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CC QU TRNH HA HC v HA L TRONG CNG NGH MI TRNG

Chng : HP PH

TS. TRNH BO SN

GiI THIU

GiI THIU
HP c d trong x l: Pha hp ph- b HP: R-K (chim a s), R-L. - kh thi: n-hexan, benzen, toluen, VOCs, bng GAC, khi ng c nh CO, NOx - nc thi: cht nhum axit bng GAC (Walker, 1997), NO3bng sepiolite, PAC (Ozturk, 2004) - nc cp: cc cht hu c, tr. ion - nhim t: d lng thuc BVTV bng GAC, VSV trong t, nc mt,
Cht b hp ph (adsorbent)

Cht b hp ph (adsorbate)

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NGUYN L C BN LC HP PH Cc phn t trong pha lu cht c th b gi li trn b mt pha rn bng cc loi lc sau: (i)lc ht phn t (van der Waals) v lc ht tnh in; yu, TN qtr hp ph vt l; Qtr HP vt l l qtr ta nhit gim nng lng t do (H<0) v entropy (ii) Lk ha hc; bn, khng TN qtr hp ph ha hc. HP vt l c sd rng ri v s c m t trong chng ny

NGUYN L C BN TNH CHN LC Tnh chn lc ca h hp vl ph thuc: cn bng hay ng hc. Tnh chn lc ng hc - cht HP c k.th ry p.t nh: ry p.t carbon, zeolite hay hc tng t zeolite. Cc v/l ny c k.th l rng ~ k.th p.t hn ch c/ng TD ca ptu b HP Tnh chn lc cao da vo k.th p.t ca l rng v cht HP

NGUYN L C BN TNH CHN LC Vd: qtr phn tch hydrocarbon mch thng t isomer vng v nhnh ca chng bng cht hp 5A zeolite. kim sot qtr la chn ng hc ca cht HP k.th ry p.t iu chnh kch thc l rng. -/v carbon: iu chnh qtr chy

NGUYN L C BN TNH CHN LC Tnh chn lc cn bng: iu chnh s cn bng gia lc tnh in v lc van der Waals: thay i bn cht ha hc b mt hoc kch thc l rng. /v cht HP carbon, Oh b mt l cch n gin nhng hiu qu lm b mt c tnh phn cc hn lm tng tnh chn lc ca vl HP

-/v zeolite: trao i ion

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NGUYN L C BN TNH CHN LC

NGUYN L C BN TNH CHN LC Vi cht HP Zeoloite: thay i bn cht ca cation bng pp tr. ion hay iu chnh t l siliconaluminum quyt nh mt cation HP trn b mt khng phn cc (silica tinh khit hay carbon khng b Oh) ch yu bng lc van der Waals qui lut i lc ~ KLPT

B MT K NC v A NC
Nc - phn cc mnh HP mnh trn b mt phn cc do lc ht tnh in Cc cht hp phn cc (zeolites, silica gel, hay nhm hot tnh) cht HP a nc (hydrophilic) >< b mt khng phn cc s ko c tng tc tnh in vi nc HP cht hu c hay cht HP k nc (hydrophobic) Cht hp k nc nh than hot tnh, silicalite: - Silicalite c i lc vi nc rt thp, thng c sd tch ru v cc cht hu c khc ra khi dd long.

HP BNG NGNG T MAO QUN

p sut hi cn bng trong 1 l rng hay mao qun GiM bi hiu ng ca sc cng b mt.

Cht b HP lng ngng t trong 1 l rng nh p < pbh

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HP BNG NGNG T MAO QUN

CHT HP PH
t c kh nng hp cao th cht hp phi c: din tch b mt ring cao cu trc xp cao vi l rng nh Mt s cht hp thng thng c th c phn loi nh sau:
Phn b kch thc l rng

vng ngng t mao dn dn dn m rng nh hng ng cn bng ng nhit. tnh chn lc tuyt i b mt i Cn trnh tnh trng ny trong cc qtr chit tch Tuy nhin, hiu ng ny cng nng cao kh nng ht nc ca cc cht HP l rng ln nh silica gel hay alumina mt m cao.

Phn cc b mt Phn cc Khng phn cc

Hp Zeolites Silicalites kth ry phn t carbon

Rng Nhm hot tnh, silica gel Than hot tnh

CHT HP PH
Bng 2 trnh by c tnh v d ca cht HP v nh hnh

CHT HP PH
Bng 3 trnh by c tnh v d ca cc cht HP polymer

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CHT HP PH
Bng 4 trnh by c tnh v d ca cht HP tinh th

MT S CHT HP PH CNG NGHIP TIU BiU

Theo Dabrowski (2001)

Cht hp v nh hnh (amorphous)

Cht hp v nh hnh (amorphous)

Cht hp v nh hnh nh silica gel, than hot tnh, nhm hot tnh c din tch ring b mt (SSA-specific surface area) cao 200 1000 m2/g ; mt vi loi than hot tnh cn c SSA n 1500 m 2/g. Nhng vl c SSA cao c t l l rng kth rt nh cao khng thch hp cho hp cht c kth ptu ln. S khc nhau gia carbon kh, c sd hp kh c KLPT nh, v carbon lng, c sd hp cht c KLPT ln trong pha lng, nm ch kch thc ca l rng. Trong cht hp vh, kth l rng phn b trong khong rng, t vi nm n um

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Cht hp v nh hnh (amorphous)

Trong cht hp vh, kth l rng phn b trong khong rng, t vi nm n um IUPAC p/loai nh sau: -Micropore < 2 nm k -Mesopore 2 5 nm k -Macropore > 50 nm k

Cht hp tinh th (crystalline)

Trong cht hp tinh th: zeolite v nhng cht ging zeolite nh silicalite,phosphate aluminium microporous, -kch thc l rng c xc nh bi cu trc tinh th - khng c phn b v kch thc l rng.

Cht ht m (desiccants)
Cht ht m: silica gel, nhm hot tnh, zeolite giu aluminium (4A hay 13X) ht hi nc trong kk Cn c phn cc cao v SSA cao

Cht ht m (desiccants)
Hnh 3 trnh by ng hp cb ng nhit cho 1 s vl ht m c hnh dng khc nhau,

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CN BNG TRONG HP - NH LuT HENRY S cn bng ca cht b HP trong pha lu cht v pha rn tun theo nguyn tc nhit-ng. ng cn bng ng nhit: biu din s tng quan gia n. cht b HP trong pha rn hay ti trng, q, vi n. trong pha lu cht hay p sut ring phn, p, T = const. Nhn chung, qtr HP vly trn b mt ng nht T thp, ng ng nhit s c dng ng thng H s gc trong vng T thp thng c gi l hng s Henry, K.

CN BNG TRONG HP - NH LuT HENRY Hng s cb nhit ng, K, ph thuc T v tun theo pt vant Hoff (1) Vi H0 l nhit gii hn ca qtr hp k chun (zero coverage???) Hng s Henry K - t l ca nng b hp v trong pha lu cht. (2) i vi pha hi l tng, p = cRT v K = RTK ; - H0 = - U0 + RT (3)

CN BNG TRONG HP - NH LuT HENRY l Henry ph hp trong cc tr.hp m n. cht b HP long n mc: (i) khng c s cnh tranh trn bm cht rn v (ii) khng c s tng tc gia nhng phn t b HP. T cao th c hai y/t trn tr nn quan trng. HP ng nhit c phn thnh 5 loi khc nhau (hnh 4) Loi I - cht HP microporous; Khc - l HP a lp hoc ngng t mao dn

CN BNG TRONG HP - NG NHIT LANGMUIR Qtr HP ng nhit loi I thng c trnh by bng m hnh Langmuir l tng: (4) Vi: qs l gii hn bo ha; b hng s cn bng; K = bqs b khi T M hnh Langmuir c p dng kh rng ri trong cc tr.hp HP pha kh.

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CN BNG TRONG HP - NG NHIT LANGMUIR Theo m hnh ny th nhit HP khng ph thuc ti trng, nhng thc t khng xy ra. -v cht b HP phn cc trn cht HP phn cc (lc tnh in chim u th): nhit HP khi q gii thch -v cht b HP khng phn cc trn cht HP khng phn cc (lc van der Waals chim u th): nhit HP khi q gii thch do lc ht lin phn t

CN BNG TRONG HP - NG NHIT FREUNDLICH ng nhit Freundlich thng p dng cho hp hydrocarbon ln than hot tnh (5)

CN BNG TRONG HP HP A THNH PHN M hnh Langmuir c th p dng cho h 2 hay a thnh phn (6)

CN BNG TRONG HP - L THUYT D/DCH HP L TNG Thuyt ny gi nh rng pcb cho mi cu t = t l mol ca n trong pha lu cht v pcb ca cu t nguyn cht cng ptng. d on s cn bng a cu t t d liu ng nhit n cu t. Gi thit ny ng cho 1 s trng hp nh hn hp HC hp trn than. Tuy nhin 1 s trng hp khng th p dng l thuyt ny nh s hnh thnh azeotrope v tnh chn lc.

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NG HC HP PH - BN CHT /v HP ha hc puhh gia cht b HP v b mt rn h.s tc p, k, tun theo l Arrhenius: k = k0e-E/RT (10) E nng lng hot ha E ph thuc ng nht b mt HP v tng tc gia cht b HP/HP Tc HP hh thng thng c tnh theo: (11) k, k hng s ph thuc T.

NG HC HP PH - BN CHT ng hc HP vt l l mt qu trnh rt nhanh nh hng bi tr lc qtr truyn khi > bn cht ca ng hc HP Tuy nhin, trong iu kin nht nh, s kt hp ca q tr khuch tn v h.s cb HP, K, c tnh t (1) hnh thnh bn cht ca qtr HP hot ha.

NG HC HP PH

NG HC HP PH T hnh 6, cht b HP l rng khi tip xc vi pha lu cht s cho it nht l 2 v thng l 3 tr lc khc nhau: (i) Tr lc lp phim bn ngoi; (ii) Tr lc khuch tn bn trong: nu l rng c cu hnh kp (macro- micro-), tr lc (ii) c chia thnh: tr lc KT macropore v micropore. Ty thuc v cu trc l rng v k, 1 trong hoc tt c cc tr lc trn s hng n tc truyn khi

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NG HC HP PH- TR LC LP PHIM LU CHT BN NGOI Mt ht chm trong lu cht lun lun c bao bc bi lp phim lu cht hay lp bin m mi s hp ph hay gii hp u phi thng qua n. B dy ca lp phim hay tr lc ca qtr truyn khi ph thuc vo ch thy ng ca mi trng T nhng d liu ca tr lc lp phim, c ch qtr kh.tn, c th tnh c tc HP trong ch m

NG HC HP PH- Khuch tn macropore Ch ng trong macropore c th theo 1 s c ch: KT khi phn t (bulk molecular), KT Knudsen, KT b mt v dng chy Poiseuille. Trong h lng: KT khi ptu chim u th; Trong h kh: KT Knudsen v KT b mt chim u th d/chy Poiseuille thng thng t tc ng vd dng chy p lc xuyn qua l rng di chch lch p sut.

NG HC HP PH- Khuch tn micropore Trong l rng rt nh (k l hi > k phn t) ptu KT khng th thot ra khi trng lc ca tng l rng C ch Knudsen khng cn ng na KT xy ra bi qtr nhy t ni ny n ni khc, ging nh KT b mt, qtr KT ny ph thuc cht ch vo T v C. ng lc tc ng cho qtr KT ny thc s l chnh lch th ha hc hn l chnh lch C S khc bit ny khng quan trng trong dd long ni m cc qui lut nhit-ng l tng c p dng >< Ngc li rt quan trng /v tr.hp nng cao v trong KT micropore v KT b mt.

NG HC CT HP PH Trong hu ht cc qtr hp, cht hp t/xc vi pha lu cht trong 1 ct cha vt liu hp. Tm hiu v ng hc ct hp thit k v ti u ha qtr. Cn thit k m hnh d on nng u ra theo n. u vo v tc dng chy

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NG HC CT HP PH - L THUYT CN BNG

HP PH - TCH KH

HP PH - TCH LNG

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