ?

Natural Gas Upgrading 240 Pressure (bars) P=0.025 200 Adsorbed gas (mg/g) P=0.050 P=0.100 160 P=0.200 P=0.400 P=0.600 120 P=1.00 CO 2 P=1.50 P=2.0 80 P=3.0 P=4.0 P=5.0 40 New zeolite New zeolite CH 4 0 8 TO 2 8 TO 2 10 20 30 40 50 60 70 3.7 x 3.7 Å 3.7 x 3.7 Å Temperature (ºC)

Molecular Sieve Technology for CO 2 capture Molecular Sieve Technology for CO 2 capture Feed Enriched CH 4 10 psi pressure drop PRODUCT Compressor 30 psia C1, C2 Pressure Swing FEED Absorption High Pressure 5 psia C1, C2, C3, C4 + TAIL GAS CO 2 , H 2 O Vacuum Compressor CO 2 , H 2 O, C3 + , Lost HCs

Natural Gas Upgrading Typical amine Process Acid Gas Sweet Gas Lean Amine Stripper Condenser (Steel) Reflux Pump Reboiler Sour Gas Fuel Rich Amine Heating Medium Flash Tank Exchanger Booster Pump Filter