Chuong 8

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CHNG 8 Hap phu (adsorption)

Thc s Lm Vnh Sn 1
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Hp ph - hp th ???
Thc s Lm Vnh Sn
Hp ph
Adsorptive
Release
Adsorbate Uptake
Chat hap phu ran

Thc s Lm Vnh Sn
Hp ph - Adsorption
Khi nim:
Hp ph l s li cun cc phn t kh, hi (adsorbate) bi b mt cht rn (adsorbent). ng dng phng php hp ph lm sch kh c hm lng tp cht kh v hi nh. Trong cng nghip thng tin hnh qu trnh hp ph lm sch v sy kh khng kh, tch cc hn hp kh hay hi thnh tng cu t, tin hnh qu trnh xc tc d th trn b mt phn chia pha.
Thc s Lm Vnh Sn 4
Phn loi
Hp ph vt l: c im: Lc hp ph l lc Van der Waals l hin tng tng tc thun nghch ca cc lc ht gia cc phn t ca cht rn v ca cht b hp ph. Qu trnh hp ph l qu trnh thun nghch hon ton. Nhit to ra khng ng k. C th hp ph nhiu lp hay mt lp.
Thc s Lm Vnh Sn 5
Phn loi
Hp ph ha hc: (hay hp ph hot ha) L kt qu ca s tng tc ha hc gia cht rn v cht b hp ph. Nhit pht trong hp ph ha hc thng ln c nhit phn ng. Qu trnh thng l khng thun nghch.
Thc s Lm Vnh Sn
Hap phu tren be mat ran

Hp ph vt l Lc Lp hp ph Nhit hp ph chn lc Nhit Van de Waal a lp Thp (10-40 kJ/mol) Thp Thp Hp ph ho hc lin kt ha hc n lp Cao ( >40 kJ/mol) cao cao
Hp ph trao i (Exchange)
l l l l
C c tnh ht bng tnh in L qu trnh trao i ion Ion tch in cao b ht > ion ho tr thp hn (ion ho tr 1). Ion kch thc nh b htLm Vnh Sn nhiu hn Thc s
7
Hp ph - Adsorption
Ch : Trong thc t, cc loi hp ph c th xy ra ng thi tu theo iu kin thc hin qu trnh m hp ph loi ny c th chim u th hn loi kia.
Thc s Lm Vnh Sn
C ch
Qu trnh hp ph c thc hin bng cch cho tip xc hai pha khng ha tan pha rn (cht hp ph) vi pha kh. Cht b hp ph s i t pha kh n pha rn cho n khi nng ca dung cht phn b gia hai pha t cn bng. V nguyn tc cc k thut c s dng thc hin qu trnh tip xc gia hai pha khng ha tan u c th thc hin c cho qu trnh hp ph. Khuch tn ngoi Hp ph trn b mt Khuch tn trong Lm Vnh Sn Thc s
ng dng x l kh
Trong k thut x l nhim khng kh, phng php hp ph c dng thu hi v s dng li hi ca cc cht hu c, kh mi thi ra ca cc nh my sn xut thc phm, thuc da, nhum, ch bin kh t nhin, cn ngh tng hp hu c. c bit u vit: Cht kh chy hay khng chy c. Cht c gi tr cao cn thu hi. Cht c nng thp trong kh thi m cc qu trnh khc khng p dng c.
Thc s Lm Vnh Sn 10
ng dng x l kh
iu kin bnh thng khi hp ph kh trong hn hp vi khng kh, khng kh khng b hp ph. Hp ph kh v hi trong hn hp khng kh n gin hn nhiu so vi hp ph cht tan trong dung mi.
Thc s Lm Vnh Sn
11
u im nhc im
u im: Hiu qu cao D vn hnh Khng cn x l kh thi X l nhiu cht Thu hi cht qu Nhc im: Chi ph vn hnh cao Cn ti sinh vt liu hp ph B nh hng bi s Lm Vnh Snhu c khc cc cht Thc
12
Cht hp ph
Vt liu dng lm cht hp ph l cc vt liu xp vi b mt ring ln, c to thnh do tng hp nhn to hoc do t nhin. Vt liu hp ph c rng ln do nhiu mao qun li ti nm bn trong khi vt liu Yu cu i vi cht hp ph Kh nng hp ph cao Phm vi p dng rng C bn c hc cn thit C kh nng hon nguyn d dng Gi thnh r
Thc s Lm Vnh Sn 13
Cht hp ph
Trong a s trng hp, cht hp ph (cht rn) phi lin kt thun nghch vi cc cu t cht hp ph c th ti s dng cht hp ph. Phn lm 3 nhm chnh: Vt liu khng phn cc Vt liu c cc Vt liu m trn b mt ca chng xy ra qu trnh hp ph ha hc v qu trnh lm thay i cu trc ca phn t kh.
Thc s Lm Vnh Sn 14
Cht hp ph
Kch thc l rng (ng knh mao qun) ng vai tr quan trng lm cho vt liu hp ph c tnh cht chn lc. Cc cht hp ph cng nghip ph bin Than hot tnh Silicagen Nhm Zeolites
Thc s Lm Vnh Sn 15
Thc s Lm Vnh Sn
16
Cht hp ph
Micropores < 2nm (or 20A): mao dn nh Mesopores 2-50nm (or 20-500A) Macropores >50 nm (or 500A): ng dn/khe h i vi tng loi cht b hp ph, l rng ca cht hp ph nh hng mt cch linh ng v c th gy ra gii hp khng hon ton
Thc s Lm Vnh Sn 17
Vt liu xp - Porous Materials
Thc s Lm Vnh Sn
18
Than hot tnh

L mt cht gm ch yu l nguyn t carbon dng v nh hnh (bt), mt phn na c dng tinh th vn grafit. Than hot tnh c din tch b mt ngoi rt ln, nu tnh ra n v khi lng th l t 500 n 2500 m2/g Than hot tnh c th tch l xp vo khong 0.24 0.48 cm3/g. Nhc im c bn ca than hot tnh l km bn c hc v d chy.
Thc s Lm Vnh Sn 19
Than hot tnh

B mt ring rt ln ca than hot tnh l h qu ca cu trc x rng m ch yu l do tha hng t nguyn liu hu c xut x, qua qu trnh sy nhit cao, trong iu kin thiu kh. Phn ln cc vt rng - nt vi mch, u c tnh hp th rt mnh v chng ng vai tr cc rnh chuyn ti (k ni).
Thc s Lm Vnh Sn
20
Cc dng than hot tnh phn loi theo kch thc

Thc s Lm Vnh Sn 21
Than hot tnh dng ht v dng bt

(GAC PAC)
Thng s Tng din tch b mt T trng th tch T trng ht Kch thc ht n v m2/g kg/m3 kg/L m GAC PAC
700 1300 800 -1800 400 500 1.0 1.5 600 900 360 740 1.3 1.4 5 50
GAC: granular activated carbon PAC: powdered activated carbon

Thc s Lm Vnh Sn 22
Zeolites
L cc nhm silic, cha cc oxit kim loi kim v kim th. Cng thc ha hc tng qut ca zeolit l Me2/nO. Al2O3.xSiO2.7H2O. Zeolit c kh nng hp ph hi cc hp cht phn cc v cc cht c ni i trong phn cc, ngoi ra zeolit cn c kh nng ln hp th hi nc. Zeolit gi c hot tnh cao nhit tng i ln (150- 250oC). Th tch l xp nh lng cha cht hp ph t hn so vi cc cht hp hp ph khc.
Thc s Lm Vnh Sn 23
Zeolites
clinoptilolite
Thc s Lm Vnh Sn
http://www-2.cs.cmu.edu/~adg/images/minerals/tsilicates/clinop.jpg PDF created with FinePrint pdfFactory Pro trial version http://www.fineprint.com
24 gmelinite
Zeolite-4A, Na12[Al12Si12O48]
Silicon framework
A portion of the aluminosilicate network

Thc s Lm Vnh Sn 25
http://www.molecules.org/otherinorganic_C.html PDF created with FinePrint pdfFactory Pro trial version http://www.fineprint.com
5A
Pore size 5A
Zeolites
12
Pore size 8A
Modernite Pore size 3-8 A
http://chemmac1.usc.edu/bruno/zeodat/MFI.html
Thc s Lm Vnh Sn
26
Silicagen
L oxit Silic v nh hnh ngm nc (SiO2.n H2O). Th tch l xp ca cc silicagen khong 0.3 1.2 cm3/g. Din tch b mt 300 750 m2/g ng dng: hp ph cht phn cc, cc hi v kh d ngng t. i lc mnh vi hi nc silicagen ng dng sy kh cc mi trng kh khc nhau. Silicagen khng chy, c nhit ti sinh thp (100 2000C ) v bn c hc. B ph hy bi cc git m.
Thc s Lm Vnh Sn 27
Qu trnh phn ring bng hp ph

Cc qu trnh phn ring Phn ring pha kh Paraffin / isoparaffi, cht thm N2/O2 CO, CH4, N2, NH3 / H2 H2O/etanol Lm sch dng kh H2O kh cracking, kh thin thin, khng kh CO2 / C2H2, kh thin nhin .... Hp cht lu hunh / kh thin nhin H2 SO2 / kh thi Mi / khng kh
Thc s Lm Vnh Sn
Cht hp ph Zeolit Zeolit Zeolit, than hot tnh Zeolit Silic, alumina, zeolit Zeolit Zeolit Zeolit Silicagen...
28

Cht hp ph t tnh ng dng u im Gi r nht dng trong x l nhim mi trng Cht hp ph duy nht hp ph O2 Nhc im Kh ti sinh nu b ng cn, c th bt chy khi ti sinh Khng cng dng no khc ngoi phn ring khng kh Khng hu qu bng ZMS khi tch cc vt H2O trong dng kh Tch cc cht B mt k nhim c nc hp ph Than hot tnh cc cht hu gc hu c c trong nc v khng kh Ry phn t carbon (CMC) Phn ring trn c s khuch tn khc nhau trong ht Cht hp ph ho nc nng sut cao Sn xut N2 t khng kh
Silicagel
Lm kh dng kh, i khi lm tch hidrocacbon t dng kh
Nng sut cao hn ry phn t zeolit (ZMS)
Thc s Lm Vnh Sn
29

Cht hp ph t tnh ng dng Lm kh khng kh u im Nng sut cao hn ZMS Nhc im Khng hiu qu bng ZMS khi tch cc vt nc trong dng kh Nng sut thp hn cc loi cht hp ph khc. Mc hn than hot tnh Nng sut cao, cht hp Alimina hot ph ho tnh nc B mt ht nc, phn cc, rnh u n
Ry phn t zeolit (ZMS)
Kh nc, phn ring khng kh
Phn ring da trn phn cc hnh hc
silicalite
B mt k Tch cc C th t nc, c cht hu c b d hn trng hp t dng kh than hot ph tng t tnh than hot Thc s Lm Vnh Sn tnh
30

Cht hp ph Cht hp ph cao phn t t tnh Thng l copolymer ca stryren/ divinyl benzen ng dng Tch cc cht hu c t dng kh u im Khng gp vn nh than hot tnh Nhc im Mc hn than hot tnh nhiu
B mt phn Tch H2S, Tt khi tch Kinh t khi tch Cht hp ph ng la chn SO2 c nng cc vt cht t hn khng thun vi cu t thp gy 100kg/ngy nghch ca dng kh trong dng nhim cht b hp ph kh Bn hot Tch cc Cht hp ph ho trn cht cht hu c sinh hc mang xp khi dng kh Khng cn ti sinh T l tch thp hn cc cht hp ph khc
31
Thc s Lm Vnh Sn
Cc nhn t nh hng n qu trnh hp ph

nh hng ca mi trng nh hng ca bn cht cht hp ph Tnh cht ca cht b hp ph nh hng ca thi gian, nhit , p sut, m Khi nhit tng ln, kh nng khuch tn vt cht gim xung dn n gim s hp ph p sut cng cao, kh nng hp ph cng tt. m cng thp, kh nng hp ph cng tt.
Thc s Lm Vnh Sn 32
Phng php ti sinh

Cn thit phi ti sinh cht hp ph thu hi cu t hp ph v phc hi kh nng hp ph ca cht hp ph. Chi ph ti sinh chim t 40 70% tng chi ph ca qu trnh lm sch kh. Cc phng php ti sinh: Gia tng nhit Ht cu t bng cht hp ph khc mnh hn Gim p sut
Thc s Lm Vnh Sn 33
Phng php ti sinh

Nh hp ph bng nhit c thc hin bng cch nung cht hp ph bo ho n nhit xc nh bng tip xc trc tip vi hi nc, khng kh hoc kh tr nng, hoc lm nng qua thnh vi dng kh tr thi qua. Cc tc nhn dng tch cc cht kh, v hi ra khi cht hp ph: Dng hi nc bo ho hoc hi nc qu nhit. Dng hi ca cc cht hu c. Dng kh tr.
Thc s Lm Vnh Sn 34
Phng php ti sinh

Qu trnh gi hp l qu trnh o ngc ca hp ph Tc nh ph thuc vo: Cht hp ph Tnh cht l ho ca cht b hp ph. Nhit ti sinh c nh hng ln hn n hiu qu ca qu trnh nh hp so vi p sut. Khi ti sinh cht hp ph nn thc hin p sut bng p sut lc hp ph.
Thc s Lm Vnh Sn 35
Phng php ti sinh

Nh hp ph bng cch gim p sut thc hin theo hai phng n: Gim p sut nu qu trnh hp ph din ra p sut d. To chn khng nu giai on hp ph c thc hin p sut thng.
Thc s Lm Vnh Sn
36
Phng php ti sinh

Trong cc thit b cng nghip th cht hp ph c ti sinh bng cch thi hi nc qu nhit u im:
n gin, t tn km, hiu qu cao nhit cao 1000C hi c th gii thot hu ht cht nhim hp ph trong pha rn. C th thu hi c cht b hp ph trong pha hi. Hi nc c entanpi cao hn nhiu so vi khng kh nng nhit vt liu hp ph nng cao nhanh Thc s Lm Vnh Sn 37
ng dng x l
Hp ph hi dung mi:
Thu hi hi dung mi va c ngha sinh thi do lng tht thot hi dung mi hng nm vo khong 600 800 ngn tn. Hi dung mi ch yu r r t qu trnh bo qun, vn chuyn v s dng. S dng cc cht hp ph c l xp mn: than hot tnh, silicagen, keo nhm, zeolit, thy tinh l xp
Thc s Lm Vnh Sn
38
Hp ph NOx
ng dng x l NO t hiu qu thp do tnh tr ca NO thnh oxt c s oxi ha ln hn. NOx hp th mnh bi than hot tnh, khi tip xc vi NOx than c th chy hoc n. Than c bn c hc thp Khi phc hi NOx NO Kh nng hp ph silicangen thp hn than hot tnh nhng bn c hc, khng chy s dng rng ri hn. Nng cn li trong kh thi cn 0,005%.
Thc s Lm Vnh Sn 39
Hp ph NOx
NOx c th c hp ph bng than bn c tnh kim trong thit b tng si. Hn hp kh cha 0,1 2,0%NOx, thi gian tip xc pha 1,6 3s hiu qu x l 96 99%. X l kh thi t xng sn xut axit sunfuric: 0,3 0,4% NOx, 0,3%SO2 v 0,3g/m3 sng H2SO4, lu lng 60.000m3/h. Lng than bn 25 35 kg than bn kh/1000m3 kh. Thit b mi nm thu hi 2.520 tn NOx, 3.200 tn SO2, 95 tn H2SO4, bn nit cha 15 25% nitrat v sunphat amoni.
Thc s Lm Vnh Sn 40
Hp ph SOx
Cht hp ph s dng l: vi, dolomit (CaCO3.MgCO3) hoc vi. tng hot tnh ca cht hp ph ha hc thm vo mt s mi v c hay oxit mangan. Phng php oxit mangan c s dng trong thc t Khi nng SO2 trong kh thi 0,15% (th tch) phng php oxit mangan cho hiu qu 90%.
Thc s Lm Vnh Sn 41
X l halogen v cc hp cht
X l kh flo:
Nng cc hp cht flo trong kh thi cng nghip dao ng ln. Cho php gim nng hp cht flo xung n 10 50mg/m3. t c yu cu x l cao hn dng phng php hp ph. Cht hp ph dng l vi, keo nhm, florua, nefelin xienit.
Thc s Lm Vnh Sn 42
X l halogen v cc hp cht
X l HF: Vt liu hp ph: vi nhit > 3500C, t = 7,6s, trn b mt vi xy ra phn ng vi HF CaF2. X l kh vi nng HF 0,58% (th tch) c th t hiu qu 95%, nng cn li 0,028% X l clo v clorua hydro: Kh clo c hp ph bi cc cht rn hu c: lignin, lignin sunfomat canxi Hp ph clorua hydro dng oxit st, clorua oxit ng trong hn hp vi oxit magi, sunphat v photphat ng, ch, Thc s Lm Vnh Sn 43 cadmi.
Hp ph cht hu c cha lu hunh

X l H2S:
Vt liu hp ph: hydroxit st, than hot tnh, zeolit Hp ph H2S bng hydroxit st: 2Fe(OH)3 + 3H2S Fe2S3 + 6H2O Fe2S3 + 1,5O2 + 3H2O 2Fe(OH)3 + 3S Cht hp ph c iu ch t bn ly hoc ph thi sn xut Al2O3 t qung boxit c m 50 55%, cha 45 48%Fe2O3 Khi nng kh thi 20 25g/m3 gim nng H2S xung cn 0,02g/m3.
Thc s Lm Vnh Sn 44
Hp ph H2S
Hp ph H2S bng than hot tnh: Than hot tnh hp ph mnh, H2S cn b oxi ha bi oxi trong kh thi khi c than lm xc tc. H2S + 0,5O2 S +H2O Trong than din ra phn ng xc tc chuyn ha H2S: H2S + 2O2 H2SO4 Lng lu hunh c cha trong than hot tnh l 200 520kg/m3.
Thc s Lm Vnh Sn 45
Hp ph H2S
Hp ph H2S zeolit (NaA, CaA, NaX):
NaX c kh nng hp ph H2S ln nht. Trong thnh phn hn hp kh c cha oxi, xy ra phn ng oxi ha H2S thnh S gim hot tnh cht hp ph. Nh hp bng hi nc thi bng kh sch nhit t 300 3500C. Gi thnh vt liu kh cao.
Thc s Lm Vnh Sn
46
Hp ph hp cht hu c lu hunh
Trong kh thi cng nghip: cacbon disunfua (CS2), cacbon oxit sunfua (COS), thiofin (C4H4S), mercaptan (RSH), ru thioete (R-S-R) thp.
Cht hp ph ha hc: oxit km, st, ng v mt s kim loi khc. Nhit lm sch 200 4000C Cht hp ph than hot tnh, zeolit hp ph mnh thiofin, CS2, hp ph yu COS v disunfua.
Thc s Lm Vnh Sn 47
X l hi thy ngn
Ngun gc pht sinh: kh thi nh my luyn kim mu, nhit nng, ha cng nghip
Thy ngn v cc hp cht tn ti trong kh thi dng hi hoc aerosol. Vt liu hp ph: than hot tnh Khng kh c oxi v hi nc xy ra phn ng oxi ha mnh lit SO2 H2SO4 SO2 + H2O + 0,5O2 H2SO4 Axit to thnh lin kt vi hi thy ngn HgSO4
Thc s Lm Vnh Sn 48
X l mi
im khc bit: Tp cht c nng thp Nhim v ti s dng cht hp ph khng t ra. X l mt th tch kh ln p sut kh quyn tr lc thit b x l thp S dng lp vt liu hp ph mng. Thng s dng than hot tnh kh mi. Tha mn yu cu: Kh nng hp ph ln Tr lc nh
Thc s Lm Vnh Sn 49
X l mi
Cc iu kin k thut i vi than hot tnh trong h thng x l mi c trnh by di y: Hot tnh theo CCl4, % gi CCl4, % Khi lng ring biu kin cng (th nghim trong my nghin bi), Kch thc ht (mm) 50 30 0,04 % 80 5-14
Thc s Lm Vnh Sn
50
M hnh tnh ton

M hnh hp ph
Da tren ng can bang hap phu ng ng (du kho at en ieu kien can bang) ng Cac yeu to anh hng en qua trnh hap phu:
n n n n
Tnh chat cua chat b hap phu Tnh chat vat lieu hap phu Tnh chat pha kh (pH, nhiet o) Tng tac khi co nhieu chat b hap phu
ng ang nhiet hap phu mo ta ng ng moi quan he gia: chat b hap phu tren chat hap phu va nong o can bang tren chat hap ng ng phu
Thc s Lm Vnh Sn
51
Lc hp ph - Adsorptive Forces
Thc s Lm Vnh Sn 52
Phn loi thit b hp ph

Hp ph tnh: Pha kh c cho chuyn ng qua tng ht cht hp ph c nh Cht hp ph c chiu cao t 0,3 1,2 m trn tm c c l. Dng kh nhp liu c thi t trn xung. Phng thc lm vic:
l
Phng thc bn giai on: hp ph, nh hp, sy, lm lnh (nng cao) Phng thc ba giai on: hp ph, nh hp, lm lnh. (nng trung bnh v nh) Phng thc hai giai on: hp ph, nh hp.
Thc s Lm Vnh Sn
53
Hp ph tnh
l Thit
b tng c nh c loi thng ng, loi nm ngang, loi hnh vnh khn. b hp ph ht tng mng tnh b hp ph ht, tnh, dy
l Thit l Thit
Nhc im hp ph tnh:
l l
Vng bo ha khng ng u m xy ra theo lp. Phn bo ha vn chim ch v lm hao nng lng. Lng ph vt liu khi thay th
Thc s Lm Vnh Sn 54
Thit b c lp vt liu chuyn ng

Thit b hp ph tng si Dng kh thi qua lp vt liu hp ph lm lp vt liu hp ph chuyn ng v sau ri xung lm qu trnh hp ph xy ra ng u. Thit b hp ph tng xoay Vt liu hp ph nm trong mt c cu xoay c v qu trnh xoay chuyn lm qu trnh hp ph xy ra u n cc lp khc nhau.
Thc s Lm Vnh Sn
55
Thc s Lm Vnh Sn
Gas Purification 56
Thc s Lm Vnh Sn
57
H thng lp vt liu quay
Mycock et al., 1995 Thc s Lm Vnh Sn 58
H thng lp vt liu tng si
Thc s Lm Vnh Sn
59
X l mi
Thc s Lm Vnh Sn
60
Decentralized Multiple Hearth Thc s Lm Regeneration Facility Vnh Sn

61
Thit b hp ph
Thc s Lm Vnh Sn
62
Thc s Lm Vnh Sn
63
Thit b hp ph
Yu cu ra khi thit k la chn thit b hp ph: m bo thi gian chu k lm vic (hp ph) thch hp C x l s b i vi kh thi loi b cc cht khng th hp ph c X l lm gim bt nng ban u ca cht cn kh trong kh thi bo v lp vt liu hp ph khng b qu ti Phn phi dng kh i qua lp vt liu hp ph mt cch u n. m bo kh nng thay th mi hoc hon nguyn vt 64 liu hp ph sau khi Thc strng thi bo ha. t Lm Vnh Sn

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CHNG 8 Hap phu (adsorption)

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Chat hap phu ran

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Hap phu tren be mat ran

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Vt liu xp - Porous Materials

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Than hot tnh

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Than hot tnh

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Cc dng than hot tnh phn loi theo kch thc

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Than hot tnh dng ht v dng bt

GAC: granular activated carbon PAC: powdered activated carbon

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A portion of the aluminosilicate network

Modernite Pore size 3-8 A

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Qu trnh phn ring bng hp ph

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Qu trnh phn ring bng hp ph

Lm kh dng kh, i khi lm tch hidrocacbon t dng kh

Nng sut cao hn ry phn t zeolit (ZMS)

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Qu trnh phn ring bng hp ph

Ry phn t zeolit (ZMS)

Kh nc, phn ring khng kh

Phn ring da trn phn cc hnh hc

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Qu trnh phn ring bng hp ph

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Cc nhn t nh hng n qu trnh hp ph

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Phng php ti sinh

Phng php ti sinh

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Phng php ti sinh

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