• No results found

Adsorption Properties of MFI-Type Zeolite Films for Upgrading of Biofuels

N/A
N/A
Info
Download
Protected

Academic year: 2022

Share "Adsorption Properties of MFI-Type Zeolite Films for Upgrading of Biofuels"

Copied!
198
0
0

Loading.... (view fulltext now)

Download now ( 198 Page )

Full text

(1)DOC TOR A L T H E S I S. ISSN 1402-1544 ISBN 978-91-7583-781-9 (print) ISBN 978-91-7583-782-6 (pdf) Luleå University of Technology 2016. Amirfarrokh Farzaneh Adsorption Properties of MFI-Type Zeolite Films for Upgrading of Biofuels. Department of Civil, Environmental and Natural Resources Engineering Division of Chemical Engineering. Adsorption Properties of MFI-Type Zeolite Films for Upgrading of Biofuels. Amirfarrokh Farzaneh. Chemical Technology.

(2)

(3) ‘ –‘”ƒŽŠ‡•‹• . †•‘”’–‹‘”‘’‡”–‹‡•‘ˆ

(4) Ǧ›’‡‡‘Ž‹–‡ ‹Ž•ˆ‘”’‰”ƒ†‹‰‘ˆ‹‘ˆ—‡Ž•   ‹”ˆƒ””‘Š ƒ”œƒ‡Š   .     —Ž‡¤‹˜‡”•‹–›‘ˆ‡ Š‘Ž‘‰› ‡’ƒ”–‡–‘ˆ‹˜‹Žǡ˜‹”‘‡–ƒŽƒ†ƒ–—”ƒŽ‡•‘—” ‡•‰‹‡‡”‹‰ ‹˜‹•‹‘‘ˆŠ‡‹ ƒŽ‰‹‡‡”‹‰ Š‡‹ ƒŽ‡ Š‘Ž‘‰›  ‡„”—ƒ”›ʹͲͳ͹ . .

(5) Cover image and graphics designed by Kazhal Malekzadeh. Printed by Luleå University of Technology, Graphic Production 2017 ISSN 1402-1544 ISBN 978-91-7583-781-9 (print) ISBN 978-91-7583-782-6 (pdf) Luleå 2017 www.ltu.se.

(6)  . . DzŠ‡ Š‹‰Š‡•– ‹• –‘ —†‡”•–ƒ† –Šƒ– ƒŽŽ ˆƒ – ‹• ”‡ƒŽŽ› –Š‡‘”›Ǥ Š‡ „Ž—‡ ‘ˆ –Š‡ •› ”‡˜‡ƒŽ• –‘ —• –Š‡ „ƒ•‹  Žƒ™ ‘ˆ ‘Ž‘”Ǥ ‡ƒ” Š ‘–Š‹‰ „‡›‘† –Š‡ ’Š‡‘‡ƒǡ –Š‡› –Š‡•‡Ž˜‡• ƒ”‡ –Š‡ –Š‡‘”›Ǩdz ‘Šƒ‘Žˆ‰ƒ‰˜‘ ‘‡–Š‡ .

(7)

(8)

(9) .

(10) .

(11) . .

(12) Abstract ‹–Š–Š‡†‡’Ž‡–‹‰”‡•‡”˜‘‹”•‘ˆˆ‘••‹Žˆ—‡Ž•ǡ‹ ”‡ƒ•‹‰‡˜‹”‘‡–ƒŽ ‘ ‡”• ˆ‘”ˆŽ—‡Ǧ‰ƒ•‡‹••‹‘•ˆ”‘ˆ‘••‹ŽǦˆ—‡Ž ‘„—•–‹‘ƒ†‰”‘™‹‰™‘”Ž†’‘’—Žƒ–‹‘ǡ –Š‡ ‡‡† ˆ‘” –Š‡ †‡˜‡Ž‘’‡– ‘ˆ ‡™ •—•–ƒ‹ƒ„Ž‡ ˆ—‡Ž• ‹• ‰”‡ƒ–‡” –Šƒ ‡˜‡”Ǥ ‘™‡˜‡”ǡ–‘„‡ƒ„Ž‡–‘ ‘’‡–‡™‹–Š–‘†ƒ›ǯ•ƒ–—”‡–‡ Š‘Ž‘‰‹‡•ˆ‘”’”‘†— –‹‘ ‘ˆˆ—‡Ž•ˆ”‘ˆ‘••‹Ž•‘—” ‡•ǡ‡™‡ˆˆ‹ ‹‡–’”‘ ‡••‹‰ƒŽ–‡”ƒ–‹˜‡•ˆ‘”—’‰”ƒ†‹‰‘ˆ „‹‘ˆ—‡Ž•—•–„‡†‡˜‡Ž‘’‡†Ǥ ‹‘ˆ—‡Ž• ’”‘†— ‡† „› ‡Ǥ‰Ǥ ˆ‡”‡–ƒ–‹˜‡ ’”‘ ‡••‡• Šƒ˜‡ „‡ ‘‡ ’”‘‹•‹‰ ƒŽ–‡”ƒ–‹˜‡• –‘ ˆ—‡Ž• ’”‘†— ‡† ˆ”‘ ˆ‘••‹Ž •‘—” ‡•Ǥ ‡ ‘˜‡”› ‘ˆ „‹‘ˆ—‡Ž• „› •‡Ž‡ –‹˜‡ ‡„”ƒ‡• ƒ† ƒ†•‘”„‡–• Šƒ• „‡‡ ‹†‡–‹ˆ‹‡† ƒ• ’”‘‹•‹‰ ‡‡”‰› ‡ˆˆ‹ ‹‡–”‡ ‘˜‡”›”‘—–‡•Ǥ

(13) ’ƒ”–‹ —Žƒ”ǡœ‡‘Ž‹–‡„ƒ•‡†ƒ†•‘”„‡–•ƒ†‡„”ƒ‡• •Š‘™‰”‡ƒ–’‘–‡–‹ƒŽ‹–Š‹•ƒ”‡ƒǤ 

(14)  –Š‹• ™‘”ǡ –Š‡ ƒ†•‘”’–‹‘ ’”‘’‡”–‹‡• ‘ˆ 

(15) Ǧ–›’‡ œ‡‘Ž‹–‡ ˆ‹Ž• ™‡”‡ •–—†‹‡† —•‹‰insituȋƒ––‡—ƒ–‡†–‘–ƒŽ”‡ˆŽ‡ –‹‘ȌΫ 

(16) ȋ ‘—”‹‡”–”ƒ•ˆ‘”‹ˆ”ƒ”‡†Ȍ •’‡ –”‘• ‘’› ‹ ‘”†‡” –‘ —†‡”•–ƒ† –Š‡ ƒ†•‘”’–‹‘ ’”‘’‡”–‹‡• ‘ˆ –Š‡•‡œ‡‘Ž‹–‡• ™‹–Š ƒ •’‡ ‹ƒŽ ˆ‘ —• ‘ –Š‡ ƒ†•‘”’–‹‘ ‘ˆ ‘Ž‡ —Ž‡• ”‡Ž‡˜ƒ– ˆ‘” „‹‘ˆ—‡Ž ’”‘†— –‹‘Ǥ ”ƒ†‹–‹‘ƒŽŽ›ǡ œ‡‘Ž‹–‡• ƒ”‡ •›–Š‡•‹œ‡† ƒ– Š‹‰Š ’  Ž‡ƒ†‹‰ –‘ –Š‡ ˆ‘”ƒ–‹‘ ‘ˆ ’‘Žƒ” •‹Žƒ‘Ž †‡ˆ‡ –• ‹ –Š‡ ˆ”ƒ‡™‘” ƒ† ”‡†— ‹‰ –Š‡ ƒ†•‘”’–‹‘ •‡Ž‡ –‹˜‹–› –‘™ƒ”† ƒŽ ‘Š‘Ž• ‹ ƒŽ ‘Š‘ŽȀ™ƒ–‡” ‹š–—”‡•Ǥ  –Š‡ ‘–”ƒ”›ǡ •›–Š‡•‹• ƒ– ‡ƒ” ‡—–”ƒŽ ’  ƒ† ‹ –Š‡ ’”‡•‡ ‡ ‘ˆ ˆŽ—‘”‹†‡ ‹‘• ”‡•—Ž–• ‹ ƒ Ž‘™ †‡•‹–› ‘ˆ •–”— –—”ƒŽ†‡ˆ‡ –•Ǥ™‘•‹Ž‹ ƒŽ‹–‡Ǧͳˆ‹Ž•™‡”‡•–—†‹‡†‹–Š‹•™‘”ǡ‘‡’”‡’ƒ”‡† —•‹‰ ˆŽ—‘”‹†‡ ƒ† –Š‡ ‘–Š‡” ‘‡ —•‹‰ Š›†”‘š‹†‡ ƒ• ‹‡”ƒŽ‹œ‹‰ ƒ‰‡–Ǥ ‹‰Ž‡Ǧ ‘’‘‡–ƒ†•‘”’–‹‘‹•‘–Š‡”•‘ˆ„—–ƒ‘Žƒ†™ƒ–‡”˜ƒ’‘”‹„‘–Š•‹Ž‹ ƒŽ‹–‡Ǧͳ ˆ‹Ž• ™‡”‡ †‡–‡”‹‡† ƒ– †‹ˆˆ‡”‡– –‡’‡”ƒ–—”‡• —•‹‰ Ǧ 

(17)  •’‡ –”‘• ‘’›Ǥ Š‡ ƒ‰—‹” ƒ† ‹’• ƒ†•‘”’–‹‘ ‘†‡Ž• ™‡”‡ •— ‡••ˆ—ŽŽ› ˆ‹––‡† –‘ ‡š’‡”‹‡–ƒŽ†ƒ–ƒǡƒ†–Š‡ˆ‹––‡†’ƒ”ƒ‡–‡”•‘„–ƒ‹‡†‹–Š‹•™‘”™‡”‡‹˜‡”› ‰‘‘† ƒ‰”‡‡‡– ™‹–Š ˜ƒŽ—‡• ”‡’‘”–‡† ‹ –Š‡ Ž‹–‡”ƒ–—”‡Ǥ †•‘”„‡† ƒ‘—–• ‘ˆ „—–ƒ‘Žƒ†™ƒ–‡”ˆ”‘„‹ƒ”›˜ƒ’‘”‹š–—”‡•™‡”‡‡š–”ƒ –‡†ˆ”‘–Š‡‹ˆ”ƒ”‡† •’‡ –”ƒ ƒ• ™‡ŽŽ ƒ• –Š‡ ƒ†•‘”’–‹‘ •‡Ž‡ –‹˜‹–‹‡•Ǥ Š‡ •‹Ž‹ ƒŽ‹–‡Ǧͳ ˆ‹Ž ’”‡’ƒ”‡† ‹ ˆŽ—‘”‹†‡‡†‹—™ƒ•ˆ‘—†–‘„‡•‹‰‹ˆ‹ ƒ–Ž›‘”‡„—–ƒ‘Ž•‡Ž‡ –‹˜‡†—‡–‘–Š‡ Ž‘™‡”†‡•‹–›‘ˆ†‡ˆ‡ –•‹–Šƒ–•ƒ’Ž‡Ǥ ‹‘‰ƒ• ȋ‡–Šƒ‡Ȍ ‹• ƒ‘–Š‡” ’”‘‹•‹‰ „‹‘ˆ—‡Ž –Šƒ– ‹• ‘‘Ž› ’”‘†— ‡† „› ƒƒ‡”‘„‹ †‡‰”ƒ†ƒ–‹‘‘ˆ„‹‘ƒ••Ǥ ‘™‡˜‡”ǡ„‡ˆ‘”‡‹–ƒ›„‡—•‡†ǡ ‘–ƒ‹ƒ–• Šƒ˜‡ –‘ „‡ ”‡‘˜‡† ˆ”‘ –Š‡ ‰ƒ•Ǣ –™‘ ‘ˆ –Š‡ ‘•– ƒ„—†ƒ– ‘–ƒ‹ƒ–• ‹ .

(18) „‹‘‰ƒ• ƒ”‡ ƒ”„‘ †‹‘š‹†‡ ƒ† ™ƒ–‡” ˜ƒ’‘”Ǥ —Ž–‹ ‘’‘‡– ƒ†•‘”’–‹‘ ‘ˆ ‡–Šƒ‡ǡ ƒ”„‘†‹‘š‹†‡ƒ†™ƒ–‡”˜ƒ’‘”‹œ‡‘Ž‹–‡ƒǦǦͷŠƒ•–Š‡”‡ˆ‘”‡„‡‡ •–—†‹‡†ƒ–˜ƒ”‹‘—• ‘’‘•‹–‹‘•ƒ†–‡’‡”ƒ–—”‡•—•‹‰Ȃ 

(19) •’‡ –”‘• ‘’›Ǥ ƒ–‡” ƒ† ƒ”„‘ †‹‘š‹†‡ ™‡”‡ ’”‡ˆ‡”‡–‹ƒŽŽ› ƒ†•‘”„‡† ‘˜‡” ‡–Šƒ‡ ™‹–Š –Š‡ Š‹‰Š‡•– •‡Ž‡ –‹˜‹–› –‘™ƒ”†• ™ƒ–‡”Ǥ Š‡ Š‹‰Š •‡Ž‡ –‹˜‹–› –‘™ƒ”†• ™ƒ–‡” ™ƒ• ƒ• ”‹„‡† –‘ ƒ†•‘”’–‹‘ ‘ˆ ™ƒ–‡” ‘ ’‘Žƒ” •‹–‡• ƒ••‘ ‹ƒ–‡† ™‹–Š ƒŽ—‹— ƒ† •–”— –—”ƒŽ †‡ˆ‡ –• ‹ –Š‡ ˆ‘” ‘ˆ •‹Žƒ‘Ž ‰”‘—’• ƒ† •—„•‡“—‡– ˆ‘”ƒ–‹‘ ‘ˆ ƒ†•‘”„‡† ™ƒ–‡” Ž—•–‡”• ƒ– –Š‡•‡ ’‘Žƒ” •‹–‡•Ǥ Š‡ ƒ†•‘”„‡† ‘ ‡–”ƒ–‹‘• ‘„–ƒ‹‡† ™‡”‡ ‘’ƒ”‡† –‘ ’”‡†‹ –‹‘• „› –Š‡

(20) †‡ƒŽ †•‘”„‡† ‘Ž—–‹‘ Š‡‘”› ȋ

(21) ȌǤ Ž–Š‘—‰Š –Š‡ ƒ†•‘”„‡† ‘ ‡–”ƒ–‹‘• ’”‡†‹ –‡† —•‹‰ –Š‡

(22)  •Š‘™‡† –Š‡ •ƒ‡ –”‡† ƒ• –Š‡ ‡š’‡”‹‡–ƒŽ †ƒ–ƒǡ –Š‡

(23)  ‘—Ž† ‘– ˆ—ŽŽ› ƒ’–—”‡ –Š‡ ƒ†•‘”’–‹‘„‡Šƒ˜‹‘”‘ˆ–Š‡‰ƒ•‹š–—”‡•‹Š‹‰Š•‹Ž‹ ƒƒǦǦͷǤ             . 

(24) . .

(25) Acknowledgments  ‘”‡‘•–ǡ

(26) ™‘—Ž†Ž‹‡–‘‡š’”‡••›•‹ ‡”‡‰”ƒ–‹–—†‡–‘›•—’‡”˜‹•‘””‘ˆǤ ƒ––‹ƒ• ”ƒŠǤ Šƒ ›‘— ˆ‘” ›‘—” ‹† ‰—‹†ƒ ‡ǡ ‡ ‘—”ƒ‰‡‡–ǡ ’ƒ–‹‡ ‡ ƒ† –”—•– ‹ › ™‘”Ǥ

(27)  ƒ ˜‡”› ‰”ƒ–‡ˆ—Ž –‘ ”‘ˆǤ ‘ƒ• ‡†Ž—† ˆ‘” ‰‹˜‹‰ ‡ –Š‡ ‘’’‘”–—‹–› ‘ˆ ™‘”‹‰ ƒ– Š‡‹ ƒŽ ‡ Š‘Ž‘‰› ”‡•‡ƒ” Š ‰”‘—’ ƒ† ƒŽŽ ›‘—” ƒ†˜‹ ‡Ǥ —”–Š‡”ǡ

(28)  ™‘—Ž† Ž‹‡ –‘ –Šƒ › ‘ •—’‡”˜‹•‘”•Ǣ ••‘ Ǥ ”‘ˆǤ ŽŽƒ ‘Ž‰”‡ ƒ† ”Ǥ Ž‹•ƒ˜‡–ƒ ‘–ƒ’‘˜ƒ ˆ‘” –Š‡‹” •—’’‘”–ǡ Š‡Ž’ˆ—Ž †‹• —••‹‘• ”‡‰ƒ”†‹‰•’‡ –”‘• ‘’›ƒ†–ƒ‹‰–‹‡–‘–”›–‘ƒ•™‡”›“—‡•–‹‘•ǡ”Ǥ‹‰ Š‘—‹•ƒ ‘™Ž‡†‰‡†ˆ‘”’”‡’ƒ”‹‰–Š‡œ‡‘Ž‹–‡ˆ‹Ž•Ǥ Šƒ•–‘”Ǥ‘Ž–žƒ •‹ƒ†”‘ˆǤŽ‡‰–œ—–‹ˆ‘”‘—” ‘ŽŽƒ„‘”ƒ–‹‘ƒ† ••‘ Ǥ”‘ˆǤ ‘Šƒ‡‘—œ‘ˆ‘”Š‡Ž’‹‰‡™‹–Š‹ƒ‰‡•Ǥ

(29) Ž‹‡–‘‡š’”‡••› ƒ’’”‡ ‹ƒ–‹‘–‘–Š‡Š‡ƒ†‘ˆ‘—”†‹˜‹•‹‘ǡ”‘ˆǤŽ”‹ƒ‘˜ƒǡˆ‘”Š‡”‹†•—’’‘”–Ǥ

(30)  ƒŽ•‘‘™‡ƒ–Šƒ›‘—–‘ ڔƒƒŽŽ‹ˆ‘”Š‡Ž’‹‰‡™‹–Š’”ƒ –‹ ƒŽ’”‘„Ž‡•‹ –Š‡ Žƒ„ǡ ƒ† –‘ ‡Ž‹ ‰•–”ڏ ˆ‘” Š‡Ž’‹‰ ‘—– ™‹–Š ƒ†‹‹•–”ƒ–‹˜‡ ™‘”Ǥ

(31)  ƒ ”‡ƒŽŽ› ‰”ƒ–‡ˆ—Ž –‘ ƒœŠƒŽ ƒŽ‡œƒ†‡Š ˆ‘” –Š‡ ”‡ƒ–‹˜‡ †‡•‹‰ ‘ˆ –Š‡ ‰”ƒ’Š‹ • ƒ† ‘˜‡”‹ƒ‰‡Ǥ 

(32)  ™‘—Ž† Ž‹‡ –‘ ƒ ‘™Ž‡†‰‡ ™‡†‹•Š ‡•‡ƒ” Š ‘— ‹Ž ȋȌ ˆ‘” ˆ‹ƒ ‹ƒŽŽ› •—’’‘”–‹‰–Š‹•™‘”Ǥ ’‡ ‹ƒŽ –Šƒ• –‘ ”Ǥ ƒ‹Ž ‘”‡Ž•‹› ˆ‘” „‡‹‰ ƒ ˆƒ–ƒ•–‹  ˆ”‹‡†ǡ ˜‡”› Š‡Ž’ˆ—Ž ‘ŽŽ‡ƒ‰—‡ ƒ† •— Š ƒ ”‡•’‘•‹„Ž‡ ‡–‘” ™Š‘ ‹–”‘†— ‡† ‡ –‘ ‡˜‡”› ’‘••‹„Ž‡ ’‡”•‘

(33)  ‡‡†‡† –‘ ‘™Ǩ Šƒ• –‘ ”Ǥ ‹†•ƒ› ŠŽ‹ ˆ‘” ‘—” ˆ”—‹–ˆ—Ž ‘ŽŽƒ„‘”ƒ–‹‘ ƒ† –Š‡ ‰”‡ƒ– –‹‡ ™‡ Šƒ† ™‘”‹‰ –‘‰‡–Š‡”ǡ ƒ† –‘ ”Ǥ ƒ‹‡Žƒ—•ƒ‘˜ƒ ˆ‘” –Š‡ —•‡ˆ—Ž †‹• —••‹‘• ƒ† ˜ƒŽ—ƒ„Ž‡ ‹’—–•Ǥ

(34)  ‡š’”‡•• › ‰”ƒ–‹–—†‡–‘”‘ˆǤ‘„‹ƒ•‹ Šƒ”†•ˆ‘”›‘—”Š‡Ž’ƒ†•—’’‘”–†—”‹‰›ƒ•–‡”̵• †‡‰”‡‡•–—†‹‡•ƒ†›‘—”‰”‡ƒ–ƒ†˜‹ ‡ˆ‘” ‘–‹—ƒ–‹‘‘ˆ› ƒ”‡‡”Ǥ 

(35) ›†ƒ‹Ž›™‘”

(36) Šƒ˜‡„‡‡„Ž‡••‡†™‹–Šˆ”‹‡†Ž›ƒ† Š‡‡”ˆ—Ž ‘ŽŽ‡ƒ‰—‡•ƒ† ˆ”‹‡†• ™Š‘ ƒŽ™ƒ›• •—’’‘”–‡† ‡Ǥ Šƒ• –‘ ‡˜‡”›‘‡ ƒ– Š‡‹ ƒŽ ‡ Š‘Ž‘‰› ƒ†‹˜‹•‹‘‘ˆŠ‡‹ ƒŽ‰‹‡‡”‹‰Ǩ‹ ‡

(37) •–ƒ”–‡†—‹˜‡”•‹–›—–‹Ž–‘†ƒ›ǡ

(38) ™ƒ• •‘Ž— ›–Šƒ–

(39) ‡–ƒ›ƒƒœ‹‰’‡‘’Ž‡™Š‘Šƒ˜‡„‡‡ƒŽ™ƒ›••—’’‘”–‹˜‡–‘‡ǡ ƒ†™‡Šƒ†•‘— Šˆ—–‘‰‡–Š‡”ǡ–Šƒ•–‘ƒŽŽǨ Š‘—•ƒ†•‘ˆ–Šƒ•–‘›•‹„Ž‹‰•”‡œ‘—ƒ† ƒ”œƒǨ

(40)  ƒ‘–‹ƒ‰‹‡™Šƒ– –‘†‘™‹–Š‘—–›‘—”•—’’‘”–Ǥ†ˆ‹ƒŽŽ›ǡ–‘›’ƒ”‡–•ǣ !ϡϧϳϧίΎϧ έΩΎϣ ϭ έΩ̡ ˬϡ΍ ̶̳Ωϧί έΎϣόϣ ϭ ϡϠόϣ ϥΎΑέϬϣ ί΍ ϥ΍έ̰ϳΑ αΎ̡γ. 

(41)

(42) .

(43) . 

(44)

(45)

(46) . .

(47) List of Papers ƒ’‡”Ȥǣ Adsorption of Water and Butanol in SilicaliteǦ1 Film Studied with in Situ AttenuatedTotalReflectance–FourierTransformInfraredSpectroscopy ‹”ˆƒ””‘Š ƒ”œƒ‡Šǡ ‹‰ Š‘—ǡ Ž‹•ƒ˜‡–ƒ ‘–ƒ’‘˜ƒǡ ‘Ž–ž ƒ •‹ǡ ‹†•ƒ› ŠŽ‹ǡŽŽƒ ‘Ž‰”‡ǡ ‘ƒ• ‡†Ž—†ǡƒ––‹ƒ• ”ƒŠǤLangmuirȋʹͲͳͷȌǡ͵ͳǡͶͺͺ͹Ǧ ͶͺͻͶ ƒ’‡”ȤȤǣ Adsorption of Butanol and Water Vapors in SilicaliteǦ1 Films with Low DefectDensity ‹”ˆƒ””‘Š ƒ”œƒ‡Šǡ ‹‰ Š‘—ǡ Ž‡‰ Ǥ –œ—–‹ǡ ‘Ž–ž ƒ •‹ǡ ‘ƒ• ‡†Ž—†ǡŽŽƒ ‘Ž‰”‡ƒ†ƒ––‹ƒ• ”ƒŠǤLangmuirȋ2016)ǡ͵ʹǡͳͳ͹ͺͻȂͳͳ͹ͻͺ ƒ’‡”ȤȤȤǣ A Comparative Study of the Effect of Defects on Selective Adsorption of ButanolfromBinaryVaporMixturesinSilicaliteǦ1Films ‹”ˆƒ””‘Š ƒ”œƒ‡Šǡ ‹†•ƒ› ŠŽ‹ǡ ŽŽƒ ‘Ž‰”‡ ƒ† ƒ––‹ƒ• ”ƒŠǡ ƒ—• ”‹’– ƒ’‡”Ȥǣ Colloidal DefectǦFree SilicaliteǦ1 Single Crystals: Preparation, Structure Characterization,Adsorption,andSeparationPropertiesforAlcohol/Water Mixtures ƒ Š‘—ǡ ‘Šƒ‡ ‘—œ‘ǡ ‹”ˆƒ””‘Š ƒ”œƒ‡Šǡ Ž‡‰ Ǥ –œ—–‹ǡ ƒ––‹ƒ•. ”ƒŠǡƒ† ‘ƒ• ‡†Ž—†ǡLangmuirȋʹͲͳͷȌǡ͵ͳǡͺͶͺͺΫͺͶͻͶ ƒ’‡”ǣ EffectofWaterontheAdsorptionofMethaneandCarbonDioxideinZeolite NaǦZSMǦ5StudiedUsinginSituATRǦFTIRSpectroscopy ‹†•ƒ› ŠŽ‹ǡ Žƒ†‹‹” ‡”‡œ‘˜•›ǡ ˜‡ Y„‡”‰ǡ ‹”ˆƒ””‘Š ƒ”œƒ‡Šǡ ŽŽƒ ‘Ž‰”‡ ƒ† ƒ––‹ƒ• ”ƒŠǡ The Journal of Physical Chemistry C ȋʹͲͳ͸Ȍǡ ͳʹͲǡ ʹͻͳͶͶǦʹͻͳͷʹ ƒ’‡”

(48) ǣ Ternary Adsorption of Methane, Water and Carbon Dioxide in Zeolite NaǦ ZSMǦ5StudiedUsinginSituATRǦFTIRSpectroscopy ‹†•ƒ›ŠŽ‹ǡ‹”ˆƒ””‘Š ƒ”œƒ‡ŠǡŽŽƒ ‘Ž‰”‡ǡ ‘ƒ• ‡†Ž—†ƒ†ƒ––‹ƒ•. ”ƒŠǡTheJournalofPhysicalChemistryC,—„‹––‡†

(49) .

(50) TothereadersǣŠ‹•†‘ –‘”ƒŽ–Š‡•‹•‹•ƒ•—ƒ”›‘ˆ”‡•‡ƒ” Š’‡”ˆ‘”‡†‹–Š‡ ’ƒ’‡”• Ž‹•–‡† ƒ„‘˜‡ǡ ƒ† –Š‡ ”‡ƒ†‡”• ƒ”‡ ‡ ‘—”ƒ‰‡† –‘ ”‡ƒ† –Š‡ –Š‡•‹• ‹ ‘Œ— –‹‘™‹–Š–Š‡’ƒ’‡”•Ǥ Š‡ƒ—–Š‘”ǯ• ‘–”‹„—–‹‘–‘–Š‡’ƒ’‡”•ǣ

(51) Ǥ.

(52)

(53) Ǥ.

(54)

(55)

(56) Ǥ.

(57) Ǥ Ǥ 

(58) Ǥ. ‡”ˆ‘”‡† –Š‡ Ǧ 

(59)  ‡š’‡”‹‡–ƒŽ ™‘”ǡ ‹–‡”’”‡–‡† –Š‡ ”‡•—Ž–• ™‹–Š ‘Ǧƒ—–Š‘”•ƒ†™”‘–‡–Š‡ˆ‹”•–†”ƒˆ–ƒ†™”‘–‡–Š‡ƒ—• ”‹’–™‹–Š –Š‡ ‘Ǧƒ—–Š‘”•Ǥ ‡”ˆ‘”‡† –Š‡ Ǧ 

(60)  ‡š’‡”‹‡–ƒŽ ™‘”ǡ ‹–‡”’”‡–‡† –Š‡ ”‡•—Ž–• ™‹–Š ‘Ǧƒ—–Š‘”• ƒ† ™”‘–‡ –Š‡ ˆ‹”•– †”ƒˆ– ƒ’ƒ”– ˆ”‘ –Š‡  •‡ –‹‘ ƒ†™”‘–‡–Š‡ƒ—• ”‹’–™‹–Š–Š‡ ‘Ǧƒ—–Š‘”•Ǥ ‡”ˆ‘”‡† –Š‡ ‡š’‡”‹‡–ƒŽ ™‘”ǡ ‹–‡”’”‡–‡† –Š‡ ”‡•—Ž–• ™‹–Š ‘Ǧ ƒ—–Š‘”•ƒ†™”‘–‡–Š‡ˆ‹”•–†”ƒˆ–ƒ†™”‘–‡–Š‡ƒ—• ”‹’–™‹–Š–Š‡ ‘Ǧ ƒ—–Š‘”•Ǥ ‡”ˆ‘”‡† –Š‡ Ǧ 

(61)  ‡š’‡”‹‡–ƒŽ ™‘”ǡ ƒ† ”‡Žƒ–‡† †ƒ–ƒ ‡˜ƒŽ—ƒ–‹‘ƒ††‹• —••‹‘Ǥ ‡˜‹‡™ƒ††‹• —••‹‘”‡‰ƒ”†‹‰–Š‡‡š’‡”‹‡–ƒŽ™‘”Ǥ ‡˜‹‡™ƒ†’ƒ”–‹ ‹’ƒ–‹‘‹–Š‡‡š’‡”‹‡–ƒŽ™‘”Ǥ.  ‡‡”Ǧ”‡˜‹‡™‡†‘ˆ‡”‡ ‡‘–”‹„—–‹‘•ȋ‘–‹ Ž—†‡†‹–Š‡–Š‡•‹•Ȍǣ i. ƒ”œƒ‡ŠǡǤƒ† ”ƒŠǡǤǢ‹ƒ”›ƒ†•‘”’–‹‘‘ˆ„—–ƒ‘Žƒ†™ƒ–‡”˜ƒ’‘”‹ •‹Ž‹ ƒŽ‹–‡Ǧͳ ˆ‹Ž •›–Š‡•‹œ‡† ‹ Ǧ ‡†‹ƒ —•‹‰ ‹Ǧ•‹–— Ǧ 

(62)  •’‡ –”‘• ‘’›ǡ Oral presentation at 18th International Zeolite Conferenceǡ —‡ ʹͲͳ͸ǡ ‹‘ †‡ ƒ‡‹”‘ǡ”ƒœ‹Ž ii. ŠŽ‹ǡ ǤǢ ƒ”œƒ‡Šǡ ǤǢ ‘Ž‰”‡ǡ ǤǢ ‡†Ž—†ǡ ǤǢ ”ƒŠǡ ǤǢ ‡”ƒ”› ƒ†•‘”’–‹‘‘ˆ‡–Šƒ‡ǡ™ƒ–‡”ƒ† ƒ”„‘†‹‘š‹†‡‹œ‡‘Ž‹–‡ƒǦǦͷ•–—†‹‡† —•‹‰ ‹Ǧ•‹–— Ǧ 

(63)  •’‡ –”‘• ‘’›ǡ Oral presentation at 12th International Conference on the Fundamentals of Adsorptionǡ —‡ ʹͲͳ͸ǡ ”‹‡†”‹ Š•Šƒˆ‡ǡ. ‡”ƒ› iii. ƒ”œƒ‡ŠǡǤǢŠ‘—ǡǤǢ ‡†Ž—†ǡǤƒ† ”ƒŠǡǤǢ†•‘”’–‹‘‘ˆƒ–‡”ƒ†ͳǦ —–ƒ‘Ž ‹ 

(64)  ‡‘Ž‹–‡ ‹Ž• •–—†‹‡† ™‹–Š ‹Ǧ•‹–— Ǧ 

(65)  ’‡ –”‘• ‘’›ǡ ‘•–‡” ’”‡•‡–ƒ–‹‘ ƒ–ȉ͸–Š

(66) –‡”ƒ–‹‘ƒŽ ‡‘Ž‹–‡ ‡„”ƒ‡ ‡‡–‹‰ ǡ —‡ ʹͲͳ͵ǡ ‡Œ—

(67) •Žƒ†ǡ‘—–Š‘”‡ƒ . . .

(68) Table of Contents Abstract..................................................................................................................................V Acknowledgments...........................................................................................................VII ListofPapers.......................................................................................................................IX PartA........................................................................................................................................1 Chapter1. Introduction................................................................................................3. ͳǤͳǤ ‹‘ˆ—‡Ž•ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͵ 1.1.1.. Biobutanol....................................................................................................................... 4. 1.1.2.. Biogas.............................................................................................................................. 4. ͳǤʹǤ †•‘”’–‹‘ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͷ 1.2.1.. Adsorbents...................................................................................................................... 6. 1.2.2.. Zeolites............................................................................................................................ 6. 1.2.3.. Adsorptionisotherms......................................................................................................9. 1.2.4.. Mixedgasadsorption....................................................................................................11. ͳǤ͵Ǥ  ‘’‡‘ˆ–Š‡’”‡•‡–™‘”ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳ͵ Chapter2. Theory........................................................................................................15. ʹǤͳǤ Ǧ 

(69) ‡ Š‹“—‡ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳͷ 2.1.1.. Chapter3. Determinationofadsorbateloadinginthefilm............................................................15. Experimental...........................................................................................19. ͵ǤͳǤ

(70) •–”—‡–ƒ–‹‘ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳͻ ͵ǤʹǤ ‹Ž›–Š‡•‹•ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳͻ ͵Ǥ͵Ǥ †•‘”’–‹‘š’‡”‹‡–•ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳͻ Chapter4. SummaryofResults...............................................................................23. ͶǤͳǤ ‹ŽŠƒ”ƒ –‡”‹œƒ–‹‘ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤʹ͵ 4.1.1.SilicaliteͲ1films(PapersȻͲIII)...............................................................................................23 4.1.2.NaͲZSMͲ5film(PapersVͲVȻ)................................................................................................25. ͶǤʹǤ†•‘”’–‹‘‘ˆ™ƒ–‡”ƒ†„—–ƒ‘Ž‹–Š‡•‹Ž‹ ƒŽ‹–‡Ǧͳȋƒ’‡”•ȤǦ

(71) ȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤʹ͸ 4.2.1.Infraredspectra...................................................................................................................26 4.2.2.Adsorptionisotherms..........................................................................................................28 4.2.3.Adsorptionofbutanolandwaterfrombinarymixtures.....................................................34. 

(72) .

(73) ͶǤ͵Ǥ †•‘”’–‹‘ ‘ˆ ™ƒ–‡”ǡ ‡–Šƒ‡ ƒ† ƒ”„‘ †‹‘š‹†‡ ‹ ƒǦǦͷ ˆ‹Ž ȋƒ’‡”•Ǧ

(74) ȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͶͲ 4.3.1.Infraredspectra...................................................................................................................40 4.3.2.Adsorbedconcentrations....................................................................................................41 4.3.3.Adsorptionselectivities.......................................................................................................43. Conclusions.........................................................................................................................45 FutureWork.......................................................................................................................47 References...........................................................................................................................49 PartB.....................................................................................................................................57 ƒ’‡”•

(75) Ǧ

(76)   . 

(77)

(78) . .

(79) Part A. ͳ.

(80) . ʹ. .

(81) Chapter 1. Introduction. 1.1. Biofuels  Ž‘„ƒŽ ™ƒ”‹‰ ‹•ƒ –‘’‹  –Šƒ– ‹ ”‡ƒ•‹‰Ž› ƒ––”ƒ –• –Š‡ ƒ––‡–‹‘ ‘ˆ –Š‡ ™‘”Ž†Ǥ  ——Žƒ–‹‘‘ˆ‰”‡‡Š‘—•‡‰ƒ•‡•‹–Š‡ƒ–‘•’Š‡”‡Šƒ•„‡‡‹†‡–‹ˆ‹‡†ƒ•‘‡ ‘ˆ –Š‡ ƒ‹ ”‡ƒ•‘• ˆ‘” ‰Ž‘„ƒŽ ™ƒ”‹‰Ǥͳ ‘”‡‘˜‡”ǡ „‡ ƒ—•‡ ‘ˆ –Š‡ ‘–‹—‘—• ‹ ”‡ƒ•‡‘ˆ–Š‡™‘”Ž†’‘’—Žƒ–‹‘ƒ†Š‹‰Š†‡ƒ†‘ˆ‡‡”‰›ǡ–Š‡ ‘•—’–‹‘‘ˆ ˆ‘••‹Ž ˆ—‡Ž• Šƒ• ‹ ”‡ƒ•‡† †”ƒƒ–‹ ƒŽŽ›Ǥʹ Š‡•‡ ‘ ‡”• Šƒ˜‡ ‹•’‹”‡† • ‹‡–‹•–• –‘•‡ƒ” Šˆ‘”‘”‡‡˜‹”‘‡–ƒŽŽ›ˆ”‹‡†Ž›ƒŽ–‡”ƒ–‹˜‡ˆ—‡Ž•Ǥ ‹‘ˆ—‡Ž• ƒ”‡ ‹–‡”‡•–‹‰ ƒŽ–‡”ƒ–‹˜‡• –‘ –Š‡ ˆ‘••‹Ž ˆ—‡Ž• —•‡† –‘†ƒ› ˆ‘” •‡˜‡”ƒŽ ”‡ƒ•‘•ǣ –Š‡ ƒ‹ ”‡ƒ•‘ ‹• –Šƒ– –Š‡› ’”‡•‡– ƒ •—•–ƒ‹ƒ„Ž‡ ƒŽ–‡”ƒ–‹˜‡ –‘ ˆ‘••‹Ž ”‡•‘—” ‡•Ǥ —”–Š‡”ǡ „‹‘ˆ—‡Ž• ƒ”‡ ‡ƒ•‹Ž› ƒ˜ƒ‹Žƒ„Ž‡ ˆ”‘ ‘‘ „‹‘ƒ•• •‘—” ‡• ƒ†•Š‘™ƒ›‘–Š‡”„‡‡ˆ‹–•ˆ‘”–Š‡‡˜‹”‘‡–ǡ‡ ‘‘›ǡƒ† ‘•—‡”•Ǥ͵ ‹‘ˆ—‡Ž• ˆ‘” –Š‡ –”ƒ•’‘”–ƒ–‹‘ •‡ –‘” ‘’”‹•‡• „‘–Š Ž‹“—‹† ƒ† ‰ƒ•‡‘—• ˆ—‡Ž• ’”‘†— ‡† ˆ”‘ „‹‘ƒ••Ǥ ‘‰ –Š‡ Ž‹“—‹† „‹‘ˆ—‡Ž•ǡ –™‘ ˆ—‡Ž• †‘‹ƒ–‡ –Š‡ ƒ”‡––‘†ƒ›ǡƒ‡Ž›‡–Šƒ‘Ž’”‘†— ‡†˜‹ƒˆ‡”‡–ƒ–‹‘‘ˆ•—‰ƒ”•ƒ†„‹‘†‹‡•‡Ž ‘ˆˆƒ––›ƒ ‹†‡–Š›Ž‡•–‡”ȋ ȌǦ–›’‡’”‘†— ‡†ˆ”‘˜‡‰‡–ƒ„Ž‡‘‹Ž•Ǥ‹‘†‹‡•‡Ž‘ˆ –Š‡ Ǧ–›’‡‹•’”‘†— ‡†˜‹ƒ ƒ–ƒŽ›–‹ –”ƒ•‡•–‡”‹ˆ‹ ƒ–‹‘‘ˆ˜‡‰‡–ƒ„Ž‡‘‹Ž•™‹–Š ‡–Šƒ‘ŽǤ –Šƒ‘Ž ƒ† „‹‘†‹‡•‡Ž ƒ”‡ ‘‘Ž› „Ž‡†‡† ‹ ‰ƒ•‘Ž‹‡ ƒ† †‹‡•‡Žǡ ”‡•’‡ –‹˜‡Ž›ǡ –‘ ”‡†— ‡ –Š‡ ƒ”„‘ ˆ‘‘–’”‹–Ǥ ˆ –Š‡ •—•–ƒ‹ƒ„Ž‡ ‰ƒ•‡‘—• –”ƒ•’‘”–ƒ–‹‘ ˆ—‡Ž•ǡ   ȋ ‘’”‡••‡† „‹‘‰ƒ•Ȍ ‹• –Š‡ †‘‹ƒ–‹‰ ˆ—‡Žǡ Š‘™‡˜‡”  ȋ†‹‡–Š›Ž ‡–Š‡”Ȍ ’”‘†— ‡† ˆ”‘ Dz‰”‡‡dz ‡–Šƒ‘Ž Šƒ• ƒŽ•‘ Šƒ˜‡ •Š‘™ ‰‘‘†ˆ—‡Ž’”‘’‡”–‹‡•ǤͶ Ž–Š‘—‰Šǡ –Š‡”‡ Šƒ• „‡‡ •‘‡ •— ‡•• ‹ ”‡’Žƒ ‹‰ ȋƒ– Ž‡ƒ•– ’ƒ”–‹ƒŽŽ›Ȍ ˆ—‡Ž• ’”‘†— ‡† ˆ”‘ ˆ‘••‹Ž ”‡•‘—” ‡• ™‹–Š •—•–ƒ‹ƒ„Ž‡ ƒŽ–‡”ƒ–‹˜‡•ǡ ƒ• Š‹‰ŠŽ‹‰Š–‡† ƒ„‘˜‡ǡ –Š‡”‡ ‹• •–‹ŽŽ ƒ ‡‡† ˆ‘” ‹’”‘˜‹‰ –Š‡ ‡ˆˆ‹ ‹‡ › ‘ˆ ‡š‹•–‹‰ ’”‘ ‡••‡• ƒ• ™‡ŽŽ ƒ• ˆ‘” †‡˜‡Ž‘’‹‰ ‡™ ’”‘ ‡••‡• ˆ‘” ’”‘†— ‹‰ „‹‘ˆ—‡Ž•Ǥ ‘” ‡šƒ’Ž‡ǡ ˆ‘” „‹‘‰ƒ•ǡ ‡ˆˆ‹ ‹‡– ’”‘ ‡••‡• ˆ‘” •ƒŽŽ • ƒŽ‡ ’”‘†— –‹‘ ‘ˆ „‹‘‰ƒ• •Š‘—Ž† „‡ †‡˜‡Ž‘’‡†ǡƒ†‘–Š‡Ž‹“—‹†•‹†‡ǡ–Š‡”‡ƒ”‡‘”‡’”‘‹•‹‰Ž‹“—‹†„‹‘ˆ—‡Ž•–Šƒ ‡–Šƒ‘Ž ‡Ǥ‰Ǥ „‹‘„—–ƒ‘Žǡ „—– –‘†ƒ› –Š‹• ’”‘ ‡•• •—ˆˆ‡”• ˆ”‘ –‘‘ Žƒ”‰‡ •‡’ƒ”ƒ–‹‘ ‘•–•Ǥ Š‡”‡ˆ‘”‡ǡ ‘˜‡Ž ‡ˆˆ‹ ‹‡– ’”‘ ‡••‡•ǡ ˆ‘” ‹•–ƒ ‡ǡ „ƒ•‡† ‘ ƒ†•‘”„‡– ‘” ‡„”ƒ‡–‡ Š‘Ž‘‰‹‡••Š‘—Ž†„‡†‡˜‡Ž‘’‡†Ǥ  ͵.

(82) 1.1.1. Biobutanol ˜‡”› ‘’‡–‹–‹˜‡„‹‘ˆ—‡Žˆ‘”—•‡‹‹–‡”ƒŽ ‘„—•–‹‘‡‰‹‡•‹•ͳǦ„—–ƒ‘Ž ȋŠ‡”‡ƒˆ–‡” ”‡ˆ‡””‡† –‘ ƒ• „—–ƒ‘ŽȌǤ —–ƒ‘Žǡ Ž‹‡ ‡–Šƒ‘Žǡ ƒ „‡ —•‡† ƒ• ƒ ƒ††‹–‹˜‡ –‘ ‰ƒ•‘Ž‹‡ „—– ƒ› ƒŽ•‘ „‡ „Ž‡†‡† ‹ •ƒŽŽ‡” ƒ‘—–• –‘ †‹‡•‡ŽǤͷ —–ƒ‘Ž ‹• ‹ ƒ› ƒ•’‡ –• ƒ „‡––‡” ƒ†‹†ƒ–‡ –Šƒ ‡–Šƒ‘Ž ƒ• ”‡’Žƒ ‡‡– –‘ ‰ƒ•‘Ž‹‡ „‡ ƒ—•‡ ‘ˆ ‹–• ˆƒ˜‘”ƒ„Ž‡ ˆ—‡Ž ’”‘’‡”–‹‡•ǡ •— Š ƒ• Š‹‰Š‡” •’‡ ‹ˆ‹  Š‡ƒ– ˜ƒŽ—‡ ƒ† ƒŽ•‘ „—–ƒ‘Ž ‹• •‹‰‹ˆ‹ ƒ–Ž› ‘”‡ ƒŠ›†”‘—• ‘’ƒ”‡† –‘ ‡–Šƒ‘Ž ™Š‹ Š•—„•–ƒ–‹ƒŽŽ›”‡†— ‡•–Š‡”‹•‘ˆ™ƒ–‡” ‘–ƒ‹ƒ–‹‘‘ˆ–Š‡ˆ—‡ŽǤ —–ƒ‘Ž ƒ „‡ ’”‘†— ‡† „› ˆ‡”‡–ƒ–‹‘ —•‹‰ •—‰ƒ”• ˆ”‘ †‹ˆˆ‡”‡– ”‡‡™ƒ„Ž‡ „‹‘ƒ•• ”‡•‘—” ‡• ‹ Ž—†‹‰ ‘”ǡ ™‘‘†ǡ Ž‹‰‘ ‡ŽŽ—Ž‘•‹  Š›†”‘Ž›•ƒ–‡• ‡– Ǥ ˜‹ƒ –Š‡  ȋƒ ‡–‘‡ǡ „—–ƒ‘Žǡ ƒ† ‡–Šƒ‘ŽȌ ˆ‡”‡–ƒ–‹‘ ’”‘ ‡•• —•‹‰ ‡Ǥ‰Ǥ –Š‡Clostridiumacetobutylicum•–”ƒ‹Ǥ͸Ǧ͹ ‘™‡˜‡”ǡ‘‡‘ˆ–Š‡†‹•ƒ†˜ƒ–ƒ‰‡•™‹–Š –Š‹• ’”‘ ‡•• ‹• –Š‡ –‘š‹ ‹–› ‘ˆ „—–ƒ‘Ž –‘ –Š‡ ‹ ”‘‘”‰ƒ‹• ™Š‹ Š Ž‹‹–• –Š‡ ‘ ‡–”ƒ–‹‘‘ˆ„—–ƒ‘Ž‹–Š‡ˆ‡”‡–ƒ–‹‘„”‘–Š–‘ƒ’’”‘š‹ƒ–‡Ž›ʹͲ‰Ȁ™‹–Š ƒ ”‡Žƒ–‹˜‡ ‘’‘•‹–‹‘ ‘ˆ  ‘ˆ ƒǤ ͵ǣ͸ǣͳǤͺ Š‹• Ž‘™ ‘ ‡–”ƒ–‹‘ ƒ‡• ‹– ŠƒŽŽ‡‰‹‰ –‘ ”‡ ‘˜‡” –Š‡ „—–ƒ‘Ž ‡ˆˆ‹ ‹‡–Ž›ǡ •‹ ‡ –”ƒ†‹–‹‘ƒŽ †‹•–‹ŽŽƒ–‹‘ ‹• —•—‹–ƒ„Ž‡ ƒ• ‹– ‹• ˆƒ” –‘‘ ‡‡”‰› ‘•—‹‰Ǥͻ

(83)  ”‡ƒ•‡† ›‹‡Ž† ƒ† ’”‘†— –‹˜‹–› ‘„‹‡†™‹–Šƒ‘”‡‡‡”‰›‡ˆˆ‹ ‹‡–„—–ƒ‘Ž”‡ ‘˜‡”›–‡ Š‹“—‡™‹ŽŽ‹’”‘˜‡ –Š‡‡ ‘‘›‘ˆ–Š‡ˆ‡”‡–ƒ–‹‘’”‘ ‡••–‘ƒ”‡ƒŽ‘’–‹‘ˆ‘”’”‘†— –‹‘‘ˆ Ž‹“—‹† „‹‘ˆ—‡Ž•Ǥ

(84)  ‘”†‡” –‘ ”‡ ‘˜‡” „—–ƒ‘Ž ˆ”‘ –Š‡ ˆ‡”‡–ƒ–‹‘ „”‘–Šǡ ƒ —„‡”‘ˆ†‹ˆˆ‡”‡–”‡ ‘˜‡”›–‡ Š‹“—‡•Šƒ˜‡„‡‡•–—†‹‡†•— Šƒ•Ǣƒ†•‘”’–‹‘ǡ͹ǡ ͳͲ ’‡”˜ƒ’‘”ƒ–‹‘ǡͳͳ ‡š–”ƒ –‹‘ ƒ† ‰ƒ• •–”‹’’‹‰Ǥͳʹ ‘” ‡šƒ’Ž‡ǡ —”‡•Š‹ ‡– ƒŽǤ͹ ‹˜‡•–‹‰ƒ–‡† •‹Ž‹ ƒŽ‹–‡Ǧͳǡ „‘‡ Šƒ” ‘ƒŽȀ Šƒ” ‘ƒŽ ƒ† ’‘Ž›˜‹›Ž’›”‹†‹‡ ˆ‘” •‡’ƒ”ƒ–‹‘ ‘ˆ „—–ƒ‘Ž ˆ”‘ ˆ‡”‡–ƒ–‹‘ „”‘–Š „› ƒ†•‘”’–‹‘Ǣ ˆ”‘ –Š‡•‡ ƒŽ–‡”ƒ–‹˜‡• •‹Ž‹ ƒŽ‹–‡Ǧͳ ™ƒ• ˆ‘—† –‘ „‡ –Š‡ ‘•– ’”‘‹•‹‰Ǥ —†•Š‘‘” ‡– ƒŽǤͳ͵ ‡˜ƒŽ—ƒ–‡††‹ˆˆ‡”‡–‘’–‹‘•ˆ‘””‡ ‘˜‡”‹‰„—–ƒ‘Žˆ”‘ˆ‡”‡–ƒ–‹‘„”‘–Š•ƒ† ‘ Ž—†‡† –Šƒ– ƒ†•‘”’–‹‘Ǧ ƒ† ’‡”˜ƒ’‘”ƒ–‹‘Ǧ„ƒ•‡† ”‡ ‘˜‡”› ‘’‡”ƒ–‹‘• —•‹‰ Š›†”‘’Š‘„‹  ƒ†•‘”„‡–• Ž‹‡ Š›†”‘’Š‘„‹  œ‡‘Ž‹–‡• ™‡”‡ –Š‡ ‘•– ’”‘‹•‹‰ ‘’–‹‘•Ǥ. 1.1.2. Biogas ‹‘‰ƒ• ‹• –Š‡ ‰ƒ•‡‘—• ’”‘†— – ‘ˆ ƒƒ‡”‘„‹  †‹‰‡•–‹‘ ‘ˆ ‘”‰ƒ‹  ƒ––‡” ƒ† ƒ ”‡‡™ƒ„Ž‡•‘—” ‡ˆ‘”‡–Šƒ‡’”‘†— –‹‘Ǥ‡‘ˆ–Š‡ƒ‹ƒ†˜ƒ–ƒ‰‡•‘ˆ„‹‘‰ƒ• ‹• –Šƒ– ƒ ˜ƒŽ—ƒ„Ž‡ ˆ—‡Ž ƒ „‡ ’”‘†— ‡† ™Š‹Ž‡ †‡•–”‘›‹‰ †‹•‡ƒ•‡Ǧ ƒ—•‹‰ ’ƒ–Š‘‰‡• ƒ† ƒ– –Š‡ •ƒ‡ –‹‡ †‡ ”‡ƒ•‹‰ –Š‡ ˜‘Ž—‡ ‘ˆ †‹•’‘•‡† ™ƒ•–‡ ’”‘†— –•ǤͳͶ ‘”‡‘˜‡”ǡ –Š‡ ”‡•‹†—‡ ˆ‘”‡† ƒ› ‹ ƒ› ƒ•‡• „‡ —•‡† ƒ• ˆ‡”–‹Ž‹œ‡”Ǥͳͷ Š‡ ‡–Šƒ‡ —’‰”ƒ†‡† ˆ”‘ „‹‘‰ƒ• ƒ „‡ —•‡† ˆ‘” Š‡ƒ– ƒ† ‡Ž‡ –”‹ ‹–› ’”‘†— –‹‘‘”ƒ•ˆ—‡Žˆ‘”˜‡Š‹ Ž‡•–‘”‡†— ‡‡‹••‹‘•ƒ† ‘•—’–‹‘‘ˆˆ‘••‹Ž Ͷ.

(85) ˆ—‡Ž•Ǥͳ͸ ‹‘‰ƒ• ƒ‹Ž› ‘–ƒ‹• ‡–Šƒ‡ǡ –Š‡ †‡•‹”‡† ’”‘†— –ǡ ƒ† ƒ —„‡” ‘ˆ ‘–ƒ‹ƒ–•Ǥ ˆ –Š‡•‡ ‘–ƒ‹ƒ–•ǡ –Š‡ ‘•– ƒ„—†ƒ– ƒ”‡ ƒ”„‘ †‹‘š‹†‡ǡ ™ƒ–‡”ǡ‹–”‘‰‡ǡƒ†•—Žˆ—” ‘’‘—†•ǤŠ‡ ‘’‘•‹–‹‘‘ˆ–Š‡„‹‘‰ƒ•‰‡‡”ƒŽŽ› †‡’‡†• ‘ –Š‡ ˆ‡‡†•–‘  ƒ† –Š‡ ’”‘ ‡••‹‰ ‘†‹–‹‘•Ǥ ‘™‡˜‡”ǡ –›’‹ ƒŽŽ› „‹‘‰ƒ• ‘–ƒ‹•ͷͷΨ–‘͹ͷ؏‡–Šƒ‡ǡ͵ͲΨ–‘ͶͷΨ ƒ”„‘†‹‘š‹†‡ƒ†‫ͳ׽‬Ψ–‘ ͳͷΨ ™ƒ–‡” ƒ† ‹–”‘‰‡Ǥͳ͹ Š‡ ‘–ƒ‹ƒ–• „‘–Š Ž‘™‡” –Š‡ •’‡ ‹ˆ‹  ‡‡”‰› ‘–‡– ‘ˆ –Š‡ ‰ƒ• ƒ† ƒ› ‹†— ‡ ’”‘„Ž‡• ™‹–Š ‘””‘•‹‘ ‘ˆ Šƒ†Ž‹‰ ‡“—‹’‡– ȋ•–‘”ƒ‰‡ –ƒ•ǡ ’‹’‡Ž‹‡•ǡ ‡‰‹‡ ’ƒ”–• ‡– ǤȌ Ž‡ƒ†‹‰ –‘ ‡š’‡•‹˜‡ ƒ‹–‡ƒ ‡ ‘•–•Ǥ—Žˆ—”Ǧ ‘–ƒ‹‹‰•’‡ ‹‡•ƒŽ•‘Ž‡ƒ†–‘–Š‡—†‡•‹”‡†‡‹••‹‘ ‘ˆʹƒ†”‹•‘ˆˆ‘”ƒ–‹‘‘ˆ’ƒ”–‹ Ž‡•™Š‡ ‘„—•–‡†Ǥ‡˜‡”ƒŽ–‡ Š‹“—‡•ˆ‘” —’‰”ƒ†‹‰‘ˆ„‹‘‰ƒ•‡š‹•––‘†ƒ›ǡƒ†–Š‡›ƒ”‡ ‘–‹—ƒŽŽ›„‡‹‰‹’”‘˜‡†Ǥ•—ƒŽŽ› –‡ Š‹“—‡• †‡˜‡Ž‘’‡† ˆ‘” –Š‡ Ž‘•‡Ž› ”‡Žƒ–‡† ’”‘ ‡••ǡ —’‰”ƒ†‹‰ ‘ˆ ƒ–—”ƒŽ ‰ƒ•ǡ ƒ”‡ƒŽ•‘ƒ†‘’–‡†ƒ†—•‡†ˆ‘”—’‰”ƒ†‹‰‘ˆ„‹‘‰ƒ•ǤŠ‡‘•– ‘‘–‡ Š‹“—‡• ƒ”‡ ƒ„•‘”’–‹‘ǡ ˆ‘ŽŽ‘™‡† „› ’”‡••—”‡ •™‹‰ ƒ†•‘”’–‹‘ ȋȌǡ ”›‘‰‡‹  ƒ† ‡„”ƒ‡„ƒ•‡†–‡ Š‘Ž‘‰‹‡•ǤͳͺŠ‡•‡–‡ Š‘Ž‘‰‹‡•ƒ”‡Š‘™‡˜‡”„‡•–•—‹–‡†ˆ‘” ”‡Žƒ–‹˜‡Ž› Žƒ”‰‡ • ƒŽ‡ ƒ’’Ž‹ ƒ–‹‘•ǡ ’‡”Šƒ’• ™‹–Š ‡š ‡’–‹‘ ‘ˆ ‡„”ƒ‡ ’”‘ ‡••‡• –Šƒ– „‡ ƒ—•‡ ‘ˆ –Š‡‹” ‘†—Žƒ” †‡•‹‰ ˆƒ ‹Ž‹–ƒ–‡ ‡ƒ•› • ƒŽ‡ —’ ‘” • ƒŽ‡ †‘™Ǥͳͻ  •‹’Ž‡” ƒŽ–‡”ƒ–‹˜‡ ‹• ™ƒ–‡” • ”—„„‹‰ ™Š‹ Š ”‡‘˜‡• „‘–Š ƒ”„‘ †‹‘š‹†‡ ƒ† Š›†”‘‰‡ •—Žˆ‹†‡ ˆ”‘ „‹‘‰ƒ• ƒ• –Š‡•‡ ‘’‘‡–• ƒ”‡ — Š ‘”‡ •‘Ž—„Ž‡–Šƒ‡–Šƒ‡‹™ƒ–‡”ƒ‹‰‹–ƒ‘’–‹‘ǤŠ‡ƒ‹†”ƒ™„ƒ ™‹–Š–Š‹• ‡–Š‘†‹•–Šƒ–‹–”‡“—‹”‡•Žƒ”‰‡ƒ‘—–•‘ˆ™ƒ–‡”ǡ‘†‘”’”‘„Ž‡•ȋˆ”‘–Š‡ ʹ ˜‡–‡†Ȍ ƒ† Š‹‰Š ‡Ž‡ –”‹ ‹–› ‘•—’–‹‘Ǥͳͻ Ž–Š‘—‰Š ƒŽŽ ‘ˆ –Š‡ –‡ Š‹“—‡• ‡–‹‘‡†ƒ„‘˜‡ƒ”‡ —””‡–Ž›‡’Ž‘›‡†ˆ‘”—’‰”ƒ†‹‰„‹‘‰ƒ•ǡ–Š‡”‡‹••–‹ŽŽŠ—‰‡ ’‘–‡–‹ƒŽ ˆ‘” ‹’”‘˜‹‰ –Š‡ ’‡”ˆ‘”ƒ ‡ „› ‘’–‹‹œ‹‰ –Š‡ –‡ Š‘Ž‘‰‹‡• ˆ‘” –Š‡ –ƒ”‰‡–ƒ’’Ž‹ ƒ–‹‘ǤʹͲ. 1.2. Adsorption †•‘”’–‹‘‘•‘Ž‹†•‹•ƒ’Š‡‘‡‘™Š‹ ŠŠƒ’’‡•™Š‡ƒ•‘Ž‹†•—”ˆƒ ‡‹• ‡š’‘•‡† –‘ ƒ Ž‹“—‹† ‘” ‰ƒ•ǡ ƒ† –Š‡ •’‡ ‹‡• ‹ –Š‡ ˆŽ—‹† ƒ†Š‡”‡ –‘ –Š‡ •—”ˆƒ ‡Ǥ †•‘”’–‹‘‹•†‡ˆ‹‡†ƒ•–Š‡‡”‹ Š‡–‘ˆ–Š‡•’‡ ‹‡•‘ˆ–Š‡ˆŽ—‹†‹–Š‡˜‹ ‹‹–› ‘ˆ –Š‡ •—”ˆƒ ‡Ǥʹͳ Š‡ ƒ†•‘”’–‹‘ ’”‘ ‡•• ‹˜‘Ž˜‡• –™‘ ‘’‘‡–•ǣ adsorbent ƒ† adsorbateǤ †•‘”„‡– ‹• –Š‡ •—„•–ƒ ‡ ‘ –Š‡ •—”ˆƒ ‡ ‘ˆ ™Š‹ Š ƒ†•‘”’–‹‘ –ƒ‡• ’Žƒ ‡ǡ ƒ† ƒ†•‘”„ƒ–‡ ‹• –Š‡ •—„•–ƒ ‡ ™Š‹ Š ‹• „‡‹‰ ƒ†•‘”„‡† ‘ –Š‡ •—”ˆƒ ‡ ‘ˆ –Š‡ ƒ†•‘”„‡–Ǥ ƒ•‡† ‘ –Š‡ ƒ–—”‡ ‘ˆ –Š‡ „‘†‹‰ „‡–™‡‡ –Š‡ ƒ†•‘”„ƒ–‡ ‘Ž‡ —Ž‡ ƒ† –Š‡ •‘Ž‹† •—”ˆƒ ‡ǡ ƒ†•‘”’–‹‘ ƒ „‡ Žƒ••‹ˆ‹‡† ƒ• ‡‹–Š‡” chemical adsorption ȋ Š‡‹•‘”’–‹‘Ȍ ™Š‹ Š ‹˜‘Ž˜‡• ‘˜ƒŽ‡– „‘†‹‰ ‘” physicaladsorptionȋ’Š›•‹•‘”’–‹‘Ȍ™Š‹ Š‘ —”•–Š”‘—‰Š™‡ƒ‡”‹–‡”ƒ –‹‘• ˆ‘”‡šƒ’Ž‡ ƒ—•‡†„›˜ƒ†‡”ƒƒŽ•ˆ‘” ‡•ǤʹʹǦʹ͵. ͷ.

(86) Š‡ ’Š‡‘‡‘ ‘ˆ ƒ†•‘”’–‹‘ Šƒ• ˆƒ• ‹ƒ–‡† • ‹‡–‹•–• ˆ‘” ƒ ˜‡”› Ž‘‰ –‹‡Ǥ Š‡ ’”ƒ –‹ ƒŽ ƒ’’Ž‹ ƒ–‹‘• ‘ˆ ƒ†•‘”’–‹‘ ƒ”‡ ˜‡”› ‹’‘”–ƒ– ˆ”‘ ‹†—•–”‹ƒŽ ƒ† ‡˜‹”‘‡–ƒŽ ’”‘–‡ –‹‘ ƒ•’‡ –•Ǥ ‘” ‡šƒ’Ž‡ǡ ƒ†•‘”’–‹‘ ‹• ‹˜‘Ž˜‡† ‹ ’—”‹ˆ‹ ƒ–‹‘ ‘ˆ ™ƒ–‡”ǡ •‡™ƒ‰‡•ǡ ƒ‹” ƒ† •‘‹Ž•Ǥ ƒ”–‹ —Žƒ”Ž›ǡ ‹ –Š‡ ’‡–”‘Ž‡— ”‡ˆ‹‹‰ ƒ† ’‡–”‘ Š‡‹ ƒŽ ‹†—•–”‹‡•ǡ ƒ†•‘”’–‹‘ „ƒ•‡† ’”‘ ‡••‡• ƒ”‡ ‡š–‡•‹˜‡Ž›—•‡†ƒ†”‡ƒ•‘ƒ„Ž›™‡ŽŽǦ‘™ǤʹͶǦʹ͸. 1.2.1. Adsorbents ‡˜‡”ƒŽ ƒ†•‘”„‡–• •— Š ƒ• ƒ –‹˜ƒ–‡† ƒ”„‘ǡ œ‡‘Ž‹–‡• ƒ† •‹Ž‹ ƒ ‰‡Ž Šƒ˜‡ „‡‡ —•‡† ‹ †‹ˆˆ‡”‡– ‹†—•–”‹ƒŽ ’”‘ ‡••‡•Ǥʹ͹ ‘”‘—• •‘Ž‹†• ƒ”‡ ‹’‘”–ƒ– ƒ†•‘”„‡–• „‘–Š ˆ‘” • ‹‡–‹ˆ‹  ”‡•‡ƒ” Š ƒ† ‹†—•–”‹ƒŽ ƒ’’Ž‹ ƒ–‹‘•Ǥʹͺ  ‰‘‘† ’‘”‘—• ƒ†•‘”„‡–•Š‘—Ž†„‡ƒ„Ž‡–‘’”‘˜‹†‡Š‹‰Šƒ†•‘”’–‹‘ ƒ’ƒ ‹–›ǡŠ‹‰Š•‡Ž‡ –‹˜‹–›ƒ† ˆƒ•– ‹‡–‹ • ˆ‘” ƒ ‡ˆˆ‹ ‹‡– ƒ†•‘”’–‹‘ ’”‘ ‡••Ǥ

(87)  ‘”†‡” –‘ •ƒ–‹•ˆ› –Š‡•‡ ”‡“—‹”‡‡–•ǡ –Š‡ ’‘”‘—• ƒ†•‘”„‡– •Š‘—Ž† Šƒ˜‡ ”‡ƒ•‘ƒ„Ž› Š‹‰Š •—”ˆƒ ‡ ƒ”‡ƒ ™‹–Š ƒ Š‹‰Š †‡•‹–› ‘ˆ ƒ†•‘”’–‹‘ •‹–‡• ȋ ƒ’ƒ ‹–›Ȍ ƒ† ”‡Žƒ–‹˜‡Ž› Žƒ”‰‡ ’‘”‡ ‡–™‘” ƒ† •ƒŽŽ ’ƒ”–‹ Ž‡ •‹œ‡ –‘ ˆƒ ‹Ž‹–ƒ–‡ ƒ •Š‘”– †‹ˆˆ—•‹‘ ’ƒ–Š ȋ‹‡–‹ •ȌǤʹͻ ‘”‘—•ƒ–‡”‹ƒŽ•ƒ›„‡ Žƒ••‹ˆ‹‡†‹–Š”‡‡ ƒ–‡‰‘”‹‡•ǣ͵Ͳ ‹ ”‘•’‘”‡•ǣ†δʹ ‡•‘’‘”‡•ǣʹδ†δͷͲ ƒ ”‘’‘”‡•ǣ†εͷͲ Š‡ ˆƒ – –Šƒ– †‹ˆˆ‡”‡– •’‡ ‹‡• ƒ› •Š‘™ †‹ˆˆ‡”‡– ƒˆˆ‹‹–‹‡• ˆ‘” ƒ ’ƒ”–‹ —Žƒ” •—”ˆƒ ‡ ƒ› „‡ ‡š’Ž‘‹–‡† ˆ‘” •‡’ƒ”ƒ–‹‰ †‹ˆˆ‡”‡– •’‡ ‹‡• ˆ”‘ ƒ ‹š–—”‡Ǥ †•‘”’–‹‘ ‹ œ‡‘Ž‹–‡• ˆ‹†• ‡š–‡•‹˜‡ ƒ’’Ž‹ ƒ–‹‘• ‹ ‹†—•–”›Ǥ ‘” ‡šƒ’Ž‡ǡ ’—”‹ˆ‹ ƒ–‹‘ ‘ˆ ƒ–—”ƒŽ ‰ƒ• •–”‡ƒ•ǡ ‰ƒ• †”›‹‰ǡ •‡’ƒ”ƒ–‹‘ ‘ˆ ƒ”‘ƒ–‹ • ƒ† ƒ‹” •‡’ƒ”ƒ–‹‘ ƒ”‡ •‘‡ ‘ˆ –Š‡ ‘•– ‹’‘”–ƒ– ‘‡” ‹ƒŽ ƒ’’Ž‹ ƒ–‹‘• ‘ˆ ƒ†•‘”„‡–•Ǥ͵ͳ. 1.2.2. Zeolites ‡‘Ž‹–‡• ™‡”‡ †‹• ‘˜‡”‡† „› ™‡†‹•Š ‹‡”ƒŽ‘‰‹•–ǡ š‡Ž ”‡†”‹ ”‘•–‡†–ǡ ‹ –Š‡ͳͺ–Š ‡–—”›Ǥ͵ʹ ‡‘„•‡”˜‡†–Šƒ–ƒŽƒ”‰‡ƒ‘—–‘ˆ•–‡ƒ™ƒ•’”‘†— ‡†ˆ”‘ ™ƒ–‡” ƒ†•‘”„‡† ‹ –Š‡ ƒ–‡”‹ƒŽ ™Š‡ ‹– ™ƒ• Š‡ƒ–‡† —’Ǥ Š‡ ƒ‡ œ‡‘Ž‹–‡ ‹• ‘”‹‰‹ƒŽŽ›ˆ”‘ ”‡‡™‘”†•zeo‡ƒ‹‰Dz–‘„‘‹Ždzǡƒ†lithios‡ƒ‹‰Dz•–‘‡dzǤ͵͵ ‡‘Ž‹–‡• ƒ”‡ ‹ ”‘’‘”‘—• ‹‘”‰ƒ‹  ƒ–‡”‹ƒŽ• ‘•‹•–‹‰ ‘ˆ –Š”‡‡ †‹‡•‹‘ƒŽ ‡–™‘”• ‘ˆ ‹–‡”Ž‹‡† –‡–”ƒŠ‡†”ƒ of alumina (AlO4) ƒ† silica (SiO4)ǡ –‘‰‡–Š‡” ™‹–Š Šƒ”‰‡Ǧ„ƒŽƒ ‹‰ ƒ–‹‘••— Šƒ•ƒΪǡ Ϊǡ‡– Ǥ™‹–Š‹–Š‡‹”’‘”‡•Ǥ͵ͶŠ‡‹ȀŽ ”ƒ–‹‘ ‹• ‹’‘”–ƒ– ƒ• ‹– –‘ ƒ Žƒ”‰‡ ‡š–‡– †‹ –ƒ–‡• ‡Ǥ‰Ǥ –Š‡ Š›†”‘’Š‘„‹ ‹–› ‘ˆ –Š‡ œ‡‘Ž‹–‡ǡ –Š‡ Š‹‰Š‡” –Š‡ ƒŽ—‹— ‘–‡– ȋ•ƒŽŽ‡” ‹ȀŽ ”ƒ–‹‘Ȍ –Š‡ ‘”‡. ͸.

(88) Š›†”‘’Š‹Ž‹ –Š‡œ‡‘Ž‹–‡‰‡–•ǤŠ—•ǡ„›ƒŽ–‡”‹‰–Š‡ƒŽ—‹— ‘–‡–‘ˆ–Š‡œ‡‘Ž‹–‡ǡ ‘‡ ƒ› –ƒ‹Ž‘” –Š‡ ƒ†•‘”’–‹‘ ’”‘’‡”–‹‡•ǡ •‘ –Šƒ– –Š‡ œ‡‘Ž‹–‡ ˆƒ˜‘”• ‡‹–Š‡” Š›†”‘’Š‹Ž‹ ‘”Š›†”‘’Š‘„‹ ƒ†•‘”„ƒ–‡•Ǥ‘‡‘–Š‡”’”‘’‡”–‹‡•‘ˆœ‡‘Ž‹–‡•ǡ•— Šƒ• –Š‡”ƒŽ •–ƒ„‹Ž‹–› ƒ† ‹‘ ‡š Šƒ‰‡ ƒ’ƒ ‹–›ǡ ƒ”‡ ƒŽ•‘ •‹‰‹ˆ‹ ƒ–Ž› †‡’‡†‡– ‘ ‹ȀŽ”ƒ–‹‘Ǥ͵ͷ ‡‘Ž‹–‡• ƒŠƒ˜‡†‹ˆˆ‡”‡–’‘”‡•‹œ‡ƒ†–‘’‘Ž‘‰‹‡•ǤŠ‡’‘”‘•‹–›‘ˆœ‡‘Ž‹–‡•‹• ƒ‡••‡–‹ƒŽ–‡”–‘†‡ˆ‹‡–Š‡•–”— –—”‡‘ˆ–Š‹•ƒ–‡”‹ƒŽǤ‡‘Ž‹–‡•ƒ”‡†‡ˆ‹‡†ƒ• ‹ ”‘’‘”‘—• ƒ–‡”‹ƒŽ• ™‹–Š ’‘”‡ •‹œ‡• ‹ –Š‡ ”ƒ‰‡ ͲǤ͵ –‘ ͳǤ͵ Ǥ͵͸ ‡ ƒ—•‡ ‘ˆ –Š‡‹” ™‡ŽŽǦ†‡ˆ‹‡† ’‘”‡ •›•–‡ǡ ‹ ‘„‹ƒ–‹‘ ™‹–Š –Š‡ ƒ„‹Ž‹–› –‘ –ƒ‹Ž‘” –Š‡ ƒŽ—‹— ‘–‡–ƒ†–Š‡’‘••‹„‹Ž‹–›–‘‹‘Ǧ‡š Šƒ‰‡–Š‡ƒ–‡”‹ƒŽ•ǡœ‡‘Ž‹–‡•Šƒ˜‡ ˆ‘—† ƒ› ƒ’’Ž‹ ƒ–‹‘• ‹ ‹†—•–”›ǡ ˆ‘” ‹•–ƒ ‡ǡ ƒ• ™ƒ–‡” •‘ˆ–‡‡”• ‹ †‡–‡”‰‡–•ǡ͵͹ •Šƒ’‡ •‡Ž‡ –‹˜‡ ƒ–ƒŽ›•–•͵ͺ ‹ –Š‡ ‘‹Ž ”‡ˆ‹‹‰ ƒ† ’‡–”‘ Š‡‹ ƒŽ ‹†—•–”‹‡•ƒ†ƒ••‡Ž‡ –‹˜‡ƒ†•‘”„‡–•ˆ‘”•‡’ƒ”ƒ–‹‰‰ƒ•‘”Ž‹“—‹†‹š–—”‡•Ǥ͵ͻ ‡‘Ž‹–‡• ƒ”‡ ’”‹ƒ”‹Ž› —•‡† ‹ ’‘™†‡” ˆ‘”ǡ „—– –Š‡› ƒ ƒŽ•‘ „‡ ’”‡’ƒ”‡† ƒ• ˆ‹Ž• ‘ †‹ˆˆ‡”‡– –›’‡• ‘ˆ ‘”‰ƒ‹  ȋ‡Ǥ‰Ǥ ’‘Ž›‡”ǡ ‡ŽŽ—Ž‘•‡Ȍ ‘” ‹‘”‰ƒ‹  ȋ‡Ǥ‰Ǥ ‡–ƒŽǡ ‘” ‡”ƒ‹ Ȍ •—’’‘”–• ˆ‘” ‡ Šƒ‹ ƒŽ •–ƒ„‹Ž‹–›ǤͶͲ Š‡•‡ œ‡‘Ž‹–‡ ˆ‹Ž• •Š‘™ ‰”‡ƒ– ’‘–‡–‹ƒŽ ‹ •‡˜‡”ƒŽ †‹ˆˆ‡”‡– ƒ’’Ž‹ ƒ–‹‘ ƒ”‡ƒ• •— Š ƒ•ǣ membranes, •–”— –—”‡†catalysts‘”adsorbentsƒ†ƒ• Š‡‹ ƒŽsensorsǤͶͳǦͶ͵ ‘†ƒ›ǡ ‘”‡ –Šƒ ʹ͵Ͳ –›’‡• ‘ˆ œ‡‘Ž‹–‡• ƒ”‡ ‘™ ƒ† Žƒ••‹ˆ‹‡† „› –Š‡

(89) –‡”ƒ–‹‘ƒŽ ‡‘Ž‹–‡ ••‘ ‹ƒ–‹‘ ȋ

(90) ȌǤͶͶ ƒ Š ˆ”ƒ‡™‘” ‹• †‡•‹‰ƒ–‡† ™‹–Š ƒ –Š”‡‡ǦŽ‡––‡” ‘†‡ǡ ˆ‘” ‡šƒ’Ž‡ǡ ǡ  ƒ† 

(91)  ȋǦͷ ƒ† •‹Ž‹ ƒŽ‹–‡ǦͳȌ ˆ”‘ ™Š‹ Š–Š‡Žƒ––‡”‹•‘ˆ•’‡ ‹ƒŽ‹–‡”‡•–‹–Š‹•™‘”Ǥ  . ͹.

(92)  Figure1.‘’‘Ž‘‰›‘ˆ–Š‡œ‡‘Ž‹–‡

(93) ˆ”ƒ‡™‘”ǤͶͶ.  

(94)  –Š‹• ™‘”ǡ ™‡ ˆ‘ —• ‘ –Š‡ 

(95) Ǧ–›’‡ œ‡‘Ž‹–‡Ǥ ‡‘Ž‹–‡ 

(96)  Šƒ• ƒ ’‘”‡ •›•–‡ ‘•‹•–‹‰ ‘ˆ •–”ƒ‹‰Š– ’‘”‡• ȋͲǤͷͳྶͲǤͷͷ Ȍ ‰‘‹‰ ‹ ‘‡ ”›•–ƒŽŽ‘‰”ƒ’Š‹  †‹”‡ –‹‘ȋ–Š‡bǦ†‹”‡ –‹‘Ȍƒ†‹–‡” ‘‡ –‹‰•‹—•‘‹†ƒŽ’‘”‡•ȋͲǤͷͶྶͲǤͷ͸Ȍ ‰‘‹‰‹–Š‡aǦ†‹”‡ –‹‘™‹–Šƒƒ˜‡”ƒ‰‡†‹ƒ‡–‡”‘ˆ–Š‡’‘”‡•„‡‹‰ ƒͲǤͷͷǤͶͷ ‡‘Ž‹–‡ 

(97)  ƒ› „‡ Žƒ••‹ˆ‹‡† ƒ• ‡‹–Š‡” Ǧͷ ‘” •‹Ž‹ ƒŽ‹–‡Ǧͳ †‡’‡†‹‰ ‘ –Š‡ ‹ȀŽ”ƒ–‹‘ǣ—•—ƒŽŽ›ˆ‘”‹ȀŽεʹͲͲȋ‘”Žˆ”‡‡Ȍ–Š‡œ‡‘Ž‹–‡‹• Žƒ••‹ˆ‹‡†ƒ••‹Ž‹ ƒŽ‹–‡Ǧ ͳǡ ƒ† ˆ‘” ‹ȀŽδ ʹͲͲ ‹– ‹• Žƒ••‹ˆ‹‡† ƒ• ǦͷǤͶ͸ • ‡Žƒ„‘”ƒ–‡† ƒ„‘˜‡ǡ –Š‡ Š›†”‘’Š‘„‹ ‹–› ‘ˆ –Š‡ œ‡‘Ž‹–‡ ‹• –‘ ƒ Žƒ”‰‡ †‡‰”‡‡ †‹ –ƒ–‡† „› –Š‡ ‹ȀŽ ”ƒ–‹‘Ǣ –Š‡”‡ˆ‘”‡ǡ•‹Ž‹ ƒŽ‹–‡Ǧͳ™‹–ŠŠ‹‰Š‹ȀŽ”ƒ–‹‘™‘—Ž†„‡–Š‡’”‡ˆ‡””‡†ƒ†•‘”„‡–ˆ‘” ”‡ ‘˜‡”‹‰ ƒŽ ‘Š‘Ž• ˆ”‘ †‹Ž—–‡ ƒ“—‡‘—• •‘Ž—–‹‘•Ǥ ‘” •‡’ƒ”ƒ–‹‰ ‘–ƒ‹ƒ–• ȋ ƒ”„‘†‹‘š‹†‡ƒ†™ƒ–‡”Ȍˆ”‘‡–Šƒ‡ǡ–Š‡•‹–—ƒ–‹‘‰‡–•‘”‡ ‘’Ž‹ ƒ–‡†ƒ• ƒ’‘Žƒ”œ‡‘Ž‹–‡™‘—Ž†ˆƒ˜‘”–Š‡ƒ†•‘”’–‹‘‘ˆ„‘–Š™ƒ–‡”ƒ† ƒ”„‘†‹‘š‹†‡‘˜‡” –Šƒ– ‘ˆ ‡–Šƒ‡Ǥ ‘™‡˜‡”ǡ ƒ •—ˆˆ‹ ‹‡–Ž› ’‘Žƒ” œ‡‘Ž‹–‡ ™‘—Ž† ƒ†•‘”„ ™ƒ–‡” •‹‰‹ˆ‹ ƒ–Ž› •–”‘‰‡” –Šƒ ƒ”„‘ †‹‘š‹†‡ •‘ –Šƒ– ƒŽ‘•– ‘Ž› ™ƒ–‡” ™‹ŽŽ „‡ ƒ†•‘”„‡† ˆ”‘ –Š‡ „‹‘‰ƒ•ǡ –Š—• ƒ ”‡Žƒ–‹˜‡Ž› Š›†”‘’Š‘„‹  œ‡‘Ž‹–‡ ™‹–Š Ž‘™ ƒŽ—‹— ‘–‡–ƒ›„‡•—‹–ƒ„Ž‡ˆ‘””‡‘˜‹‰„‘–Š ƒ”„‘†‹‘š‹†‡ƒ†™ƒ–‡” ˆ”‘„‹‘‰ƒ•Ǥ. ͺ.

(98) ‹’‘”–ƒ– ‘ ‡”ƒ„‘—–œ‡‘Ž‹–‡•‹•–Š‡’”‡•‡ ‡‘ˆ•–”— –—”ƒŽ†‡ˆ‡ –•‹–Š‡ Žƒ––‹ ‡ ™Š‹ Š ƒ› ’‘–‡–‹ƒŽŽ› ƒˆˆ‡ – –Š‡ •‡Ž‡ –‹˜‹–› ‘ˆ –Š‡ œ‡‘Ž‹–‡ „‘–Š ˆ‘” ƒ†•‘”’–‹‘ ƒ† ‹ ƒ–ƒŽ›•‹•Ǥ ”ƒ†‹–‹‘ƒŽŽ›ǡ œ‡‘Ž‹–‡• ƒ”‡ •›–Š‡•‹œ‡† ƒ– ’  ˜ƒŽ—‡• ƒ”‘—† ͳͲǦͳͳ ”‡•—Ž–‹‰ ‹ •‘‡ ‘ˆ –Š‡ ‹ᄙᄙ‹ „‘†• „‡‹‰ „”‘‡ǡ –Š‹• ‹ –—” ”‡•—Ž–•‹–Š‡ˆ‘”ƒ–‹‘‘ˆ‹–‡”ƒŽ•‹Žƒ‘Ž‰”‘—’•ȋ‫‹ؠ‬ᄙ ȌǤͶ͹ǦͷͳŠ‡’”‡•‡ ‡‘ˆ –Š‡•‡ •‹Žƒ‘Ž ‰”‘—’• ‹ ”‡ƒ•‡• –Š‡ ’‘Žƒ”‹–› ƒ† ‘•‡“—‡–Ž› ƒŽ•‘ ‹ ”‡ƒ•‡• –Š‡ Š›†”‘’Š‹Ž‹ ƒ–—”‡‘ˆ–Š‡œ‡‘Ž‹–‡Ǥͷʹ— Š†‡ˆ‡ –•‹‰Š–„‡—†‡•‹”ƒ„Ž‡†‡’‡†‹‰ ‘ –Š‡ ƒ’’Ž‹ ƒ–‹‘Ǥ ‘” ‡šƒ’Ž‡ǡ ƒ Š‹‰Š ‘ ‡–”ƒ–‹‘ ‘ˆ •‹Žƒ‘Ž †‡ˆ‡ –• ‹ –Š‡ •–”— –—”‡ ‘ˆ ƒŽŽǦ•‹Ž‹ ƒ œ‡‘Ž‹–‡• ƒ •‹‰‹ˆ‹ ƒ–Ž› ”‡†— ‡ –Š‡‹” •‡’ƒ”ƒ–‹‘ ’‡”ˆ‘”ƒ ‡ ˆ‘” ”‡ ‘˜‡”› ‘ˆ ƒŽ ‘Š‘Ž• ˆ”‘ ƒ“—‡‘—• ‹š–—”‡•Ǥͷ͵Ǧͷͷ ‘™‡˜‡”ǡ œ‡‘Ž‹–‡• ’”‡’ƒ”‡† ƒ– ‡ƒ”Ž› ‡—–”ƒŽ ’  ‹ ˆŽ—‘”‹†‡ ȋ ·Ȍ ‡†‹— —•—ƒŽŽ› •Š‘™ ƒ •ƒŽŽ ‘ ‡–”ƒ–‹‘ ‘ˆ •— Š †‡ˆ‡ –•ǡ –Š—• ‰‹˜‹‰ –Š‡•‡ ƒ–‡”‹ƒŽ• ƒ ‘”‡ Š›†”‘’Š‘„‹ ƒ–—”‡ƒŽ–‡”‹‰–Š‡ƒ†•‘”’–‹‘’”‘’‡”–‹‡•ǤͶ͹ǡͷ͸Ǧͷ͹ ‘•‹†‡”‹‰ ƒŽŽ –Š‡•‡ —‹“—‡’”‘’‡”–‹‡• ‘ˆ œ‡‘Ž‹–‡• ƒ† –Š‡’‘••‹„‹Ž‹–› –‘ –ƒ‹Ž‘” –Š‡’”‘’‡”–‹‡•‘ˆ–Š‡œ‡‘Ž‹–‡ǡ‹–‹•‘–•—”’”‹•‹‰–Šƒ–— Š‡ˆˆ‘”–Šƒ•„‡‡†‡˜‘–‡† –‘‹˜‡•–‹‰ƒ–‡”‡ ‘˜‡”›‘ˆ˜ƒŽ—ƒ„Ž‡ Š‡‹ ƒŽ•ˆ”‘†‹Ž—–‡ˆ‡”‡–ƒ–‹‘•‘Ž—–‹‘•ǡͺǡ ͳ͵ǡͷͺ”‡‘˜‹‰ ‡”–ƒ‹ Žƒ••‡•‘ˆ’‘ŽŽ—–ƒ–•ˆ”‘ƒ‹”‘”™ƒ–‡”ͷͻƒ†•‡˜‡”ƒŽ‘–Š‡” ƒ’’Ž‹ ƒ–‹‘•‹–Š‡’—”‹ˆ‹ ƒ–‹‘ƒ†•‡’ƒ”ƒ–‹‘‘ˆ‰ƒ•‡•ƒ†Ž‹“—‹†•Ǥ͸Ͳ. 1.2.3. Adsorptionisotherms †•‘”’–‹‘ ‹• —•—ƒŽŽ› †‡• ”‹„‡† „› ƒ†•‘”’–‹‘ ‹•‘–Š‡”•Ǥ  ƒ†•‘”’–‹‘ ‹•‘–Š‡” ”‡Žƒ–‡• –Š‡ ƒ‘—– ‘ˆ ƒ†•‘”„ƒ–‡ǡ ƒ– ‡“—‹Ž‹„”‹—ǡ ‘ ƒ ‰‹˜‡ ƒ‘—– ‘ˆ ƒ†•‘”„‡– ƒ• ƒ ˆ— –‹‘ ‘ˆ ’ƒ”–‹ƒŽ ’”‡••—”‡ ‘” ‘ ‡–”ƒ–‹‘ ‘ˆ ƒ†•‘”„ƒ–‡ ‹ –Š‡ ˆŽ—‹††‡–‡”‹‡†ƒ–ƒ ‡”–ƒ‹ ‘•–ƒ––‡’‡”ƒ–—”‡Ǥƒ›†‹ˆˆ‡”‡–‘†‡Ž•Šƒ˜‡ „‡‡†‡”‹˜‡†–‘†‡• ”‹„‡ƒ†•‘”’–‹‘‹•‘–Š‡”•Ǥ‘‡ ‘‘‘†‡Ž•‘ˆ–‡—•‡† ˆ‘”†‡• ”‹„‹‰ƒ†•‘”’–‹‘‹œ‡‘Ž‹–‡•ƒ”‡‰‹˜‡„‡Ž‘™Ǥ ‹Ȍ. q qs. LangmuirǣŠ‡ƒ‰—‹”‘†‡Ž‹•’”‘„ƒ„Ž›–Š‡‘•– ‘‘‘†‡Ž—•‡† –‘†‡• ”‹„‡ƒ†•‘”’–‹‘‹œ‡‘Ž‹–‡•ǤŠ‡ƒ‰—‹”‹•‘–Š‡”‹•„ƒ•‡†‘–Š‡ ƒ••—’–‹‘•–Šƒ––Š‡”‡‹•ƒ†›ƒ‹ ‡“—‹Ž‹„”‹—„‡–™‡‡‘Ǧ‹–‡”ƒ –‹‰ ƒ†•‘”„‡† ‘Ž‡ —Ž‡• ƒ† –Š‡ ‘Ž‡ —Ž‡• ‹ –Š‡ ˆ”‡‡ ‰ƒ• ’Šƒ•‡ǡ –Š‡ •—”ˆƒ ‡ Šƒ• ƒ •’‡ ‹ˆ‹  —„‡” ‘ˆ ‡“—‹˜ƒŽ‡– •‹–‡• ™Š‡”‡ –Š‡ ‘Ž‡ —Ž‡• ƒ „‡ ƒ†•‘”„‡†ƒ†‡ƒ Š•‹–‡‹• ƒ’ƒ„Ž‡‘ˆŠ‘Ž†‹‰ƒ–‘•–‘‡‘Ž‡ —Ž‡Ǥ͸ͳŠ‹• ‘†‡Ž‹•‡š’”‡••‡†ƒ•ǣ bP 1  bP . ȋͳȌ. ™Š‡”‡ q ‹• –Š‡ ƒ†•‘”„‡† ‘ ‡–”ƒ–‹‘ ‘ˆ ƒ†•‘”„‡† •’‡ ‹‡•ǡ qs ‹• –Š‡ •ƒ–—”ƒ–‹‘ Ž‘ƒ†‹‰‹Ǥ‡Ǥ–Š‡ƒš‹—ƒ‘—–ƒ†•‘”„‡†’‘••‹„Ž‡ǡP‹•–Š‡’ƒ”–‹ƒŽ’”‡••—”‡‘ˆ. ͻ.

(99) –Š‡ƒ†•‘”„ƒ–‡‹–Š‡‰ƒ•’Šƒ•‡ƒ†b‹•–Š‡ƒ‰—‹”ƒ†•‘”’–‹‘’ƒ”ƒ‡–‡”ǤŠ‡ ƒ‰—‹” ƒ†•‘”’–‹‘ ’ƒ”ƒ‡–‡”• ƒ”‡ ”‡Žƒ–‡† –‘ –Š‡ Š‡ƒ– ‘ˆ ƒ†•‘”’–‹‘ ȋοHadsȌ ™Š‹ Š”‡ˆŽ‡ –•–Š‡ƒˆˆ‹‹–›‘ˆ–Š‡ƒ†•‘”„ƒ–‡ˆ‘”–Š‡ƒ†•‘”„‡–•—”ˆƒ ‡ǤŠ‡Š‡ƒ–‘ˆ ƒ†•‘”’–‹‘ ƒ› „‡ †‡–‡”‹‡† —•‹‰ –Š‡ Ž‹‡ƒ” ˜‡”•‹‘ ‘ˆ –Š‡ ˜ƒǯ– ‘ˆˆ ‡“—ƒ–‹‘ǣ͸ʹ ln b . 'H ads 'S ads  RT R . ȋʹȌ. ™Š‡”‡ǡοSads‹•–Š‡‡–”‘’› Šƒ‰‡—’‘ƒ†•‘”’–‹‘ǡR‹•–Š‡‰ƒ• ‘•–ƒ–ƒ†T‹• –Š‡–‡’‡”ƒ–—”‡Ǥ †•‘”’–‹‘ ‹• ƒ ‡š‘–Š‡”‹  ’”‘ ‡•• ƒ† –Š‡”‡ˆ‘”‡ –Š‡ Š‡ƒ– ‘ˆ ƒ†•‘”’–‹‘ ‹• ‡‰ƒ–‹˜‡ ™Š‹ Š ‡ƒ• –Šƒ– –Š‡ ƒ‘—– ƒ†•‘”„‡† ƒ– ƒ ‡”–ƒ‹ ’ƒ”–‹ƒŽ ’”‡••—”‡ †‡ ”‡ƒ•‡• ™‹–Š ‹ ”‡ƒ•‹‰ –‡’‡”ƒ–—”‡ǡ –Š‹• ‹• ƒŽ•‘ ”‡ˆŽ‡ –‡† ‹ †‡ ”‡ƒ•‹‰ bǦ ˜ƒŽ—‡• ™‹–Š ‹ ”‡ƒ•‹‰ –‡’‡”ƒ–—”‡•Ǥ Š‡ Š‡ƒ– ‘ˆ ƒ†•‘”’–‹‘ ƒ› „‡ ‘„–ƒ‹‡† ˆ”‘‡š’‡”‹‡–•„›†‡–‡”‹‹‰ƒ†•‘”’–‹‘‹•‘–Š‡”•ƒ–†‹ˆˆ‡”‡––‡’‡”ƒ–—”‡• ƒ†–Š‡”‡ƒˆ–‡”’Ž‘––‹‰Ž(b)˜‡”•—•1/T™Š‹ Š•Š‘—Ž†”‡•—Ž–‹ƒŽ‹‡ƒ”ˆ— –‹‘ ™‹–Š–Š‡•Ž‘’‡‘ˆο‫ܪ‬௔ௗ௦ Τܴ Ǥ Š‡ Š‡ƒ– ‘ˆ ƒ†•‘”’–‹‘ ‹• ”‡Žƒ–‡† –‘ –Š‡ ‡‡”‰› ‘ˆ –Š‡ ‹–‡”ƒ –‹‘• ™Š‹ Š ƒ”‡ ƒ –‹˜‡ †—”‹‰ –Š‡ ƒ†•‘”’–‹‘ ’”‘ ‡••ǡ ƒ† ‹– ”‡’”‡•‡–• –Š‡ •–”‡‰–Š ‘ˆ –Š‡ ‹–‡”ƒ –‹‘•„‡–™‡‡–Š‡ƒ†•‘”„ƒ–‡‘Ž‡ —Ž‡•ƒ†–Š‡ƒ†•‘”„‡–Ǥ͸͵ ‹‹Ȍ. q. Sips: Š‡ ƒ‰—‹” ƒ†•‘”’–‹‘ ‘†‡Ž †‡• ”‹„‡• ƒ†•‘”’–‹‘ ‹•‘–Š‡”• „› ƒ••—‹‰ ‹†‡ƒŽ ƒ†•‘”’–‹‘ „‡Šƒ˜‹‘”Ǥ ‘™‡˜‡”ǡ ‹ ƒ ”‡ƒŽ •‹–—ƒ–‹‘ǡ –Š‡ •—”ˆƒ ‡ Š‡–‡”‘‰‡‡‹–› ‹• ƒ ‘•‹†‡”ƒ„Ž‡ ’”‘’‡”–› ‘ˆ ƒ ƒ†•‘”„‡–ǡ ƒ• –Š‡ •—”ˆƒ ‡ ‹• ‡˜‡” ˆ”‡‡ ‘ˆ †‡ˆ‡ –•ǡ Š‡‹ ƒŽ ‹’—”‹–‹‡•ǡ ‰‡‘‡–”‹ ƒŽ †‹•Ž‘ ƒ–‹‘•ǡ‡– Ǥ‘•‡“—‡–Ž›ǡ–Š‡‡‡”‰›‘ˆ–Š‡ƒ†•‘”’–‹‘•‹–‡•™‹ŽŽ˜ƒ”› ˆ‘”ƒ”‡ƒŽ•—”ˆƒ ‡ǡƒ†–Š‹•‹•ƒ ‘—–‡†ˆ‘”‹–Š‡‹’•ƒ†•‘”’–‹‘‘†‡ŽǤ͵Ͳ Š‡ ‹’• ‘†‡Ž ‹• ƒ ‘„‹ƒ–‹‘ ‘ˆ –Š‡ ƒ‰—‹” ƒ† ”‡—†Ž‹ Š ‹•‘–Š‡”• ˆ‘” ’”‡†‹ –‹‰ ƒ†•‘”’–‹‘ ‘ Š‡–‡”‘‰‡‡‘—• ƒ†•‘”’–‹‘ •›•–‡•Ǥ͸ͳŠ‡‹’•‘†‡Ž‹•‰‹˜‡„›‡“—ƒ–‹‘ȋ͵ȌǤ qsat. bP1 n  1 bP1 n. ȋ͵Ȍ.

(100)  –Š‹• ‡“—ƒ–‹‘ǡ qsat ‹• –Š‡ •ƒ–—”ƒ–‹‘ Ž‘ƒ†‹‰ǡ P ‹• –Š‡ ’ƒ”–‹ƒŽ ’”‡••—”‡ ‘ˆ ƒ†•‘”„ƒ–‡ ‹ –Š‡ ‰ƒ• ’Šƒ•‡ǡ b ‹• –Š‡ ƒ‰—‹” ƒˆˆ‹‹–› ’ƒ”ƒ‡–‡”ǡ ƒ† n ‹• –Š‡ ”‡—†Ž‹ Š‡š’‘‡–ȋŠ‡–‡”‘‰‡‡‹–›ˆƒ –‘”Ȍ™Š‹ Š‹•–Š‡ƒ††‹–‹‘ƒŽ’ƒ”ƒ‡–‡”‹ –Š‡ ‹’• ‘†‡Ž ‘’ƒ”‡† –‘ –Š‡ ƒ‰—‹” ‘†‡Ž ƒ† ‹• —•—ƒŽŽ› ‰”‡ƒ–‡” –Šƒ —‹–›Ǥ͸Ͷ

(101) ˆ –Š‡ ”‡—†Ž‹ Š ‡š’‘‡– ȋnȌ ‹• —‹–›ǡ –Š‡ ƒ‰—‹” ‡“—ƒ–‹‘ ™‹ŽŽ „‡ ͳͲ.

(102) ‘„–ƒ‹‡†™Š‹ Š‹• ‘‘Ž›ƒ’’Ž‹ ƒ„Ž‡ˆ‘”‹†‡ƒŽ•—”ˆƒ ‡•Ǥ͸ͷŠ‡˜ƒŽ—‡‘ˆnˆ‘”ƒ Š‘‘‰‡‡‘—• ƒ–‡”‹ƒŽ ‹• ‘‡ǡ ƒ† ‹– ‹• ‰”‡ƒ–‡” –Šƒ ‘‡ ˆ‘” Š‡–‡”‘‰‡‡‘—• ƒ–‡”‹ƒŽ•Ǥ Š—•ǡ –Š‡ Žƒ”‰‡” –Š‡ ”‡—†Ž‹ Š ‡š’‘‡–ǡ ‹– ‹’Ž‹‡• –Š‡ ‰”‡ƒ–‡” –Š‡ Š‡–‡”‘‰‡‡‹–›‘ˆ–Š‡•›•–‡Ǥ ͳǤʹǤͶǤ Mixedgasadsorption 

(103)  ‘•– ƒ•‡•ǡ ƒ†•‘”’–‹‘ •›•–‡• ‹˜‘Ž˜‡ ‘”‡ –Šƒ ‘‡ ‘’‘‡–Ǥ Š‡”‡ˆ‘”‡ǡ‹– ‹•‘ˆ‰”‡ƒ–‹’‘”–ƒ ‡–‘—†‡”•–ƒ†ƒ†•‘”’–‹‘•›•–‡•‹˜‘Ž˜‹‰ ‘’‡–‹–‹‘ „‡–™‡‡ ‘Ž‡ —Ž‡• ‘ˆ †‹ˆˆ‡”‡– –›’‡• ˆ‘” ‡˜ƒŽ—ƒ–‹‘ ‘ˆ ƒ†•‘”„‡–• ƒ†‹–‡”’”‡–ƒ–‹‘‘ˆ–‡ Š‹ ƒŽƒ†•‘”’–‹‘’”‘ ‡••‡•Ǥ ‘”ƒ‡ˆˆ‹ ‹‡–•‡’ƒ”ƒ–‹‘ ’”‘ ‡••„ƒ•‡†‘ƒ†•‘”’–‹‘ǡ•—ˆˆ‹ ‹‡–Ž›Š‹‰Šƒ†•‘”’–‹‘•‡Ž‡ –‹˜‹–›‹•”‡“—‹”‡†ǡ ‹Ǥ‡Ǥ–Šƒ–‘‡‘ˆ–Š‡ ‘’‘‡–•ƒ†•‘”„•’”‡ˆ‡”‡–‹ƒŽŽ›–Šƒ–Š‡‘–Š‡” ‘’‘‡–•Ǥ i). SelectivityǣŠ‡ƒ†•‘”’–‹‘•‡Ž‡ –‹˜‹–›ȋȽȌ‹•†‡ˆ‹‡†ƒ•–Š‡‘Ž‡ˆ”ƒ –‹‘ ‘ˆ–Š‡ ‘’‘‡–•ȋXiƒ†XjȌ‹–Š‡ƒ†•‘”„‡†’Šƒ•‡†‹˜‹†‡†„›–Š‡‘Ž‡ ˆ”ƒ –‹‘•‹–Š‡Ž‹“—‹†‘”‰ƒ•’Šƒ•‡ȋYiƒ†YjȌǣ Xi X j. D ij. Yi Y j. . ȋͶȌ. 

(104) ƒ’Š›•‹ ƒŽƒ†•‘”’–‹‘•›•–‡ǡ•‡Ž‡ –‹˜‹–›ƒ›†‡’‡†‘†‹ˆˆ‡”‡ ‡•‹‡‹–Š‡” ‡“—‹Ž‹„”‹— ‘” ‹‡–‹ •Ǥ ‘™‡˜‡”ǡ ‘•– ‘ˆ –Š‡ ƒ†•‘”’–‹‘ „ƒ•‡† •‡’ƒ”ƒ–‹‘ ’”‘ ‡••‡•†‡’‡†‘‡“—‹Ž‹„”‹—„ƒ•‡†•‡Ž‡ –‹˜‹–›Ǥ͵ͳ ‡•’‹–‡‹–•‹’‘”–ƒ ‡ǡƒ†•‘”’–‹‘†ƒ–ƒˆ‘”—Ž–‹ ‘’‘‡–‹š–—”‡•ƒ”‡• ƒ”‡• „‡ ƒ—•‡ –Š‡•‡ ‡ƒ•—”‡‡–• ƒ”‡ „‘–Š †‹ˆˆ‹ —Ž– ƒ† ˜‡”› –‹‡ ‘•—‹‰Ǣ –Š‡”‡ˆ‘”‡ǡ”‡Ž‹ƒ„Ž‡‘†‡Ž•ˆ‘”’”‡†‹ –‹‰—Ž–‹ ‘’‘‡–ƒ†•‘”’–‹‘ˆ”‘•‹‰Ž‡Ǧ ‘’‘‡– ƒ†•‘”’–‹‘ †ƒ–ƒ ƒ”‡ Š‹‰ŠŽ› †‡•‹”ƒ„Ž‡Ǥ Š‡ ‹†‡ƒŽ ƒ†•‘”„‡† •‘Ž—–‹‘ –Š‡‘”› ȋ

(105) Ȍ ‹• ‘‡ •— Š ‘†‡Ž –Šƒ– ‹• ˆ”‡“—‡–Ž› —•‡† ˆ‘” ’”‡†‹ –‹‰ —Ž–‹ ‘’‘‡–ƒ†•‘”’–‹‘‹œ‡‘Ž‹–‡•Ǥ ii). The ideal adsorbed solution theory (IAST): Š‡

(106)  ‘•–‹–—–‡ ƒ –Š‡”‘†›ƒ‹ ƒŽŽ› ‘•‹•–‡– ‡–Š‘† ˆ‘” ’”‡†‹ –‹‰ ƒ†•‘”’–‹‘ ‡“—‹Ž‹„”‹— ˆ‘” —Ž–‹ ‘’‘‡– ‹š–—”‡• „› ƒ‹‰ —•‡ ‘ˆ –Š‡ •‹‰Ž‡ ‰ƒ• ƒ†•‘”’–‹‘ ‹•‘–Š‡”• ƒ† Šƒ• „‡ ƒ—•‡ ‘ˆ –Š‹• ƒ––”ƒ –‹˜‡ ˆ‡ƒ–—”‡ ‰ƒ‹‡†’‘’—Žƒ”‹–›ǤŠ‡

(107) ™ƒ•†‡˜‡Ž‘’‡†„››‡”•ƒ†”ƒ—•‹–œƒ† ‹•„ƒ•‡†‘–Š”‡‡ƒ••—’–‹‘•ǣ͸͸ 

(108) Ǥ Š‡ —Ž–‹ ‘’‘‡– ‹š–—”‡ „‡Šƒ˜‡• Ž‹‡ ƒ ‹†‡ƒŽ •‘Ž—–‹‘ ȋ‡“—ƒŽ ‡ƒ•–”‡‰–Š‘ˆ‹–‡”ƒ –‹‘„‡–™‡‡–Š‡‘Ž‡ —Ž‡•‹–Š‡•‘Ž—–‹‘Ȍ ƒ– ‘•–ƒ–’”‡••—”‡ƒ†–‡’‡”ƒ–—”‡Ǥ

(109)

(110) Ǥ Š‡•—”ˆƒ ‡ƒ”‡ƒƒ˜ƒ‹Žƒ„Ž‡ˆ‘”ƒŽŽƒ†•‘”„ƒ–‡•‹•–Š‡•ƒ‡Ǥ ͳͳ.

(111)

(112)

(113)

(114) Ǥ. †•‘”„‡–‹•‹‡”–Ǥ. Š‡

(115)  Šƒ• „‡‡ ’”‘˜‡ –‘ ƒ —”ƒ–‡Ž› †‡• ”‹„‡ –Š‡ —Ž–‹ ‘’‘‡– ƒ†•‘”’–‹‘ „‡Šƒ˜‹‘” ˆ‘” ƒ› ƒ†•‘”„ƒ–‡• ‹ œ‡‘Ž‹–‡•ǡ ‡•’‡ ‹ƒŽŽ› ˆ‘” •ƒŽŽ ƒ† ™‡ƒŽ› ‹–‡”ƒ –‹‰ •’‡ ‹‡•Ǥ͸͹Ǧ͸ͺ ‘™‡˜‡”ǡ ˆ‘” •–”‘‰Ž› ‹–‡”ƒ –‹‰ ‹š–—”‡• ‡Ǥ‰Ǥ Š›†”‘‰‡Ǧ„‘†‹‰ ƒ†•‘”„ƒ–‡• ‘” ™Š‡ ’ƒ ‹‰ ‡ˆˆ‡ – ‰‡–• ‹’‘”–ƒ–ǡ –Š‡

(116)  ˆ”‡“—‡–Ž›ˆƒ‹Ž•‹’”‡†‹ –‹‰–Š‡ƒ‘—–ƒ†•‘”„‡†Ǥ͸ͻǦ͹Ͳ 

(117)  –Š‹• ™‘”ǡ –Š‡

(118) †‡ƒŽ ƒ†•‘”„‡† •‘Ž—–‹‘ –Š‡‘”› ™ƒ• —•‡† ˆ‘” ’”‡†‹ –‹‰ –Š‡ ƒ‘—– ‘ˆ ƒ†•‘”„‡† ™ƒ–‡”ǡ ‡–Šƒ‡ ƒ† ƒ”„‘ †‹‘š‹†‡ ˆ”‘ ‰ƒ• ‹š–—”‡• ƒ† –Š‡•‡ ’”‡†‹ –‹‘• ™‡”‡ ‘’ƒ”‡† –‘ ‡š’‡”‹‡–ƒŽŽ› †‡–‡”‹‡† ƒ†•‘”„‡† ‘ ‡–”ƒ–‹‘• –‘ –‡•– –Š‡ ƒ’’Ž‹ ƒ„‹Ž‹–› ‘ˆ

(119)  –‘ –Š‡ ǦͷȀ‡–Šƒ‡Ȁ ƒ”„‘ †‹‘š‹†‡Ȁ™ƒ–‡”•›•–‡Ǥ     . ͳʹ. .

(120) 1.3. Scopeofthepresentwork Š‡• ‘’‡‘ˆ–Š‡’”‡•‡–™‘”™ƒ•–‘•–—†›ƒ†•‘”’–‹‘‘ˆ„—–ƒ‘Žƒ†™ƒ–‡”‹ •‹Ž‹ ƒŽ‹–‡Ǧͳˆ‹Ž•ƒ–†‹ˆˆ‡”‡––‡’‡”ƒ–—”‡•ƒ†–‘‡š–”ƒ –“—ƒ–‹–ƒ–‹˜‡ƒ†•‘”’–‹‘ †ƒ–ƒǡ‹–Š‡ˆ‘”‘ˆƒ‰—‹”ƒ†‹’•’ƒ”ƒ‡–‡”•ƒ†Š‡ƒ–•‘ˆƒ†•‘”’–‹‘ǡ—•‡ˆ—Ž ˆ‘” ‡˜ƒŽ—ƒ–‹‰ –Š‡ ’‡”ˆ‘”ƒ ‡ ‘ˆ •‹Ž‹ ƒŽ‹–‡Ǧͳ ƒ†•‘”„‡–• ƒ† ‡„”ƒ‡•Ǥ

(121)  ’ƒ”–‹ —Žƒ”ǡ–Š‡‡ˆˆ‡ –‘ˆ‹–‡”ƒŽ•–”— –—”ƒŽ†‡ˆ‡ –•‘–Š‡ƒ†•‘”’–‹‘ƒ†„—–ƒ‘Ž ƒ†™ƒ–‡”‹•‹Ž‹ ƒŽ‹–‡Ǧͳˆ‹Ž•™ƒ•–‘„‡‡Ž— ‹†ƒ–‡†Ǥ ‘”‡‘˜‡”ǡ –Š‡ in situ Ǧ 

(122)  ‡–Š‘† ™ƒ• —•‡† –‘ •–—†› —Ž–‹ ‘’‘‡– ƒ†•‘”’–‹‘‘ˆ™ƒ–‡”ǡ‡–Šƒ‡ƒ† ƒ”„‘†‹‘š‹†‡‹Ǧͷœ‡‘Ž‹–‡ǤŠ‡‘„Œ‡ –‹˜‡ ™ƒ• –‘ †‡–‡”‹‡ –Š‡ ƒ†•‘”’–‹‘ •‡Ž‡ –‹˜‹–‹‡• ƒ† –‘ ƒ••‡•• –Š‡ ’‡”ˆ‘”ƒ ‡ ‘ˆ –Š‡

(123) –‘ƒ —”ƒ–‡Ž›’”‡†‹ ––Š‡ƒ†•‘”„‡†ƒ‘—–•†—”‹‰‹š–—”‡ƒ†•‘”’–‹‘Ǥ   . . ͳ͵.

(124) . ͳͶ.

(125) Chapter 2. Theory. 2.1. ATRǦFTIRTechnique ‹†Ǧ

(126) ˆ”ƒ”‡† •’‡ –”‘• ‘’› ȋ

(127) Ȍ ‹• ƒ ”‡Ž‹ƒ„Ž‡ ‡–Š‘† ˆ‘” Šƒ”ƒ –‡”‹œƒ–‹‘ǡ ‹†‡–‹ˆ‹ ƒ–‹‘ƒ†“—ƒ–‹ˆ‹ ƒ–‹‘‘ˆƒ›•—„•–ƒ ‡•Ǥ‡‘ˆ–Š‡ƒ†˜ƒ–ƒ‰‡•‘ˆ

(128)  •’‡ –”‘• ‘’› ‹• –Šƒ– –Š‡ •’‡ –”ƒ ƒ „‡ ‘„–ƒ‹‡† ˆ”‘ ƒ ™‹†‡ ”ƒ‰‡ ‘ˆ •‘Ž‹†•ǡ Ž‹“—‹†•ƒ†‰ƒ•‡•ƒ•Ž‘‰ƒ•–Š‡›ˆ—Žˆ‹ŽŽ–Š‡•‡Ž‡ –‹‘”—Ž‡•ǤȗŠ‡ ‘„‹ƒ–‹‘‘ˆ

(129)  •’‡ –”‘• ‘’›™‹–Š–Š‡–Š‡‘”‹‡•‘ˆ”‡ˆŽ‡ –‹‘Šƒ•’”‘˜‡–‘„‡ƒ’‘™‡”ˆ—Ž‡–Š‘† ˆ‘” •—”ˆƒ ‡ ƒƒŽ›•‹•Ǥ Š”‡‡ •’‡ ‹ˆ‹ 

(130)  ”‡ˆŽ‡ –ƒ ‡ •ƒ’Ž‹‰ –‡ Š‹“—‡• ‡š‹•–ǣ͹ͳ •’‡ —Žƒ” ”‡ˆŽ‡ –ƒ ‡ǡ †‹ˆˆ—•‡ ”‡ˆŽ‡ –ƒ ‡ ƒ† ‹–‡”ƒŽ ”‡ˆŽ‡ –ƒ ‡Ǥ

(131)  –Š‹• ™‘”ǡ AttenuatedTotalReflectionǦFourierTransformInfrared(ATRǦFTIR)Spectroscopyǡ ™Š‹ Š ‹• ƒ ‹–‡”ƒŽ ”‡ˆŽ‡ –‹‘ ‡–Š‘†ǡ ™ƒ• —•‡† –‘ •–—†› –Š‡ ƒ†•‘”’–‹‘ ’”‘’‡”–‹‡•‘ˆ

(132) Ǧ–›’‡œ‡‘Ž‹–‡•Ǥ‹–Š–Š‹•–‡ Š‹“—‡ǡ‹–‹•’‘••‹„Ž‡–‘”‡ ‘”†Š‹‰Š “—ƒŽ‹–› •’‡ –”ƒ ‘ˆ ™‡ŽŽǦ†‡ˆ‹‡† –Š‹ œ‡‘Ž‹–‡ ˆ‹Ž• —†‡” ™‡ŽŽǦ ‘–”‘ŽŽ‡† ‘†‹–‹‘•Ǥ͹ʹǦ͹͵ Š‹•ǡ ‹ ‘„‹ƒ–‹‘ ™‹–Š –Š‡ ƒ„‹Ž‹–› ‘ˆ ‹ˆ”ƒ”‡† •’‡ –”‘• ‘’› –‘ †‹• ”‹‹ƒ–‡ „‡–™‡‡ †‹ˆˆ‡”‡– ‘Ž‡ —Ž‡• ƒ‡• –Š‡ Ǧ 

(133)  –‡ Š‹“—‡ ‹†‡ƒŽ ˆ‘”•–—†›‹‰‡˜‡—Ž–‹ ‘’‘‡–ƒ†•‘”’–‹‘‹œ‡‘Ž‹–‡•Ǥ. 2.1.1. Determinationofadsorbateloadinginthefilm 

(134) Ǧ 

(135) •’‡ –”‘• ‘’›ǡ–Š‡‹ˆ”ƒ”‡†„‡ƒ‹•‹–‡”ƒŽŽ›–‘–ƒŽ”‡ˆŽ‡ –‡†‹ƒ

(136) –”ƒ•’ƒ”‡– ”›•–ƒŽ‘ˆˆ‘”‡šƒ’Ž‡‹ —Žˆ‹†‡ȋȌǡ‹ ‡Ž‡‹†‡ȋ‡Ȍǡ ‹Ž‹ ‘ ‘” ‡”ƒ‹—Ǥ Š‡ ‹ˆ”ƒ”‡† „‡ƒ ƒ› ‹–‡”ƒ – ™‹–Š •ƒ’Ž‡• ‹ Ž‘•‡ ˜‹ ‹‹–› ‘ˆ –Š‡ •—”ˆƒ ‡ ‘ˆ –Š‡  ‡Ž‡‡– •‹ ‡ –Š‡ ‡Ž‡ –”‹  ˆ‹‡Ž† ‘ˆ –Š‡ ‹ˆ”ƒ”‡† ”ƒ†‹ƒ–‹‘ ƒ’‡‡–”ƒ–‡ƒ•Š‘”–†‹•–ƒ ‡‘—–•‹†‡–Š‡‡Ž‡‡–ǤŠ‡†‹•–ƒ ‡™Š‹ Š –Š‡ ‹ˆ”ƒ”‡† „‡ƒ ’”‘„‡• ƒ› „‡ ‡•–‹ƒ–‡† „› –Š‡ ’‡‡–”ƒ–‹‘ †‡’–ŠǤ Š‡ ’‡‡–”ƒ–‹‘ †‡’–Š ‹• †‡ˆ‹‡† ƒ• –Š‡ †‹•–ƒ ‡ ˆ”‘ –Š‡  ”›•–ƒŽ ™Š‡”‡ –Š‡ ‹–‡•‹–› ‘ˆ –Š‡ ‡Ž‡ –”‹  ˆ‹‡Ž† Šƒ• †‡ ”‡ƒ•‡† –‘ ƒ ˜ƒŽ—‡ ‡Ǧͳ ‘ˆ –Šƒ– ƒ– –Š‡  •—”ˆƒ ‡ǤŠ‡’‡‡–”ƒ–‹‘†‡’–Š–›’‹ ƒŽŽ›˜ƒ”‹‡•„‡–™‡‡ƒ ‘—’Ž‡‘ˆŠ—†”‡† –‘ ƒ ‘—’Ž‡ ‘ˆ ρǡ ƒ‹‰ –Š‡  ‡–Š‘† •—‹–ƒ„Ž‡ ˆ‘” •–—†›‹‰ –Š‹ ˆ‹Ž• ƒ† •—”ˆƒ ‡•ǤŠ‡’‡‡–”ƒ–‹‘†‡’–ŠȋdpȌ‹•‰‹˜‡„›ǣ͹͵ dp. O1. ȋͷȌ. 2 12 2S (sin 2 T  n21 ) .  ȗ ‘”†‹‰–‘•‡Ž‡ –‹‘”—Ž‡•ǡ˜‹„”ƒ–‹‘•ƒ”‡‘Ž›

(137) ƒ –‹˜‡‹ˆƒ‘Ž‡ —Žƒ”†‹’‘Ž‡‘‡– Šƒ‰‡•. †—”‹‰–Š‡˜‹„”ƒ–‹‘Ǥ. ͳͷ.

(138) ™Š‡”‡ɉ1‹•–Š‡™ƒ˜‡Ž‡‰–Š‘ˆ–Š‡‹ˆ”ƒ”‡†”ƒ†‹ƒ–‹‘‹•‹†‡–Š‡ ”›•–ƒŽǡn1‹• –Š‡ ”‡ˆ”ƒ –‹˜‡ ‹†‡š ‘ˆ –Š‡  ‡Ž‡‡–ǡ ƒ† ߠ ‹• –Š‡ ƒ‰Ž‡ ‘ˆ ‹ ‹†‡ ‡ ȋͶͷι ‹ –Š‹•™‘”ȌǤ —”–Š‡”ǡn21=n2/n1™Š‡”‡n2 ‹•–Š‡”‡ˆ”ƒ –‹˜‡‹†‡š‘ˆ–Š‡œ‡‘Ž‹–‡ˆ‹Ž ‘˜‡”‹‰–Š‡‡Ž‡‡–Ǥ Š‡‡‡”Ǧƒ„‡”–Žƒ™”‡Žƒ–‡•–Š‡ƒ„•‘”„ƒ ‡‘„•‡”˜‡†‹ƒ‹ˆ”ƒ”‡†•’‡ –”— –‘ –Š‡ ‘ ‡–”ƒ–‹‘ ‘ˆ –Š‡ ƒ†•‘”„ƒ–‡ ‹ –Š‡ •ƒ’Ž‡ ˆ‘” ƒ –”ƒ•‹••‹‘ ‡ƒ•—”‡‡–ǣ͹Ͷ ‫ ܣ‬ൌ Ž‘‰. ‫ܫ‬଴ ൌ ߝ݈ܿ ‫ܫ‬. ȋ͸Ȍ. ™Š‡”‡ I0 ƒ† I ƒ”‡ ‹ ‹†‡– ƒ† –”ƒ•‹––‡† ‹–‡•‹–‹‡• ‘ˆ –Š‡ ‹ˆ”ƒ”‡† „‡ƒ ”‡•’‡ –‹˜‡Ž›ǡ A ‹• –Š‡ ƒ„•‘”„ƒ ‡ǡ ɂ ‹• –Š‡ ‘Žƒ” ƒ„•‘”’–‹˜‹–›ǡ c ‹• –Š‡ ‘ ‡–”ƒ–‹‘‘ˆ–Š‡•ƒ’Ž‡ƒ†l‹•–Š‡’ƒ–ŠŽ‡‰–Š–Š”‘—‰Š–Š‡•ƒ’Ž‡Ǥ ‘™‡˜‡”ǡ –Š‹• ‡“—ƒ–‹‘ ƒ‘– „‡ —•‡† †‹”‡ –Ž› ‹ –Š‡  ‡–Š‘†Ǥ ‘’‹•͹ͷ ƒ† ‹”ƒ„‡ŽŽƒ͹͸ †‡˜‡Ž‘’‡† ƒ ‡–Š‘† –‘ †‡–‡”‹‡ ‘ ‡–”ƒ–‹‘ ‘ˆ •’‡ ‹‡• Ž‘•‡ –‘ –Š‡ ”›•–ƒŽǤŠ‡ƒ„•‘”’–‹‘’‡””‡ˆŽ‡ –‹‘ǡˆ‘”ƒ’ƒ”–‹ —Žƒ”„ƒ†ǡ‹•‰‹˜‡„›ǣ A N. n21E02H cosT. ³. f. 0. C ( z)e. 2 z d p. ȋ͹Ȍ. dz. ™Š‡”‡A‹•–Š‡‹–‡‰”ƒ–‡†ƒ„•‘”„ƒ ‡‘ˆ–Š‡„ƒ†‘ˆ‹–‡”‡•–ǡN‹•–Š‡—„‡”‘ˆ ”‡ˆŽ‡ –‹‘• ‹ –Š‡  ‡Ž‡‡– ȋʹͲ ‹ –Š‹• ™‘”Ȍǡ C(z) ‹• –Š‡ ‘ ‡–”ƒ–‹‘ ‘ˆ ƒ†•‘”„ƒ–‡ ‹ –Š‡ œ‡‘Ž‹–‡ ˆ‹Ž ™Š‹ Š ™ƒ• ƒ••—‡† –‘ „‡ ‘•–ƒ– ‹ –Š‡ ˆ‹Ž ƒ– ‡“—‹Ž‹„”‹— ƒ† œ‡”‘ ‘—–•‹†‡ –Š‡ ˆ‹Ž ȋ‡‰Ž‡ –‹‰ –Š‡ „—Ž ‰ƒ• ‘–”‹„—–‹‘ȌǤ Š‡”‡ˆ‘”‡ǡ ƒˆ–‡” ‹–‡‰”ƒ–‹‰ ‘˜‡” –Š‡ ˆ‹Ž –Š‹ ‡••ǡ –Š‡ ˆ‘ŽŽ‘™‹‰ ‡š’”‡••‹‘ ‹• ‘„–ƒ‹‡†ǣ A N. n21 E02 d p C 2 cos T. H 1 e. 2d a d p.

(139). . ȋͺȌ. ™Š‡”‡da ‹•–Š‡–Š‹ ‡••‘ˆ–Š‡ˆ‹ŽǤ —”–Š‡”ǡ–Š‡†‹•–ƒ ‡”‡“—‹”‡†–‘‘„–ƒ‹–Š‡ •ƒ‡ ƒ„•‘”„ƒ ‡ ‹ ƒ –”ƒ•‹••‹‘ ‡ƒ•—”‡‡– ƒ• ‹ Ǧ 

(140)  ‹• †‡ˆ‹‡† ƒ• ‡ˆˆ‡ –‹˜‡–Š‹ ‡••ǡdeǣ de. n21 E02 d p. ȋͻȌ. 2 cosT . ƒ† de ‹• †‡’‡†‡– ‘ –Š‡ ’‘Žƒ”‹œƒ–‹‘ ‘ˆ –Š‡ ‹ˆ”ƒ”‡† ”ƒ†‹ƒ–‹‘ ƒ† ƒ „‡ ‡•–‹ƒ–‡†ƒ•ǣ. ͳ͸.

References

Download now ( PDF - 198 Page - 9.34 MB )

Related documents

“It feels like this is good for many people” The multiple rationales of municipal owned food production

It has an overall objective of creating “a competitive food supply chain that increases overall food production while achieving the relevant national environmental objectives,

Simulation of transient adsorption in MFI films

Regarding the boundary conditions for heat transfer, at the substrate-zeolite interface the temperature will remain constant, and equal to the reference

Multicomponent Separation Performance of MFI-type Zeolite Membranes

Mixture separation by zeolite membranes is based on transport of components through the membrane [1,17]. Due to the polycrystalline structure of a zeolite membrane, molecules can

Adsorption properties of synthetic iron oxides: as(V) adsorption on goethite (alpha-FeOOH)

According to the Brunauer’s classification the isotherm obtained when N 2 adsorption was performed in synthetic goethite powder (not shown) belong to the isotherms of type

Assessment of IT Services: The Need for a Service Perspective

The purpose of CMMI is to provide a compre- hensive integrated set of guidelines for providing superior services (SEI 2006). To suggest enhancements of IRP, we have structured

Alternative seeding methods for growing MFI zeolite films

Their study showed the presence of amorphous precursor nanoparticles in the solution and then the apparition of a second larger particles population at least 2 hours after

Solvent adsorption in SFC: Adsorption of methanol under supercritical conditions

Adsorption measurements (see 1.3) near or above the critical point do not follow the Langmuir model of adsorption, see 1.2.2; increasing adsorption with increasing pressure

Adsorption Studies with Liquid Chromatography: Experimental Preparations for Thorough Determination of Adsorption Data

Important steps along the way include the choice of separation system and of suitable analytes, preparation of mobile phases and sample solutions, calibration, determination