Nhua Trao Doi Ion

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Su tm bi: www.daihoc.com.vn

Ti liu tham kho

1. Robert H. Perry, Don W. Green, James O. Maloney, Perrys Chemical
engineers Handbook, Chapter 16 Adsorption and ion exchange, 1999
2. Ronald W. Rousseau, Handbook of separation process technology, 1987,
chapter 13.
3. A. Tager, Physical Chemistry of Polymer, 1972
4. F.C Nachod, J. Schubert, Ion Exchange resin, 1956, Academic press inc.
5. Andrei A. Zagorodni, Ion Exchange Materials Properties and Applications,
2007

1
1. Gii thiu chung ...............................................................................................1
1.1. Lch s pht trin ca vt liu trao i ion 1
1.2. Cc loi vt liu trao i ion 1
1.2.1. Vt liu t nhin 2
1.2.1.1. Loi v c 2
1.2.1.2. Loi hu c 2
1.2.1.3. Vt liu bin tnh 3
1.2.2. Vt liu tng hp 3
1.2.2.1. Vt liu v c tng hp 3
1.2.2.2. Vt liu hu c tng hp 4
1.2.3. Vt liu composite 5
1.2.4. Mng trao i ion 5
2. Nha trao i ion............................................................................................. 6
2.1. Phn loi nha trao i 7
2.2. Mt vi thut ng s dng trong k thut trao i ion 8
2.3. Cc phn ng c trng 9
2.4. Tng hp, tnh cht ht nha 9
2.4.1. Tng hp 9
2.4.2. nh gi dung lng hot ng ca ht nha 13
2.4.3. xp ca nha 14
2.4.4. Nha c xp v m 17
2.4.5. Nhit ng ca trao i ion 23
2.4.6. chn lc 26
2.4.7. ng hc qu trnh trao i 34
3. Thit b trao i ion .......................................................................................40
3.1. Chu k hot ng ca nha trao i 40
3.1.1. Ra ngc 40
3.1.2. Ti sinh 40
3.1.3. Ra 42
3.1.4. Hot ng 43
3.2. Nguyn tc thit k 44
3.3. Cc loi thit b thng dng 45

2
3.3.1. Loi tng nha c nh (fixed bed) 45
3.3.2. Loi tng ng 47
3.3.3. Loi tng si (fluidized bed) 49
3.3.4. Loi thng khuy (stirred tank) 53

1
1. Gii thiu chung
1.1. Lch s pht trin ca vt liu trao i ion
-Trong Kinh thnh ca ngi Hy lp c cp n vic tch mui trong nc
bin.
-Th k 19: Anh, c nhng ti liu vit v hin tng trao i ion
-1850: Harry Thompson v John Way (nh ho nng) cho nc phn cha nhiu
amonium i qua lp t st. Amonium b gi li trn lp t, Ca c tch ra. Ngui
ta c c cc nhn xt sau:
+Trao i ion trong t lin quan n s trao i cc ion tng ng
+Mt vi ion trao i nhanh hn ion khc
+Silicat nhm (aluminum silicate) Al
2
SiO
5
c tnh cht trao i ion
+Qu trnh trao i ion khc vi qu trnh hp ph vt l
-1858: nh ho hc ngi c chng minh rng phn ng trao i ion trong t
l mt qu trnh thun nghch.
-1876: Lemberg cng chng minh c tnh thun nghch
-u th k 20: nha trao i ion c a vo cc mc ch ng dng
-1905: Nh ho hc ngi c ng dng vo lm mm nc, s dng nha trao
i cation.
-Gans: tng hp nha trao i cation sodium aluminosilicate ng gi l zeolite.
Tng hp zeolite nm 1913 do Permutit Company (M). cacbonate zeolite c s
dng lm vt liu trao i ion nm 1935.
-Nha trao i cation trng hp formadehyde, trao i anion (sn phm trng
hp ca polyamines and formaldehyde). Cc sn phm ny c th tch loi tt cc ion
trong nc, nhng nha anion khng th tch acid yu ca Si hoc kim.
-Nm 1944, nhm cc nh nghin cu ca M, D Alelio pht trin nha trao i
cation - ng trng hp ca styrene v divinylbenzen. Nha anion loi ny c pht
trin nm 1948, c th tch hon ton cc khong trong nc v c dng rng ri
cho n ngy nay.
1.2. Cc loi vt liu trao i ion
Cc loi vt liu trao i ion c phn thnh nhiu loi ph thuc vo cc ng
dng khc nhau.
___________________________________________________________________________
Bi ging Nha trao i ion TS. L Minh c

2
Cc loi vt liu v c c s dng khi yu cu v tinh khit khng cao lm.
ci thin bn vt l ca ht nha, phng php gn cc loi vt liu trao
i ion vo mt loi vt liu khc (c th v c hoc hu c) c nghin cu v pht
trin mnh.
Vt liu trao i cn: bn ho, ho tan thp, chi ph thp.
1.2.1. Vt liu t nhin
1.2.1.1. Loi v c
Nhiu khong v c trong thin nhin c s dng: st (bentonite, kaolinite,
illite), mica v zeolite (nh analcite, chabazite, sodalite v clinoptilolite) c tnh cht
trao i ion. Trong zeolite t nhin l loi vt liu c s dng u tin trong
cng ngh trao i ion. St thng s dng lm cht n, cht chn lp cht thi
phng x. t st thng s dng trong cc thit b gin on, t khi s dng cho hot
ng dng ct v c th hn ch dng chy qua ct.
Cc loi aluminosilicate t nhin cng thng c s dng trong x l nc
thi. N hot ng nh l: vt liu trao i ion v cht lc c bit.
St v zeolite thin nhin tuy c thay th dn bi cc loi vt liu tng hp
song n vn c dng trong mt s ng dng no y do r v sn c trong thin
nhin. Mt s nhc im ca loi vt liu ny:
-Dung lng trao i thp
-Bn c thp
-Kch thc l xp khng khng ch c
-Cc ht st c khuynh hng to thnh cc ht keo
-Kh gia cng ng kch thc theo yu cu
-C th b phn hu trong mi trng acid hoc kim
1.2.1.2. Loi hu c
Mt lng ln cc cht hu c c tnh cht trao i ion nh: polysaccharides
(cellulose, algic acid, rm, than bn), proteins (nh casein, keratin v collagen) v cc
loi than (nh than bn, than nu). Mc d dung lng hot ng ca cc loi vt liu
ny thp nhng vn c s dng rng ri do gi thnh thp. Cc nhc im chnh
ca loi vt liu ny:
-Dung lng trao i thp so vi cc loi vt liu khc
___________________________________________________________________________

3
-Trng n ln v d b pettize ho
-Vt liu cenllulose v protein rt khng bn vi phng x
-Cu trc vt l km
-Tnh cht vt l khng ng nht
- chn lc km
-Khng bn khi pH nm ngoi dy pH trung tnh.
1.2.1.3. Vt liu bin tnh
ci thin dung lng trao i, chn lc mt s vt liu hu c c bin
tnh. V d vt liu trao i ion trn c s cellulose c bin tnh bng cch a thm
vo nhm phosphate, carbonic hoc nhm chc acid khc.
1.2.2. Vt liu tng hp
1.2.2.1. Vt liu v c tng hp
*Zeolites l loi vt liu v c u tin c s dng trn mt quy m ln tch
cht nhim phng x trn mt quy m ln. Zeolite l loi vt liu trn c s l
aluminosilicate, c th tng hp di dng bt, ht hoc vin.
u im ca loi ny l c th thay i tnh cht ho hc trong mt khong rng,
kch thc l xp c khng ch, bn nhit.
Nhc im:
-Chi ph cao hn so vi loi c sn trong thin nhin
-Bn ho hc, bn trong cc mi trng pH khc nghit km
-D nt, bn c hc km.
chn lc v dung lng ca zeolite c th ph hp vi cc cng ngh c
mui thp. Nu trong dng thi c mt cc ion khc, cc tm hot ng ca zeolite b
cc ion ny chim gi do s gim dung lng hot ng. V d khi c K, kh nng
trao i ca zeolite vi Ce b gim i. Trong dung dch c nng mui cao, dung
lng hot ng ca zeolite l rt nh.
*Cc hp cht ca Ti, Si-Ti
Trong nhiu nm qua, oxide v hydro oxide ca Ti c bit n kh nng tch
loi ion trong dung dch. Nm 1955 UK v sau l c v Nht s dng hydrous
titanium oxide (HTiO) tch uranium trong nc bin vi quy m ln. Cc nghin
___________________________________________________________________________

4
cu tip theo ch ra rng loi vt liu ny cng c i lc rt mnh vi ion kim loi
actinium (Ac), Sr v vi cc ion c in tch +2.
Cc sn phm loi ny tr thnh thng phm ca cng ty SrTreat ca
Finland. N c hot lc cao trong mi trng kim (pH>9). Vt liu ny c th s
dng kt hp vi cht hp th hexacyanoferrate (CsTreat).
*Hexacyanoferrates ca cc kim loi chuyn tip
Trong nhiu thp k qua, hp cht loi ny c bit nh l cht c th tch Ce
trong dung dch. Nhiu dng khc nhau ca loi vt liu ny c s dng tch Ce.
V d: Cobalt (II)-hexacyanoferrate (II).
1.2.2.2. Vt liu hu c tng hp
Ngy nay, nhm ln nht trong loi vt liu ny l nha trao i ion dng bt (5-
150m) hay dng ht (0,5-2mm). Mch hydro carbon phn b ngu nhin to nn mt
mng li rt linh ng. Trn mch ny c mang cc in tch c nh trn cc v tr
khc nhau. Nha khng tan do c cc lin kt ni ngang. Lng ni ngang s nh
hng n kch thc ht nha qua sng, kh nng trng, chuyn ng ca cc ion
linh ng, cng v bn c hc. Lng ni ngang ln, se lm tng cng ca
nha, tng bn c, t l xp v t trng trong dung mi.
Khi vt liu ny ngm trong dung mi hoc trong nc, n s trng ln. Mc
trng ph thuc vo c tnh ca c dung mi v chnh vt liu, n b nh hng bi
cc yu t sau: phn cc ca dung mi, lin kt ngang, dung lng trao i,
solvat ho mnh hay yu ca nhm c nh, kch thc solvat ca cc ion trao i,
nng dung dch.
u im ni bt ca loi vt liu ny: dung lng trao i ln, p dng rng ri,
a lnh vc, chi ph kh r so vi mt vi loi v c tng hp khc.
Cc loi nha chnh trong nhm ny l:
*Polystyrene divinylbenzene
L sn phm copolymer ca styrene v DVB. ni ngang c quyt nh bi
lng DVB. Nng DVB thp s lm cho nha mm, kh nng trng rt mnh
trong cc dung mi.
Cc nhm chc c nh (nhm c trng) c gn vo trong mng li mch
polymer to nn kh nng trao i ion. V d nh nhm SO
3
H, thng t 8 n 10
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5
nhm cho 10 vng benzene. H
+
s l ion linh ng (hay ion i counter ion) s tham
gia trao i vi cc cation trong dung dch.
Khi gn cc nhm NH
3
+
hay N
2
+
vo trong mch polymer, nha trao i anion
c to ra. Cc ion i s l OH
-
, Cl
-
.
*Phenolic
L sn phm trng ngng ca phenol v formaldehyde vi nhm OH- l nhm
c trng, c nh trong mch polymer, l loi nha trao i cation acide yu. tng
cng acid cho nha, nhm -SO
3
H c gn vo nha. Nh vy nha s c hai
chc nng - cha c nhm acid mnh SO
3
H v nhm acid yu OH.
Sn phm a trng ngng (polycondensation) ca resorcinol-formaldehyde c
s dng rng ri n tc Cs.
Cng c th gn thm nhm phosphoric acid vo mch polymer tng kh nng
lm vic ca nha.
*Acrylic
L nha trao i ion acid yu, c nhm -COOH trong mch. L sn phm
copolymer ca acrylic hay methacrylic acid vi DVB. Nhm COOH c kh nng
tch mui thp nhng trong mi trng kim n c i lc mnh vi Ca
2+
v cc ion
tng t khc. Cc nhm acid khc c th gn vo nha nh PO
3
2-
,PO
3
3-
,HPO
2-
1.2.3. Vt liu composite
L loi vt liu kt hp mt hay nhiu vt liu T ion vi cc loi vt liu khc.
To ra cc composite ny s lm tng bn c th s dng trong ct. Zeolite to
ra dng ht trn cht mang l aluminium oxide. Mt loi khc c bit n l ph
cupric ferric haxacyanoferrate trn si polyacrylic. Vt liu ny s dng tch nc
thi phng x trong nh my nguyn t.
Mt loi composite khc l s kt hp vt liu trao i v c vi magnetic Fe
3
O
4
.
Do vy s d dng tch loi ra khi bo ho nh t trng. Loi vt liu ny tr
thnh thng phm.
___________________________________________________________________________
1.2.4. Mng trao i ion
C hai loi mng trao i: ng nht (homogeneous) v khng ng nht
(heterogeneous).
Mng khng ng nht c tng hp bng cch phn tn cc loi vt liu trao
i (dng ht keo hoc ht rt min) trong nha nhit do polyethylene, polystyrene hay

6
cao su tng hp. Sau em cn, p hoc n to ra cc hnh dng khc nhau tu
thuc vo yu cu s dng (dng tm, a, bng di). Cc ht trao i phi c tip
xc vi. Khi cc ht ny bong ra khi mng, bn c hc ca mng s rt thp.
Thng th ht s chim 50-70% trong th tch mng.
Mng ng nht l sn phm trng ngng ca sulphonated phenol v
formaldehyde trong mi trng acid hay kim mnh v c dt ln thu ngn hoc
tm bn acid. Cc thng phm c tng hp bng: bay hi dung dch in ly cao
phn t. Mc d khng c ni ngang nhng mng khng tan trong nc. Trong
phng php polymer gn kt bng phng x gamma dng gn styrenen hay
styrene DVB ln mng polyethylene.
Nhc im ca loi mng trao i: gi thnh cao, bn c hc hn ch, tr
khng cao khi nng dch in ly thp, thm thu cao.
2. Nha trao i ion

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7
2.1. Phn loi nha trao i
Tnh cht trao i ca nha T ion c quyt nh bi cc nhm c trng
trong sn (khung) cao phn t ca nha v cc ion linh ng. Cc nhm ny mang
in tch m hoc dng to cho nha c tnh kim hoc acid. Cc nhm c trng
trong ionit ni vi cc ion linh ng c du ngc li bng lin kt ion. Cc ion linh
ng ny c kh nng trao i vi cc ion khc trong dung dch.
Nha trao i cation (cationit)
L nhng cht c c trng acid. Trong cu to mng li ca nha c mang
in tch m (nhm c trng mang in tch m) km theo nhm c trng c mt
cation linh ng c kh nng trao i vi cc cation khc trong dung dch.
Cc ion linh ng ca cationit thng l H, thng c gi l nha T cation
dng H. Nu thay H bng Na, nha c gi l Na-cationit
Cc nhm c trng ca cationit : -SO
3
H, -COOH, -OH (ca phenol), H
2
PO
3
-
Cc nhm c trng cng nhiu, kh nng trao i cng tng, ng thi, ho
tan trong nc ca nha cng tng. Nu tng ni ngang trong cu trc ca nha
ionit th kh nng trao i, ho tan gim nhng trng s tng. C hai loi
cationit:
o Cationit acid mnh: nhm c trng l -SO
3
H, -PO
3
H
C kh nng phn ly thnh ion linh ng, t linh ng trong tt c cc mi trng
trung tnh, kim, acid. Do kh nng trao i ca chng khng b nh hng bi pH
ca dung dch.
o Cationit acid yu: nhm c trng -COOH, -OH
Phn ly yu trong mi trng acid, kh nng trao i ph thuc vo pH ca mi
trng. Trong mi trng kim, kh nng phn ly mnh nn kh nng trao i ln.
Trong mi trng acid, kh nng phn ly thp, dn n kh nng trao i thp.
Nha trao i anion (anioit)
Cc nhm hot ng mang in tch dng, to cho anionit c tnh kim, cc
anion linh ng c th trao i vi cc anion khc trong dung dch. Nhm c trng:
kim amin bc 1, 2, 3, 4. Cc anion linh ng thng l OH, Cl. . .
o Anionit kim mnh: Nhm c trng l kim amin bc 4
___________________________________________________________________________

8
N
CH
3
H
3
C
CH
3
OH

Nhm OH nh vo nh lc tnh in. Anionit kim mnh c mc phn ly ion
tt trong tt c cc mi trng nn kh nng trao i ca chng khng ph thuc pH
ca mi trng.
o Anionit kim yu: Nhm c trng l kim amin bc 1 NH
2
, bc
2 =NH v bc N. Anionit kim yu ch phn ly trong mi trng kim yu.
2.2. Mt vi thut ng s dng trong k thut trao i ion
*Khi lng ring ca ht nha (density of resin)
* bn c hc (mechanical resistance)
*Kch thc ht nha (grain size)
*Dung lng tng (total capacity): l lng ion c trao i trong mt n v
trng lng ca nha
* Kh nng tch mui (salt splitting): lng ion Na b hp th bi nha dng H
(hay lng H i ra khi nha) trong mt n v khi lng hay mt n v th tch.
* xp (porosity)
*Dung lng trao i (exchange capacity): khi lng ion gi c trn mt n
v th tch vt liu trao i.
*Ion leakage: nng ca ion khng mong mun b tch ra trong dung dch x
l.
* ng cong Breakthrough

___________________________________________________________________________

9
2.3. Cc phn ng c trng
Qu trnh trao i vi cationit
RSO
3
H + Na
+
+ Cl
-
RSO
3
Na
+
+ H
+
+ Cl
-
2RSO
3
H

+ Ca
2+
+ 2Cl
-
(RSO
3
)
2
Ca + 2H
+
+ 2Cl
-
hoc
RCOOH + Na
+
+ OH
-
RCOONa + H
2
O
C th xem y l qu trnh ho hc d th (lng-rn). Mc ion ho ph thuc
bn cht ho hc ca nhm hot ng, tnh cht dung dch bn ngoi
V d: nhm sunlfo: ion ho tt trong mi trng acid
-COOH, OH: trong mi trng acid ion ho km hn
Cationit acid mnh: mc phn ly khng ph thuc pH
Cationit acid yu: thay i dung tch trao i theo pH
Mt c im khc: khi cationit trao i t n bo ho vi cation ny, th c
th trao i vi cation khc.
R-H
+
+ NaCl R-Na + H + Cl
-
2R-Na + CaSO
4

(R)
2
Ca + Na
+
+ SO
4
2-
Sau khi bo ho, cationit c ti sinh bng acid
R-SO
3
Na + H
+
R-SO
3
H
+
+ Na
+
(R-SO
3
)
2
Ca + 2H
+
2R-SO
3
H

+ Ca
2+
Qu trnh trao i ca anionit
Anionit kim yu (nhm amin bc 1, 2, 3): ion ho khi pH<7
Anion cha amin bc 4: ion ho trong mi trng acid yu, trung tnh, kim.
Anionit kim mnh c phn ly cao
R-OH + HCl R-Cl + H
2
O
Qu trnh ti sinh
RCl + NaOH ROH + NaCl
Qa trnh trao i ion l mt qu trnh thun nghch, phn ng ho hc d th
gia cc nhm hot ng ca nha v cc ion trong dung dch. Qu trnh trao i tun
theo nh lut tc dng khi lng.
2.4. Tng hp, tnh cht ht nha
2.4.1. Tng hp
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10
Nha phenolic (KY-1 Nga):
Cha nhm SO
3
H, v nhm hydroxyl phenol. C th i t monomer sulfo
phenol v formaldehyde hoc iu ch nha phenol formaldehyde sau sulfo ho
bng H
2
SO
4
m c.
Qu trnh qua hai giai on:
+Sulfo ho phenol: khng ch iu kin nhm sulfo gn vo v tr para
ca phenol. Tin hnh nhit di 110
o
C, t 10-13 gi, sn phm nhn c
dng lng.
+Ngng t vi formaldehyde
Thng 1 mol sulfo phenol thng ly hn 1 mol formaldehyde. Tin hnh trong
iu kin ging vi tng hp nha phenol formaldehyde. Ngng t xong em sy
100-110
o
C, trong thi gian 4-5 gi. Sn phm nhn c c cu to dng li. em
nghin, ra sch acid tha. Sng ly sn phm c kch thc 0,5 2 mm, c mu en.
D=1,0 1,2, m 15 -20%.

OH
SO
3
H
n +
n CH
2
O
OH
SO
3
H
OH
SO
3
H
CH
2
OH
CH
2
OH HO
3
S
CH
2
CH
2
Nha styrene-divinylbenzen (Ky-2 -Nga)
Polymer ho huyn ph styrene v divinylbenzen (DVB): ban u dng lng,
cho vo thng phn ng, nc. Cht hot ng b mt gi cho h c phn tn n
nh. Khuy trn, styrene/DVB hnh thnh tng khi ln, tng tc khuy, ht nh
hn c hnh thnh, tng tc khuy n khi kch thc ht t yu cu khong 1
milimet. Ti im ny, thm benzoyl peroxide vo,
___________________________________________________________________________

11
qu trnh polymer ho din ra v hnh thnh cc ht nh. Divinylbenzen l tc nhn to
ni ngang, lm cho ht c cng, khng c styrene ht nha c th ho tan trong
nc.
Polystyrene-DVB cn c hot tnh ho hc s dng lm cht trao i ion. Cc
nhm hot tnh c gn vo. Mi nhm chc c mt in tch c nh, c th cn
bng bi in tch i tng ng c th trao i vi cc ion cng in tch.
Nha cation acid mnh c to ra khi x l ht nha trong acid sunfuric m
c (gi l qu trnh sunfonat ho), nhm sunfonic acid mang in tch m, bn. Quan
trng l cc tm mang in ny phn b trn ton b ht. Qu trnh trao i ion khng
phi l mt qu trnh b mt, hn 99% kh nng trao i ion c nhn thy bn trong
ht.
Nha anion kim mnh c hot ho qua hai giai on: trc tin chloromethyl
ho, sau amin ho. Qu trnh hai bc bt u vi cng vt liu styrene/DVB c
dng cho nha cation. im khc bit l lng DVB c dng t hn, lm cho ht
xp hn. Bc phn ng u tin l gn nhm chloromethyl vo mi vng benzen
trong cu trc ca ht. Nha chloromethyl trung gian ny cn phn ng vi anim
trong qu trnh amin ho. Loi amin s dng s xc nh chc nng ca nha. Amin
thng dng l trimethylamine (TMA), s to ra nha trao i anion kim mnh loi I.
S dng dimethylanolamine (DMEA) s to ra nha anion loi 2.
ng trng hp styrene vi divinylbenzene, sau sulfo ho bng H
2
SO
4
m
c. Loi nha ny c nhm c trng l -SO
3
H, bn ho hc, bn c, bn nhit n
150
o
C. Qu trnh ng trng hp tin hnh 80
o
C, trong 18 gi, oxi ho bng H
2
SO
4

m c 100
o
C, trong 8 gi, Ag
2
SO
4
lm xc tc.
___________________________________________________________________________

12

CH=CH
2
CH=CH
2
CH=CH
2
+

___________________________________________________________________________

Ag
2
SO
4
/ H
2
SO
4
CH CH
2
CH CH
2
CH CH
2

CH CH
2
CH CH
2
CH CH
2
SO
3
H
SO
3
H

Catonit KB-4
ng trng hp ca methylmethacrylic (hoc dng mui) vi divinylbenzene
(10% so vi cu t chnh), c 1% peoxide benzoyl, ung nng 60
o
C, trong 24h, sau
x phng ho bng NaOH 2N, ra v sy.
CH
2
C
CH
3
CO
2
CH
3
CH=CH
2
CH=CH
2
+

C
H
3
C
H
3
COOC
CH CH
2
CH
2
CH CH
2
n

C
H
3
C
HOOC
CH CH
2
CH
2
CH CH
2
n

X phng ho nhm este bng NaOH
Loi nha ny bn c hc, bn ho hc, bn nhit so vi cc loi khc. nhit
160-180
o
C, cc nhm cacboxyl khng b phn hu nn rt thun li khi lm vic
nhit cao, tnh cht ng hc rt tt.

13
Anionit
Loi ny cha nhm hot ng kim amin bc 4 (-N
+
(CH
3
)
3
). Tng hp bng
cch amin ho ng trng hp chlomethyl ho ca styrene v divinylbenzene

CH=CH
2
CH=CH
2
CH=CH
2
+
n

CH CH
2
CH CH
2
CH CH
2
CH
CH CH
2
CH CH
2
CHCH
2
CH
2
Cl
n

ZnCl
2
CH
3
OCH
2
Cl

CH CH
2
CH CH
2
CHCH
2 n
CH
2
NR
3
Cl
R
3
N
CH CH
2
CH CH
2
CHCH
2 n
CH
2
NH
2
RCl
RNH
2
Nha anion kim yu
Nha anion kim mnh
2.4.2. nh gi dung lng hot ng ca ht nha
*Phng php gii hp: Dung lng hot ng n nh ca ht nha xc nh t
cc gi tr: tng lng ion c th trao i trong ct ti im cui ca breakthrough v
phn ca mi loi ion trao i c gii hp trong qu trnh ti sinh.
Trong thc t, cn ti sinh hon ton vi tc nhn ti sinh ph hp. Ct c bo
ho ti mt im breakthrough nh trc. T cc gi tr th tch nha s dng,
th tch dung dch x l, nng cc ion dung lng cc i ti im breakthrough
___________________________________________________________________________

14
c xc nh. Sau ct c gii hp vi tc nhn ti sinh c nng ph hp cho
n hon ton.
V mi quan h: % ion c tch loi -lng tc nhn ti sinh s dng
...
x
r
x
r
Qs
Q
B
B
A
A
+ +
=
Q l dung lng hot ng, Qs dung lng ti breakthrough, rA t l lng ion
A trn tng lng ion c th trao i c, x
A
phn ion A b gii hp.
tnh c % ion tch loi (hoc ngc li l % leakage) cn hot ng trng
thi cn bng xc nh i lc tng i ca ion nghin cu.
RB
RA B
A
X
X
K
C
C =
C
A
nng ion A trong dng thi ra (leakage); K l hng s cn bng; X
RA
phn
ng lng ca nha dng A.
*Phng php ct tun hon
Ct c bo ho vi mt dung dch bit nng , tc v nng ca tc
nhn ti sinh bit trc. Thng thng phi qua nhiu vng hot ng, ti sinh ht
nha c c dung lng hot ng v nng ion trong dng ra t trng thi n
nh. Dung lng hot ng xc nh: t vic o th tch cht lng x l v nng
ion cc cu t trong dung dch ti sinh. Nng ion (leakage) xc nh ct ra.
2.4.3. xp ca nha
Kh nng lm vic ca nha bnh thng hay nha chun khng ch ph
thuc vo kh nng ca ion linh ng trao i vi cc ion trong dung dch, m cn kh
nng ca cc ion thay th khuch tn su vo trong nha. Khi cht HT c ngun gc
khong s dng, kh nng thm nhp ca cc ion ph thuc vo xp ca cht HT
v kch thc ca ion thay th. Vi l xp nh, ion ln s khng c qu trnh trao i
ion.
Tng t vi cc cht HT c ngun gc t khong, ngi ta cng s dng t
XP (porosity) khi s dng nha trao i ion.
xp ca nha trao i ion c th d on bng cch cho hp thu hi ca mt
cht lng tr hay hp thu hi N
2
nhit thp. Cc phng php ny c s dng
nh gi xp thng gi l cht trao i ion chun, l nha T ion c
___________________________________________________________________________

15
copolymer ho bng phng php thng thng ca styrene hay monomer khc vi
tc nhn lin kt ngang nh divinylbenzene. Ngui ta ch ra rng: th tch l xp tng
ca nha T ion vi 2% divinylbenze l 0,004cm
3
/g, 16% divinylbenzene l
0,001cm
3
/g. Gi tr ny nh hn 10 ln i vi polymer mch thng (tuyn tnh) v
nh hn 100 ln so vi th tch l xp tng cng ca than xp loi tt. Din tch b
mt ring ca cht T ion ny khong 0,1 m
2
/g, vi cht HT c ngun gc khong
cht l 600-800 m
2
/g.
D nhin, kh nng hp th cao ca nha tiu chun khng lin quan g n
xp ca n. Cht T ion ny ch hp th cc ion nh. Cc ion ln hn nh terramycin,
penicillin v cc hot cht sinh hc khc c th b hp thu ch trong mi trng m n
c th trng. Trong trng hp ny, s c mi quan h trc tip gia kh nng hp
th ca nha T ion v trng trong mi trng (hnh 20.2).

Hp thu ion ch din ra trong mi trng lng, v vy kh nng trng ca nha
trc tin ph thuc vo kh nng hydrat ho ca cc nhm phn ly - xc nh i lc
ca nha trong nc. hydrat ho cao, nha trng tt. Mc trng ph thuc
vo ion trong dung dch. Nu kh nng hydrat ca cc ion thay th nh hn hydrat
___________________________________________________________________________

16
ho ca cc ion b thay th, trong dung dch mui hoc acid m c ht nha s b co
li do nc i ra dung dch.
Mc trng ca ht nha cng ph thuc vo s lng ni ngang trong
polymer. Lng ni ngang ln, trng s thp. nh lng mi quan h ny rt kh
v nh lng chnh xc ni ngang thng kh bit c (kh xc nh phn no trong
polymer tham gia phn ng, mc d hm lng cht to ni ngang bit c).
Trong khi trng, cu trc ca ht nha thay i ng k - ging nh cc cht
HT khng rn in hnh, v vy vi nha trao i ion xp, cm t xp vi m-
microporosity v xp gia cc phn t - intramolecular porosity khng c s
dng. Trong qu trnh hp thu trn nha T, polymer trng, c ngha, nha l mt
dung dch vi phn t trong polymer lin kt ngang v kh nng hp thu ca nha c
th d on t trng. trng cho ta d on nh lng ca tng th tch
chim bi cht lng vi phn t trong polymer xp. Thng th tch ny khng quan
trng so vi th tch l xp tng th tch ny gp hng trm ln. Trng c th gim
bn ca polymer v gim thi gian s dng ca ht nha.
Vi nha T ion, cm t kh nng thm c th dng nhng vi mt ngha c
bit.
Qu trnh trao i ion c th biu din qua nhiu cc giai on:
+Cc ion thay th di chuyn t dung dch n b mt cht HT
+Cc ion thay th di chuyn bn trong cht HT n cc tm trao i
+Phn ng trao i (ho hc) tnh cht ca phn ng trao i
+Cc ion b thay th di chuyn t tm hp thu trong cht HT n b mt
cht HT
+Di chuyn ca cc ion b thay th t b mt cht HT ra dung dch.
Kh nng thm ca nha T ion c th xc nh bi giai on 2 ca qu trnh,
ph thuc vo gi tr hp thu ion v h s khuch tn, v sau l kch thc ca ion
khuch tn v bn ca mi trng. H s khuch tn ca ion thay th, b thay th,
cng nh giai on 2, 5 ca qu trnh, s quyt nh ng hc ca qu trnh. Lng ion
b nha hp thu ph thuc vo i lc ca ion i vi nha, trng v quyt nh
ng hc hay tnh hc ca trao i ion. V vy, kh nng thm ca nha T ion ph
thuc vo ng hc, tnh hc ca trao i ion, c hai u ph thuc vo trng.
___________________________________________________________________________

17
Kh nng trng ca nha xc nh kh nng chn lc. Nha trng nhiu c th
gi ly cc ion kch thc khc nhau, c ngha chn lc km. Nha c trng
km c kh nng hp thu cc ion nh tt hn so vi cc ion ln. y l nguyn tc c
bn ca phng php li lc trao i ion, theo cch ny, cc ion mang in tch vi
cc kch thc khc nhau s b tch ra. V d, s dng nha trao i c trng thp
s tch c ion kim loi ra khi mt hn hp cao phn t nh protein - thng th
loi ny khng hp thu. Tch cc cht khong hon ton khi streptomycin thc hin
bng li ion. Anion c kch thc khc nhau cng c th c tch ra bng cch
tng t.
S dng li trao i ion theo cc trng khc nhau, c th tch cc ion vi
kch thc gn nhau ra. V d, insulin c th tch ra t hn hp cc cht hu c cao
phn t.
Cc ion c kch thc rt ln ch c th b hp thu bi nha trao i ion c
trng tt, qu trnh hp thu din ra trong ton b cht HT. Nha T c trng
thp v s dy c ca cc nhm phn ly c trong nha s lm gim kh nng hp thu
cc ion hu c (mt phn cc nhm ny b cc ion ln c nh trong nha, cc nhm
ny khng tham gia phn ng trao i). tng hp thu cc ion ln nn s dng
nha c kh nng hp thu tng cng nh ( v d nh ion Na). Vi mc ch ny, nha
cha mt lng nhm hydroxyl ln lm tng trng , cc nhm c kh nng
trao i c sp xp mt cch tng i rng ri hn (rarely). iu ny l cn thit
nh nha carboxyphenol-formaldehyde.
2.4.4. Nha c xp v m
Cc cng trnh nghin cu trong tng hp nha T ion c gng to ra cht HT c
xp tng ng vi than hot tnh. Cc n lc u tht bi khi c gng gim
ni ngang trong khung C ca copolymer v s dng cc loi monomer khc. Thay i
cu trc ca polymer bng thay i iu kin polymer ho t ra c kt qu tt hn.
Mt trong cc cch to khung C c xp v m l a thm cc cht to bt
trong qu trnh copolymer ho cc monomer cc cht ny phn hu nhit, to sn
phm kh. Tuy nhin phng php chnh to xp cho nha xp v m l thm
mt cu t th 3 khng tham gia vo phn ng, dung mi tt cho monomer v ho
tan polymer km. Dn n sn phm copolymer s trng trong mi trng ny. Cc
cht hay s dng trong copolymer ho ca styrene v divinylbenzene l n-heptane,
___________________________________________________________________________

18
isooctane, cc alcohols bc cao. Sau khi copolymer ho xong, trong dung dch nc,
c mt cc cht nh ho, cht ho tan s cha ng trong copolymer xp, c tch ra
bng chng luyn. S to ra cc l xp kch thc ln trong polymer.
Nhiu nghin cu cho rng, cu trc v c tnh ca copolymer sn phm khc
b khung vi nha trao i ion tiu chun. Copolymer tiu chun khng mu, trong
sut, nh thu tinh; nha tro i ion loi mi c gi l nha c lin kt ngang
ln hoc c xp v m l m c, trng nh sa, khi lng ring nh(density),
khi lng dung dch nh (bulk mass), cc tnh cht c hc v ng hc c ci
thin, bn ho cao.
Nghin cu chi tit xp ca loi nha mi ny cho thy rng: din tch b
mt ring ln, th tch xp tng cng ph thuc tc nhn lin kt ngang v cht ho tan
s dng trong qu trnh tng hp. Mt yu t quan trng khc l tinh khit ca
monomer, c bit l divinylbenzene. Thng phm m-divinylbenzene c kh nng
phn ng thp hn p-divinylbenzene, vi vy mt ni ngang trong sn phm
copolymer tng hp khi c divinylbenzene thng phm l thp hn mong mun.
Hnh 20.3 ch ra s ph thuc ca din tch b mt ring ca styrene/divinylbenzene
to ra v lng ni ngang khi lng n-heptane khc nhau. Cho thy rng, ngay c khi
copolymer tng hp khng c cht ho tan (pha long) din tch b mt ring ch tng
mt t ngay c khi hm lng divinylbenzene cao.

___________________________________________________________________________
Hm lng tc nhn lin kt ngang c bit nh hng r rt n xp ca
copolymer khi lng pha long tng. Nu din tch b mt trong khong 10 100m
2
/g,

19
cht lng ca nha vi gi tr ny c th t c khi tng hp vi lng ln n-
heptane v mt lng nh hn ca divinylbenzene hoc ngc li, vi lng nh n-
heptane v lng ln divinylbenzene. Hnh 20.4 lm r iu ny. Din tch b mt
ring tng ch c th khi s dng mt lng ln cht pha long v tc nhn lin kt.
Trong bng 20.1, ch ra cc s liu v din tch b mt ring v th tch l xp tng ca
mt vi copolymer c xc nh bng hp thu hi hu c v nit. S liu trong bng
ny cho thy, trong mt vi trng hp xp nit (o bng hp thu khi nit) thp
hn so vi xp methanol (o bng hp thu hi methanol). Vi cc copolymer c
xp thp, lm lnh cng nh hng ng k. Nhng vi cc copolymer rn cht c
din tch b mt ring ln, lm lnh khng nh hng my n kh nng st cht v
xp nit cao hn xp methanol.

___________________________________________________________________________

20

Nha T ion xp v m c tng hp vi xp nit khong 900m
2
/g, c
ngha gn vi than hot tnh loi tt nht.
Tng xp cng vi tng lng tc nhn lin kt s lm gim khi lng ring
ca copolymer (hnh 20.5). Tng t, trng ca copolymer trong toluene v cc
dung mi tng t s gim tng ng (hnh 20.6). iu ny c th ni ln vic tng
mt ni ngang, c ngha, l tng nng ni ngang trong copolymer khi tng lng
tc nhn to ni ngang.
___________________________________________________________________________

21
Vn t ra: cu trc ca copolymer nh th no? Ti sao xp tng khi
tng nng lin kt ngang? Vn cha r rng ny lin quan n phng php tng
hp copolymer - thng tin hnh trong dung dch. Cu tr li thng l: nh hng
ca bn cht dung mi v i lc nhit ng ca n vi polymer.
Cc kt qu th nghim cho thy vi cng mt t l dung mi-monomer trong hn
hp phn ng, cng mt lng tc nhn lin kt ngang xp ca copolymer tng khi
cht lng dung mi thp. Chng t c s nh hng ca bn cht dung mi ln hnh
dng ca mch polymer v cu thnh mch trong qu trnh tng hp.
Qu trnh polymer ho khng gian 3 chiu din ra trong dung dch hnh thnh
dng gel, c ngha, trong h hai cu t s tn ti mng lui khng gian m dung mi
c cha trong . Trong trng hp ny, thc nghim chng minh h s khng
tch ra (macrosepration). V vy gel s tn ti trong ton b th tch dung mi thm
vo v sau , dung mi bay hi, th tch tn ti c lp. Nu mng khng gian 3
chiu ca copolymer hnh thnh rn chc, n nh trong qu trnh bay hi th th tch
l xp s ng bng th tch ca dung mi chim ch. Thc vy, rn chc ca
mng khng gian ph thuc dung mi din ra qu trnh phn ng.
Nu i lc ca dung mi i vi polymer cao, ngha khc l nu dung mi rt tt
th n s lm co gin h v h tr nn n hi. Gel hnh thnh trong mt dung mi
khng tt s khng n hi m s ng cng. iu ny s nh hng n s co ngt
din ra khi dung mi bay hi. Gel n hi s co ngt nhiu hn loi khng n hi.
Cc th nghim cho thy, s co ngt ca mu khi c 20 % DVB v 93,5% th tch
toluene l 44%, trong khi mu to ra trong cng iu kin nhng c mt ca n-
decane ch l 9%. iu ny c ngha khi dung mi c tch khi gel n hi, th tch
trng cn li s ln hn nhiu so vi gel khng n hi.
iu ny c tnh ton mt cch nh lng vi gi thit ton b dung mi
c tch ra. Khi th tch l xp (Vpor) s bng th tch ca dung mi (Vsol) tr i
bin i th tch V ca mu khi co ngt.
Vpor = Vsol - V (1)
co ngt c nh ngha l t s thay i th tch ca gel vi tng th tch -
bng tng th tch ca polymer Vpol v dung mi Vsol (gi s monomer c
polymer ho hon ton v th tch ca polymer ng bng th tch ca monomer).
___________________________________________________________________________

22
Vsol Vpol
V
+
= (2)
Kt hp li ta c:
V por = Vsol - (Vpol Vsol) (3)
Th tch l xp tng cng :
d
Vpol
Vsol
Vpol
Vsol
) 1 (
Vpol.d
Vpor
Wo
+
= =

(4)
d l khi lng ring ca polymer
Trong cng thc 5 thy rng th tch l xp tng ca copolymer ph thuc vo
lng dung mi dng v co ngt , m n li ph thuc vo i lc nhit ng
ca dung mi vi copolymer v ph thuc vo lin kt ngang.
V vy, nu chng ta thay th vo biu thc 4, co ngt s l 0,44 v 0,09. Vi
Vsol/Vpol = 0,93 vi mu tng hp khi c mt toluene v n-decane th tch l xp
tng s l 0,07 v 0,81 cm
2
/g. Cc s liu ny ph hp vi thc nghim. V vy, vi
cng mt t l polymer / dung mi, vi dung mi cng km, xp cng cao.
Vi cng biu thc , c th thy rng: ngay c khi c mt dung mi tt nht
xp c ci thin bng cch tng lng dung mi nhiu hn. thy r, phng
trnh 3 s biu din vi gel c co ngt v .
Vpor = Vsol - (Vpol Vsol)
Vpor = Vsol - (Vpol Vsol)

Nu xp ca cc mu l nh nhau th
Vsol (Vpol + Vsol ) = Vsol (Vpol + Vsol) (5)
hoc
' 1
) ' ' ' ( ) ' ' 1 ( ' '
'

=
Vpol sol V
sol V (6)
' 1
) ' ' ' (
' '
) ' ' 1 (
' '
'

=
pol V
Vpol
sol V
sol V
(7)
Thay gi tr =0,44 v =0,09 vo (7), s tm c t s th tch toluene v n-
decane
___________________________________________________________________________

23
3 , 2
' '
'
=
sol V
sol V

V vy, c cng mt gi tr th tch l xp tng khong 0,820cm
2
/g vi 20%
DVB trong hn hp th th tch toluene s dng ln gp 2,3 ln th tch n-decane. Kt
qu ny ph hp vi thc nghim ca Millar copolymer c c khi lng toluene
200 -300% ca monomer).
Da trn phng trnh 4, nh hng ca lng dung mi n th tch l xp tng
vi cng mt mc lin kt ngang, c ngha, cng co ngt, c biu din. Vi
mc ch ny, chng ta vit phng trnh:
d
Vpol
Vsol

=
) 1 (
Wo (8)
R rng, trong phng trnh 8, vi cng cc iu kin, th tch l xp tng cng
s tng khi tng lng dung mi Vsol trong hn hp phn ng.
Nha c xp v m c c trng bi phn b th tch l xp theo bn knh.
Bn knh ca l xp ca nha T ion v b khung ca n t 100 dn 100A
o
, trong mt
vi trng hp c th n 100 000A
o
.
Nha trao i c xp v m khng th thay th nha thng thng (tiu
chun). C hai loi u c ng dng ring bit. Tuy vy, nha ny c nhng tnh cht
c bit. xp cao lm cho s khuch tn cc tc nhn phn ng d dng v v tnh
cht ny nhiu nhm chc c th phn ly c a vo trong nha tng kh nng
trao i. Nha xp v m c th c dng hp thu cc ion trong mi trng m
trong mi trng n khng trng, c bit trong mi trng nc. N lm tng
bn c, v cu trc ca n khng thay i khi sy. Khi dng nha xp v m, cc ion
khng sinh, cc ht keo c kch thc ln c th b tch ra
tch ht, kch thcl xp cn ln hn gp 65 ln so vi kch thc ht.
C th ni rng, yu t quyt nh trong tng hp cc loi nha mi l cc
phng php thay i cu trc. c nha T ion vi cc tnh cht , cn thit phi
bit c c tnh cu trc ca polymer v bn cht ca tng tc ca n vi cc dung
mi.

2.4.5. Nhit ng ca trao i ion
___________________________________________________________________________

24
Phn ng trao i trn nha cation dng acid c vit bng cc phng trnh
n gin:
RH + Me
+
= RMe + H
+
RH + NaCl = RNa +HCl
Hng s cn bng :
NaCl RH
HCl RNa
.a a
.a a
K = (9)
y a
RH
, a
RNa
: hot ca ion hydrogen v Na trong nha
a
NaCl
v a
HCl
: hot ca NaCl v HCl trong dung dch
Mt kh khn trong vic xc nh hng s cn bng l cn phi tnh ton chnh
xc khng ch h s hot ca cc mui trong dung dch m cn ca cc mui trong
dung dch thu c t qu tnh trao i ion, c ngha, hot a
NaCl
trong dung dch
HCl. Hot ca ion trong nha cng rt kh xc nh.
Ngoi ra l thuyt ca trao i ion phi tnh n s trng ca nha. Trong
trng hp ny nha trng c xem nh l mng thm thu, dung mi thm thu
qua, tng th tch ca nha. Cng chuyn 1 mole nc t dung dch vo nha s
bng s thay i nng lng t do Gibbs ring phn i = V
) (
.
.
ln
1 2
2 1
2 1
V V
a a
a a
RT = (10)
a
1
, a
2
: hot ca ion trao i trong dung dch
2 1
, a a : hot ca ion trong nha trao i
: p sut thm thu hay p sut trng
V
1
, V
2
: th tch ring ca ion trong cht trao i
Phng trnh 10 p dng vi s trao i ca cc ion c tnh cht gn nhau v
khng tnh n kh nng thay i trng trong qu trnh trao i. Trao i mt ion
ny vi ion khc trong cht trao i ion c th gy ra s thay i th tch. Theo Bresler
v Samsonov, trao i ion trn nha trao i c th trng c c trng nhit ng
hc l s thay i nng lng t do khi dng ion A
1
t dung dch i vo cht trao i,
ng thi dng ion A
2
i vo dung dch v chuyn dung mi t dung dch n nha
trao i hoc ngc li. Trao i ion c m t bng phng trnh:
S n A
Z
A
Z
S n A
Z
A
Z
s s
+ + + +
2
2
1
1
2
2
1
1
1 1 1 1
(11)
___________________________________________________________________________

25
y:
A
1,
A
2
: ion trong dung dch
2 1
, A A : ion b hp thu bi cht trao i ion
Z
1
, Z
2
: in tch ion
n
s
: s mole dung mi chuyn qua khi 1 mg ung lng ion trao i
S, S : dung mi trong dung dch v cht trao i ion
Bin thin nng lng t do Gibbs trong qu trnh trao i bng:

s s
G n
Z Z Z Z
G + + =
2
2
1
1
2
2
1
1
1 1 1 1
(12)

1
,
1
,
2
,
2
: ho th ca ion trong dung dch v trong cht trao i ion
G: thay i nng lng t do Gibbs trong cng vi qu trnh trao i dung mi
Theo phng trnh :
i
o
i i
a RT ln + =
s s
o o o o
G n a RT
Z Z
a RT
Z Z
a RT
Z Z
a RT
Z Z
G + + + + =
2
2
2
2
1
1
1
1
2
2
2
2
1
1
1
1
ln
1 1
ln
1 1
ln
1 1
ln
1 1

13
Ti cn bng, G=0, phng trnh tr thnh
r G n a RT
Z
a RT
Z
a RT
Z
a RT
Z
s s
+ + = +
2
2
1
1
2
2
1
1
ln
1
ln
1
ln
1
ln
1

r: l mt hng s s bng tng ho th ca cc ion trao i iu kin tiu chun.
Khi chia c hai v cho RT, ta c

RT
r
RT
G n
a RT
Z
a RT
Z
a RT
Z
a RT
Z
s s
+
+ = +
2
2
1
1
2
2
1
1
ln
1
ln
1
ln
1
ln
1

RT
G n r
Z Z
Z Z
s s
e
a a
a a

=
2 1
2 1
/ 1
2
/ 1
1
/ 1
2
/ 1
1
(14)
i lng
RT
G n r
s s
e

=K c gi l hng s trao i.
Vi cc dung dch long hot c thay bng nng . Phng trnh 14 tr
thnh
2
1
2
1
/ 1
2
/ 1
1
/ 1
2
/ 1
1
Z
Z
Z
Z
c
c
K
m
m
= (15)
___________________________________________________________________________

26
m
1
, m
2
: s ion c hp thu
c
1
, c
2
: nng ca ion trong dung dch
2.4.6. chn lc
Cn bng trao i ion trong nha trao i ph thuc nhiu vo loi nhm chc v
ni ngang. ni ngang xc nh cht ca cu trc mng li v nh th s nh
hng n xp. ni ngang khng th o trc tip v him khi ng nht.
ni ngang thay i t v ngoi n tm ca ht. Cc loi nha mi thng c
cu trc cht, sp xp trt t v thng c gi l vt liu c xp v m hoc xp
ng nht (macroreticular or isoporous materials). Loai nha ny c cu trc cc hnh
cu v m, c ni ngang cao.
Cc tnh cht quan trong ca vt liu trao i ion l:
-Bo ton in tch (a) trao i ion theo ng t lng (b) dung tch ph
thuc vo bn cht ca ion i.
-Trao i ion l mt qu trnh thun nghch
-Tc khuch tn trong ht hay xung quanh mng thng khng ch tc
trao i ion.
Vi h hai cu t
Biu thc cn bng trao i ion thng c trin khai t qui lut tc dung khi
lng hay l thuyt mng Donnan. Xt s trao i cation A v B gia nha cation v
dung dch khng cha loi cation no khc. Gi thit rng, vt liu trao i dng B,
dung dch cha cation A. Biu thc trao i c th c vit
+ + + +
+ +
B A A B
z
A
z
B
z
B
z
A
B z A Z A z B Z
Du gch pha trn k hiu vi cc loi ion trong pha nha, z
A
+
, z
B
+
l ho tr v
in tch ca ion i A v B. Hng s cn bng nhit ng K
a
c biu din:
zB
A
zA
B
zA
B
zB
A
a a
a a
Ka
) .( ) (
) .( ) (
=
Mt kh khn ln gp phi l cc h s hot , hot ca nha. Trong thc t
p dng thng gi thit rng h s hot ca pha lng bng 1, iu ny rt ng khi
dung dch long. V vy, h s hot ca pha nha thng c kt hp trong hng
s cn bng K
a
, a ra hng s chn la K
c
.
zB
A
zA
B
zA
B
zB
A A
B
C C
C C
Kc
) .( ) (
) .( ) (
) ( =
___________________________________________________________________________

27
Thng ngi ta s dng phn ion ng lng biu din nng trong dung
dch v pha rn. V vy, h hai c t tr thnh

zB
A
zA
B
zA
B
zB
A z z A
B
x y
x y
C
C
Kc
B A
) .( ) (
) .( ) (
) ( ) ( =

H s phn b m
A
c xc nh
C x
C y
C
C
m
A
A
A
A
A
= =
H s tch c nh ngha
A B
B A
B B
A A A
B
x y
x y
x y
x y
.
.
/
/
= =
Trao i ion ho tr 1: c ngha z
A
=z
B
= 1, h s chn lc tr thnh
A
B
A A
A A
A B
B A A
B c
y x
x y
x y
x y
K =
= =
) 1 (
) 1 (
.
.
) (
th c trng ca K
c
th hin hnh 13.1-1

Nu K
c
>1, ht A u tin trao i, lc ht tr r rt khi K
c
tng. Nu K
c
<1 ht A t
u tin hn ht B. chn lc ca nha trao i ion b nh hng kh ln bi ni
ngang. Nha c xp cao, t ni ngang s gim chn lc vi ion nh ny so vi
ion khc. Tng ni ngang, chn lc tng (bng 13.1-3).
___________________________________________________________________________

28

Gregor ch ra rng trng ca nha trong qu trnh trao i l kt qu ca qu
trnh thm thu , p sut thm thu ca gel c c do sc cng ca cu trc nha. Vi
iu kin cng ho tr, ion hydrat ln s t thun li v n cn phi gin mng li ra.
Bng 13.1-1 v 13.1-2 th hin cc gi tr K
c
nh mt hm ca ni ngang ca trao
i Na v H. Tng chn la khi tng ni ngang c th d on t l thuyt.

Bonner v Smith a ra chn la ca cc ion ho tr 1 ly Li lm chun so
snh. Thang chon la (bng 13.1-3) ly c s trn tham s K
a
v tng ng ch ra
chn la ci thin khi gim kch thc ca ion hydrat v tng ni ngang.
___________________________________________________________________________

29
Trao i gia ion ho tr 1 v ion ho tr 2
Lc ny z
A
=2, z
B
=1, biu thc h s chn la tr thnh
2
2
) 1 (
) 1 (
) ( ) (
A A
A A A
B c
y x
x y
C
C
K
=
Quan h gia y
A
v x
A
tr nn ph thuc nhiu vo C, nng pha lng. Gin
cn bng th hin hnh 13.1-2. R rng, u tin ca A tng nhiu khi nng
dung dch gim. Tng nng dn n lm gim chn la ca ion ho tr 2 so vi
ion ho tr 1.

Thang chn lc ca ion ho tr 2 c cho bng 13.1-4. Gi tr ca n v ly
theo ion Li. Bonner v Smith hiu chnh gi tr hng s cn bng vi gi s cc h s
hot bng s dng phng php pht trin ca Argersinger v Davidson.
=
1
0
) log( log
A
A
B
c a
C d K K

Phng trnh Gibbs-Duhem.

Trao i anion:
Cc gi tr m rng ca h s chn lc vi nha anion kim mnh ca loi
amonium bc 4 c cho bng (ca Baunman v Wheaton, Kunin v McGarvey,
Grogor v ng nghip). Gregor v ng nghip ch ra hai loi ion: loi t thay i h
___________________________________________________________________________

30
s chn la theo thnh phn v loi ph thuc thnh phn. Loi ph thuc thnh phn
c cho l hnh thnh cluster trong pha nha trong khi o loi khng ph thuc thi
phn b ngu nhin ti cn bng.

Trao i ion nhiu cu t
V l thuyt, trao i ion nhiu cu t l rt phc tp, c bit nu cc ion c ho
tr khc nhau. Cn bng trao i ca cc ion cng ho tr l n gin v chng ta gi s
rng h s chn la hay tha s tch l hng s trn c dy nng ion.
Xt hai cu t i v j, tha s tch c nh ngha
j i
j i
j
j
y x
x y .
=
(ngay c cc ion khc ho tr, gi s l hng s cng c th chp nhn c).
Nu tng s ion trao i c l n, th s c n-1 phng trnh c lp. tm cc nng
pha lng t cc nng pha rn, phng trnh trn c th c kt hp thnh

= =
j
j
k
j
i
k
i
j
i
i
j
i
i
y
y
y
y
x

Gi s c p dng cho tt c cc cu t, k k hiu cho cu t c chn tu ,
, , l bng 1. Biu thc tng t c c biu din y
i
i
j
j
k
k
i
theo x:

= =
j
j
j
k
i
i
k
j
j
j
k
i
i
x
x
x
x
y

___________________________________________________________________________

31
Nu x
i
l hng s,
j
l hm tuyn tnh ca cc gi tr y khc. Tng t, nu y
i
l
hng s, x
j
tr thnh mt hm tuyn tnh theo cc gi tr khc ca x. Xem xt h 3 cu
t A, B v C. Gi s cc ion l ho tr 1, th , , . T

A
B
A
B c
K = ) (
B
C
B
C c
K = ) (
C
A
C
A c
K = ) (
1 =
C
A
B
C
A
B

Cn bng h 3 cu t c th biu din trn gin tam gic. ng k ngang dc
u n ca gin th hin thnh phn ca mt trong cc pha (thng l pha rn):
thnh phn ca pha khc c c bng mt nhm cc ng vng quanh., mi ng
tng ng vi nng ca cc cu t. Hnh 13.1-3 gin tam gic cho h gi thit
c , . 2 =
A
B
2 =
B
C

ng quanh (trng hp ny l ng thng) vi x
A
=0,1 c c bng ni
im ct ca n vi ng y
B
=0, y
C
=0. Cc im ct c c t gin cn bng hai
cu t A-C v A-B. Vi h ho tr 1 v 2, tha s tch ( ) thay i theo thnh phn.
V vy, nh hng ca nng phi tnh n khi biu din cc s liu cn bng. Trong
trng hp nh th, cng c th v gin bc 3 tng ng v mt v d ca tha s
tch bin thin, cn bng th hin trn hnh 13.1-4. ng vin by gi l ng cong
do vy vi mt tha s tch bin thin h c th c xem nh l mt h tha s
A
B

___________________________________________________________________________

32

___________________________________________________________________________

33

___________________________________________________________________________

34

2.4.7. ng hc qu trnh trao i
ng hc ca qu trnh trao i ion c chia lm 5 bc
1. Khuch tn ca ion i qua lp dung dch n b mt cht trao i ion
2. Khuch tn ion i trong pha rn
3. Phn ng ho hc gi ion i vi cht trao i
4. Khuch tn ca ion b thay th ra khi cht trao i
5. Khuch tn b trao i t b mt cht trao i vo dung dch
Bc 4 v 5 l ngc li vi bc 1 v 2. ng hc ca qu trnh c quy nh
hoc c ch khuch tn hoc c ch trao i cht ph thuc vo bc no chm nht.
Nhn chung, khuch tn ca ion trong dung dch bn ngoi c gi l Khng ch
khuch tn mng (film diffusion control). Khi nim ny rt cn thit trong thu ng
hc. S khuch tn hay vn chuyn ion trong pha trao i c gi Khng ch khuch
tn ht. Phn ng ho hc ti cc tm trao i c th l tc khng ch qu trnh
trong mt vi trng hp c th.

___________________________________________________________________________

35
Qu trnh khuch tn
Nhn mnh rng: ng hc khuch tn n gin l trng hp l tng ca trao
i ion. Ch cn nhc cn thn vi cc h ti phn b ng v vi cc iu kin bin
c bit. Thng thng, gi thit rng ht trao i ion l hnh cu v kch thc ng
nht. Trong trng hp ny, qu trnh khuch tn tun theo inh lut Fick 1

Ji l dng khuch tn ht i c nng Ci, D l h s khuch tn. Helfferich
gii quyt vn tc trao i da trn nh lut c bn ny.
Bn cht ca bc quyt nh tc c d on khi s dng cc iu kin n
gin ca Helfferich

Khng ch khuch tn ht
Khng ch khuch tn ht

___________________________________________________________________________

36
Nu khuch tn mng nhanh hn nhiu so vi khuch tn trong ht trao i ion
th chnh lch nng trong mng lng gim ngay (hnh). Bin thin nng trong
cht trao i v khuch tn ht l bc khng ch tc . V mt nh lung, khuch
tn ht l rt phc tp v pha rn bn trong ch mt phn sn c nh l mi trng
khuch tn. Phn ln pha bn trong ht l mng li ca cht trao i v dn n c
s che chn v khng gian, ng khuch tn tr nn ngon ngho. Ngoi ra, s di
chuyn ca cc ion i b gi li trong mt mng li cc nhm ion c nh trn mng
ca cht trao i. V th, che chn khng gian v tng tc ion s dn n ng hc
khuch tn chm hn bn trong ht.
Trong iu kin th tch rt ln, phn thay i hay s t c cn bng c
biu din

Th t, ion khuch tn c linh ng khc nhau. Lc ny, nh lut Fick c
thay bng phng trnh Nernst-Planck - ng hc khuch tn mng v ht trong h l
tng c biu din

y, l in th. L thuyt Nernst-Planck d on tc thun, nghch ca
trao i ion khc nhau ng k khi linh ng ca ion i khc nhau (hnh). c tnh
ni bt ny l th hin trn ng cong nng bn trong ht. Nu mt phn ion c
trong ht l nhanh hn, th bin dch chuyn hng v tm ca ht. V vy, trong
trng hp ny, nng ca ion chuyn ng nhanh l rt nh v ngoi v cao
tm ca ht. Do , h s khuch tn gim theo hng v tm ca ht v ung l
chuyn i nhanh chng. Tnh cht ny tng t vi m hnh lin tc lp v hoc
khuch tn lp cho cc ht tng tc.
ng hc phn ng ho hc: kh nng phn ng ha hc gia ion i v cc tm
trao i c nh c nhn bit nh l mt trong nhng c ch chung ca trao i ion
trong nhng iu kin no .
___________________________________________________________________________

37

Bc khng ch tc khng cn l qu trnh khuch tn nh bnh thng m l
ng hc phn ng ho hc. Tc trao i ion c quy nh bi hng s tc ca
phn ng ho hc tng ng. Cc nh lut c bn ca ng hc c th c s dng.

ng hc phn ng ng nht: quy lut c m t bng phn ng ho hc bc
2, 2 phn t c th c xem l tng t vi qu trnh trao i ion. Mc d trao i
ion lin quan n h khng ng nht, ng hc ho hc ng nht c th p dng vi
gi thit pha trao i l mt cht phn ng tan hon ton. Tc trao i c biu
din:

___________________________________________________________________________

38

Vi C
A
, C
B
l nng ban u ca ion i trong vt trao i v dung dch ngoi.
H s k2 l hng s tc bc 2 v C c trng cho nng ion bn ngoi ca ion i
c ngun gc t pha rn ti thi im t. Phng trnh trn c vit li:

Ch : khng c s bin thin nng trong cht trao i ion v khng ph
thuc kch thc ht.
___________________________________________________________________________

39
H phn ng d th: Cc phng trnh ton s hon ton khc nu cht trao i
ion l pha rn. Cc m hnh l tng t vi cc m hnh pht trin cho cc phn ng
trong pha rn. M hnh ng hc c s dng rt ph hp trong mt s qu trnh trao
i ion no .
M hnh shell progressive hay shrinking-core gi thit rng cht phn ng rn
cha ion i A chuyn vo ht trao i hnh cu trc tin. Phn ng gia ion i v
cc tm trao i din ra trong v hay lp v to ra lp sn phm rn c gi l lp x
(ash). Ban u phn ng din ra trn b mt ngoi ca ht, lp bin gia tm phn ng
v tm khng phn ng dch chuyn dn dn vo bn trong ht, li pha sau mt lp
ph ca cc cht phn ng. Trong sut qu trnh ny, bin gii phn ng r rt di
chuyn vo bn trong c hnh thnh, to nn mt vng khng phn ng, co li theo
thi gian.
Theo c ch shell progressive c th p dng cho mt s qu trnh no . Bt
k 3 bc tip theo no, khuch tn mng, khuch tn lp x (ash) v khng ch phn
ng ho hc c th quyt nh tc , ph thuc vo iu kin ban u. Cc mi quan
h sau c xc lp trong nhng iu kin c th

Ch : cc kt qu trn gn vi cc trng hp cht phn ng pha lng tha
nhiu. Tuy nhin, nhiu tc gi khc c c cc kt qu trn vi cc hng tip cn
khc nhau.
___________________________________________________________________________

40
3. Thit b trao i ion
3.1. Chu k hot ng ca nha trao i
3.1.1. Ra ngc
y l bc u tin cn thit chun b cho qu trnh ti sinh ht nha ( s
dng ht hoc bo ho). Dng ra i t di ln.
Tc ng vt l ca ra ngc:
Tng vt liu c ti xp hn, gin ra, sp xp li lm cho dng cht lng
i t trn xung s c phn b ng u hn khi hot ng tr li.
Cn bn c ra sch khi thit b
Cc ion c phn b ng u hn trong ton b tng nha
Khi lng ring ca ht nha, kch thc ht, nht ca dung dch nh
hng n kh nng lm sch ht nha bng qu trnh ra ngc, a cc tp cht l
lng thi ra ngoi. Thng thng, nc c dng ra ngc v s dng mt lng
ln, r tin.
Trong mt iu kin no , hot ng nh mt my lc cc cht rn l lng.
Khi lm mm nc x l bng vi, lp kt ta c th hnh thnh trn tng nha trao
i. Qu trnh ra l cn thit. C th dng kh nn ph v lp kt ta ny trc khi
ra ngc. i khi ngi ta s dng cc ho cht khng ch s hnh thnh cc khi
kt ta ny.
3.1.2. Ti sinh
Sau ra ngc l qu trnh ti sinh.Tc nhn ti sinh (TNTS) s dng ph thuc
vo loi nha v loi ion s trao i. Nha anion c ti sinh bi dung dch NaOH
hoc Na
2
CO
3
. Nhiu yu t nh hng n qu trnh ti sinh:
Loi nha v lng ni ngang.
Loi tc nhn ti sinh.
Thnh phn ca tng nha sau khi hot ng.
Tc chy
Nhit
tinh khit ca TNTS
Nng ca TNTS
Thi gian tip xc
___________________________________________________________________________

41
Lng TNTS s dng
Nu tc nhn ti sinh l n ho tr, th nng ca n t nh hng n qu
trnh gii hp ca cc ion n ho tr. Nu th tch ca TNTS khng tip xc tt,
quy lut ny s b ph v.
Khi tng nng TNTS c th ci thin c kh nng gii hp cc ion ho tr 2.
Nng TNTS thng thng 2-30%, hay dng nht l 5-10%. Trong mt vi trng
hp, kt ta c th lm tt nghn tng ht nha.
V d: gii hp Ca t nha trao i cation bng H
2
SO
4
. Kt ta CaSO
4
c th
c tho i khi hot ng gin on. Dng nng TNTS long ban u, sau tng
dn n cui qu trnh gii hp.
Cc ion khc nhau, mc gn vo nha cng khc nhau do kh nng gii
hp cng khc nhau. Cui qu trnh, cc ion kh gii hp s b gi li trong tng nha,
cc ion d gii hp s b ra sch nc ra ngc. tinh khit ca TNTS cng c
ch .
V d: Cl c i lc mnh vi nha anion kim mnh loi 1. Dng NaOH (ti
sinh) c cha mt lng Cl ng k s khng tt v s gii hp khng hon ton Cl s
lm gim kh nng lm vic ca ht nha.
Tc chy ca TNTS l mt nhn t rt quan trong. Thi gian tip xc phi
m bo ti sinh t cc i. Thi gian ph thuc vo tng loi nha, loi ion cn
tch.
V d: nha cation polystyrene sulfonat ho, c 8% ni ngang, ti sinh 30 pht
bng dung dch tng ng. Cng loi nha ny, lng ni ngang l 12% th phi cn
n 60 pht.
Cc anion Cl
-
, SO
4
2-
, CO
3
2-
d dng b gii hp ra khi nha kim mnh. SiO
2

tch kh hn, thi gian tip xc l 90 pht ti sinh mt lng tng ng. Trong
lc ch cn 30 pht i vi cc ion khc. Trong trng hp c bit cn lu khi
ti sinh nha cation bng H2SO4. Khi dng chy rt nh, hoc nng TNTS qu ln,
CaSO
4
s to ra, bt kn tng nha. Khc phc bng cch tng dng chy hoc gim
nng H
2
SO
4
.
Mc gii hp s quyt nh hiu sut ti sinh v cng nh kh nng lm vic
ca ht nha. Nu TNTS s dng ng, y , cc ion c th trao i s b gii hp t
nha v nha T khi phc li kh nng lm vic. Vic ny chi ph cao, t s dng
___________________________________________________________________________

42
trong cng nghip. Ti sinh thng din ra vi mt mc nht nh, ch mt phn
dung lng ca ht nha c s dng. Cn xem xt vn kinh t ln vn hnh.
C th tng hiu qu ti snh bng cc ti s dng hoc tun hon tr li TNTS.
iu ny c th p dng vi HCl cho vic ti sinh nha T cation v khng c kt ta
sinh ra. thc hin tun hon, TNTS c chia lm hai phn:
-Phn TNTS dng 1 ln: cho chy qua nha trao i ion trc tin. Dng ra
c b i.
-Phn TNTS th 2 l sch c thu hi li, sau khi chy qua nha T v tun
hon nh l phn TNTS u tin cho vng tip theo.
Cch ny ci thin ng k hiu qu s dng cht ti sinh. S vng tun hon c
th tng nu trn ng cong gii hp tc nhn ti sinh vn cn tt. Dng ion i ra
khi nha trong sut chu trnh lm vic ph thuc vo mc ti sinh sau khi nha
bo ho. Cc ion c lin kt vi nha yu s nm pha di ca lp nha v to thnh
mt dng i ra. Trong thc t khi x l nc, ion Na i ra khi nha cation, silica
(SiO
2
) t nha anion kim mnh. S gii hp hon ton cc ion ny trong qu trnh ti
sinh cng phc tp, th dng ion i ra khi nha s cng nh trong chu k vn hnh.
Dng ion ny khng l hng s trong qu trnh vn hnh v Na cn ng li y thit
b trong qu tnh ti sinh v b gii hp bi acid c hnh thnh trong qu trnh lm
vic. Sau khi Na b gii hp ht, dng ion l nh nht. Khi Na bt u xut hin y
thng, dng li tng. Dng thi ra c th duy tr n nh hn bi ra ngc sau khi ti
sinh hn l trc ti sinh. Thnh phn ca tng s ng u hn, s dao ng ca cht
lng dng ra s gim bt.
3.1.3. Ra
Sau khi ti sinh, tng nha cn c ra sch cc tc nhn ti sinh. Giai on u
ca ra l m rng pha ti sinh v lp nha trao i vn cn tip xc vi tc nhn ti
sinh. Vi l do ny, tc ra khng ln hn tc ca qu trnh ti sinh. S thay th
ca cht ti sinh khng c ngn cn hay hn ch trong sut qu trnh ti sinh v ra;
c bit khi dng H
2
SO
4
v CaSO
4
c th kt ta. Sau khi tc nhn ti sinh c tho
ra, tc ra c th tng gim thi gian ra. Cui qu trnh ra, cht lng dng
thi ra c ci thin cho n khi tt c tc nhn ti sinh tha b ra ra ht lp nha.
Tc dng ra cui cng thng l bng vi tc dng chy lm vic (operating
flow rate). Khi cht lng i hi cao hn, cn thit s dng th tch ra ln hn c
___________________________________________________________________________

43
th tun hon nc ra v a tr li dng vo. Gim lng nc ra c th thc hin
c v iu ny rt quan trng khi phi x l mt lng ln nc. Trong thc t, thi
gian dng c th gim, tuy vy, c th dn n s tng lung nc ra.
Lng nc ra cn dng cho nha styrene l 50 gal/ft
3
. Nha T anion cn mt
lng nc ra t hn 50 gal/ft
3
i vi nha bc 4 mi hay loi kim mnh, hoc ln
hn 300 400 gal/ft
3
tu thuc loi nha, tc nhn ti sinh v iu kin ca nha.
Nha anion kim yu cn lng nc ra nhiu hn loi kim mnh, khi sn
phm kim mnh km cht lng, lng nc ra tng khi c mt nhm kim yu.
Loi nc ra cng thay i tu theo ng dng khc nhau.
i vi nc lm mm, kh ion, nc th thng thch hp vi nha cation.
Nc th khng nn s dng vi nha anion v c th xut hin kt ta CaCO
3
,
Mg(OH)
2
.
Nc mm hay nc thi ra sau vng hydro p ng yu cu. Trong mt s
trng hp mong mun s dng nc kh ion.
3.1.4. Hot ng
Sau khi ra, nha c th bt u lm vic. Vic ny cng c gi l s tho
cn v kh nng ti sinh ca nha ht trong sut qu trnh ny. Khi x l nc cht
thi cn thng dng ra tng nha sau khi ti sinh. Sau mt khong thi gian,
dng nc ra c chuyn t dng thi sang dng s dng v qu trnh lm vic bt
u. Khi x l mt cht lng, s phan long cn c hn ch. Thc hin bng cch:
tho nc ra xung mc tng nha trc khi cho cht lng x l vo. Cht lng ny
s b pha long bi nc chim trong cc khong trng ca tng ht nha, khi nng
cht lng trong nc gii hp cao, dung dch c chuyn t nc thi sang nc
thu hi. Qu trnh ny gi l lm ngt. Cui cng, chu k thi ra, ra sch cht lng
qu trnh ra khi tng nha trao i, vic ny ng vic lm ngt.
Cht lng qu trnh c th b pha long bi nc chim trong tng nha v trong
thit b; vic pha long c th gy ra s dehydrate ho ca nha do cht lng qu trnh
nu m c. Khi mt nc ht nha co li c th gy rc ri khi vn hnh thit b
cng nh c th ph v ht nha. Thng nha c ti hydrate ho dng huyn
ph, cc ht nha c th n ra t do khng b chn p ca cc ht khc. S trng ln,
co li ca ht nha c th din ra trong qu trnh ti sinh. Tc trng ca ht cn
gim thiu trnh ph v ht.
___________________________________________________________________________

44
Tc dng chy hot ng trong ct trao i ph thuc vo nht ca dung
dch x l, tc trao i, nng cht l lng. Vi nha cation dung lng ln, v
nha anion kim mnh tc trao i rt ln, c th kt thc vi chiu dy ca lp
nha t 3 n 4 inch, 2gpm/ft
3
. trao i ny s thay i, cc con s ny dng
c trng. Vi nha anion kim yu, di trao i s rng hn v loi ny rt nhy vi
dng chy. nhy ny to ra s thay i ln v kh nng trao i ca nha vi cc
tc dng chy khc nhau.
p sut trn tng trao i cng thay i theo dng chy. Nhit , nht, ca
dung dch x l.p sut ri cng b nh hng bi cc cht rn l lng. Tng nha b
ng cht li c th do cht rn l lng khi p sut d ln. p sut ri ln c th ph
v ht nha. iu ny thng xy ra khi nha T ion c lin kt ngang yu lm vic
tc dng chy ln. Nha n ra trong qu trnh tho cn, p sut ri tng trong vng
lm vic. Di p sut ln, nha b v ra gy nn mt mt nha.
Trong vng tho cn, hnh thnh cc khe rnh. iu ny gy ra do cc cht l
lng trong dung dch x l. Tng nha trao i s lc cc cht rn l lng, tch t pha
trn ca tng nha. Khi nt ra, to thnh cc khe xuyn qua lp nha, t b cn tr.
Bnh thng tng nha b nn cht tm trong chu k tho cn. Nha b ko v pha
tm, nc s chy xung theo thnh thit b.Vi ng i b ngn li, phn tng ht
nha b tho cn nhanh chng, cn tr dung dch cn x l, nha b ph v nhanh
chng.
Thit k tng trao i ion c nh hng ln n kt qu ca qu trnh trao i.
Phn b hp l dng vo l cn thit ngn cn cc nh hng ln phn trn ca tng
nha trong qu trnh lm vic. S phn b dng ra cng khng km phn quan trng v
dung dch cn x l phi chy qua ht tng nha v hiu sut trao i phi cao nht.
Phn b tc nhn ti sinh trn ton b b mt nha cng quan trng m bo
s dng ti a ht nha v cht ti sinh.
3.2. Nguyn tc thit k
Yu t quan trng trong thit k phn xng trao i ion l cu hnh ca ht nha
khi n tng tc vi dung dch. Lc trc, tng nha c nh c xem l tt nht, by
gi ta c th la chn cc cng ngh hin i hn nh: gia tng tnh, tng m ng,
tng si v thng c khuy trn. Lng cht rn l lng trong dch cp vo c th
quyt nh cc kh nng chn la. Nha tng m hot ng nh b lc hiu qu, n
___________________________________________________________________________

45
nhanh chng b tt nu c cht rn l lng, trong khi tng si c th hot ng khi
nng cht rn mn n vi trm phn triu. Thng quay c th hot ng vi lng
bn cha 20% cht rn trong , khng c ht no ln hn ht nha.
Quy m ca phn xng cng l mt yu t cn xem xt khi thit k. Vi quy
m rt nh, c th thit k loi tng c nh vi h s an ton cao n gin trong
vn hnh, khng nhiu thit b khc. Ngoi ra, s dng trao i ion dng lin tc c
th gim ng k chi ph u t vi cc phn xng ln.
Cc yu t trn kt hp vi tc dng chy cao trong tng nha m c th
tng tc phn ng. Ni chung, cc dung dch long, trong c x l vi tng c
nh hoc tng m ng, cc cht lng c hoc bn qung thng c x l bi
thng quay hay tng si.
3.3. Cc loi thit b thng dng
3.3.1. Loi tng nha c nh (fixed bed)
Loi tng c nh n gin nht c th hin trn hnh, c s dng trong mt
nh my x l nc hin i. Thng c thit k c hai u hnh a, chu p lc, c
thm cc ca cng tc. Vt liu l cc loi thp vi lp lt cao su hoc nha. Thp
chng r cng hay s dng. C th ch to bng thng (kch thc nh) bng vt liu
composite. Chiu cao ca tng nha t khi ln hn 1 m, nhng phi phn trn k t
b mt trn ca lp nha khong 1m nha gin trong qu trnh si lm sch cn
bn.
___________________________________________________________________________

46

Hng chuyn ng ca dung dch thng l t trn xung, nha nh l mt
tng m, gia cc ht khng c s chuyn ng tng i. Tng nha c bng
nhiu cch khc nhau. Cch n gin nht l y ct vo phn y ca thng, cc
ng phn phi c chn trong lp ct ny. iu ny c th gp rc ri khi cht lng
chim cc khong trng trong lp ct s to ra s trn ln ht nha v ct sau vi chu
trnh lm vic. khc phuc, c th dng mt tm sn, c c l, cc chn phn phi
(distributor cups) c bt cht vo y. Cu to ny tt nhin t tin hn. Vi cu
to ny, ton b p lc s tc ng tp trung vo tng nha trong qu trnh chy.
Ti sinh nha c th thc hin trong cng thng ny, thc hin dng t trn
xung vi cng h phn phi ny. Tuy nhin, hiu qu s cao khi dng dng ti sinh
ngc chiu. Dng tc nhn gii hp t di i ln xuyn qua tng nha, tng nha
c gi khng c si ln. Nhiu cch gi tng nha khng si ln l s dng
ng thu c nhiu l t ngay st trn b mt tng nha v thay cao su vo pha di
hoc trn tng hoc chn vo trong nha trnh s chuyn ng khi cht lng i
ngc ln trn.
Trong qu trnh lm vic, b mt trn ca nha hot ng nh lp lc hiu qu
vi cc ht nh mn trong dng cp vo. Cn thit phi ra ngc hoc lm si tng
___________________________________________________________________________

47
nha bng nc sch tch cc cht rn ny thi ra ngoi cui mt chu k lm vic.
S dng h phn phi dng y v ng thu np trn thng.
Mt k thut thng thng dng lm sch nc l s dng tng hn hp ca
nha trao i cation v anion, thng th hai tng anion v cation tch ring nhau ra.
S dng ct nha hn hp nh th c th t c tp cht rt thp. Vic ti sinh
cc ct nha ny thc hin vi cc loi nha trao i anion v cation c khi lng
ring khc nhau. Sau khi tng nha c lm si ln bng nc, nha anion s hnh
thnh mt lp ring bit trn mt ca nha cation. Hai lp c lng xung v c
ti sinh ln lt qua cc bc
+Trc tin dung dch kim c cho chy t trn xung t h thng phn phi
c t ngay st trn tng nha v c ly ra bng ng phn phi t gn b mt
phn chia ca hai lp.
+Tip n, ra nhanh loi kim v tc nhn ti sinh acid c cho vo ti lp
phn chia v ly ra di tng nha.
+Tng nha c khuy trn bng khng kh sau khi ra sch acid tha.
Cn t nht hai tng nha c nh hot ng lm sch nc c lin tc,
nhng thng c dng trong qu trnh thu hi. iu ny cho php p sut tng lun
di mc cho php, mi tng hot ng ti a trc khi ti sinh. Qu trnh c iu
khin t ng qua nhiu chu k lm vic v khng ch tc dng cp vo mt tc
tnh ton trc. Cn n 6 van t ng ng m iu khin (t ng) hon ton
hot ng ca 1 thng.
3.3.2. Loi tng ng
Loi hot ng bn lin tc c s dng l thng c tng m, ng, ngc
chiu. Thu lc c dng chuyn tng, piston hoc bm dng vn chuyn
nc. Nhiu thit k khc nhau c ngh nhng ch c hai loi tr thnh thng
phm: k thut Higgins v ca Porter (thit k, Asahi Chemical Company of Japan
pht trin). Chu k Higgins c pht trin bi I.R.Higgins v Roberts Oak Ridge
vo nm 1954, c m t trn hnh
___________________________________________________________________________

48

Hnh th hin s ca thit k vi phn trch hoc x l, cht lng chnh c
cp t trn xung. Phn ny c ni vi mt ng c ng knh ln, to thnh mt
vng lm vic lin tc, nha chuyn ng tng dn trong sut qu trnh trao i. Nh
vy s hnh thnh mt dng cc ht nha: tch, ra ngc, ti sinh, ra v li tch.
Trong qu trnh lm vic bnh thng, nha s hnh thnh nh mt lp m khi giai
on tch v ti sinh, cc van A, B, C v D s iu khin hot ng ny c c
lp vi cc cng on khc. Trong khi nha chuyn ng, dng cht lng bn ngoi b
chn li, cc van A, C v D m ra, cho php nha chuyn ng nhanh dn do nc
chim ch. Khi van A, C v D ng, bn nha c ra ngc trc khi m van B
c th lng trong phn rung.
Mt tng do R. Porter a ra nm 1956 theo thit k ca Asahi. tng ny
c Cng ty pht trin thu hi Cu trong dng thi ca cng ngh sn xut si, h
thng c pht trin rng ra trn quy m th gii x l nc.
___________________________________________________________________________

49

Phn chit hay x l gm tng m vi dng chy t di ln, n s y tng
nha ln pha trn ca thng trong qu trnh lm vic. Cui mt chu k lm vic, dng
cp c tt i v nha li ri xung y thng, ko nha c ti sinh vo trn
nh thp nh van mt chiu. Khi dng cp vo bt u tr li, phn nha pha trn h
phn phi dng vo li b y ln pha trn, phn di b y ra pha di, ra khi
thng, chuyn ln nh ca ct - ti y n b lm si ln tch cc ht nh mn.
Nha lng xung pha y ca ct ra ngc c cp vo thng ti sinh-hot ng
ging nh ct trch.
C hai loi thit k ny lm vic bnh thng vi tng nha m mng hn tng
nha bnh thng. C th lm vic tc chy rt cao, nn thng nh hn thit k
bnh thng.
3.3.3. Loi tng si (fluidized bed)
Tng nha si thng c s dng ra ngc trong qu trnh trao i
ion.Tng si nh l mt phng php tip xc ht rn vi lng c p dng t
nhng nm 40, 50.
___________________________________________________________________________

50
Kh cc ht si ln, khi lng ring ca ht ch ln hn ca cht lng mt t s
khng to ra cc bt kh ln c cc c trng si vi kh; tuy nhin xy ra hin tng
si khc nh vn chuyn ca ht v gin ca tng nha.
Mt vi thit k khc s dng tng si tng tip xc gia lng v ht nha
trnh by trong tp ch v trin khai trong phng th nghim dng pilot. Mt vn
chnh ca cc tng ny l nha chuyn ngc dng vi cht lng theo cch ny c
th khng ch tc dng nha v nha trong tng. Thun li ca tng si l tng
khng lc cc ht nha nh mn nhng cho php n ra theo sn phm lng. Cng nh,
kh khng tch lu trong tng si. Mt thun li khc l p sut ri trn tng m c
th b qua, nhng iu ny khng ng khi s dng vn tc lng nh hn nhiu lm
cho phn xng s phi ln hn.
Thit k u tin trn nguyn l tng si tip xc nha vi dung dch c
Dorr Company (cht lm mm Dorrco) ngh. Dng mt ct cha nhiu khay, trn
nha s si ln. Cht lng i t di ln, qua lp nha, nha b ko i qua cc tng,
cp vo khay pha trn nh mt bm tia cht lng (chy bng nc sn phm). Vn
chuyn nha t ct trch ly n ti sinh bng bm tia cht lng.
Mt nguyn tc hot ng khc c Cloete v Streat; George cng ng nghip
ca Phng M a cht USA ngh. K thut ny da trn nguyn tc chia ct dng
lng theo chu k nh vo mt lot tng si, cho php tng nha ng li trn cc khay.
Ton b lng trong ct c chy bng trng lc hoc bm ngc chiu khong vi
trm milimet; cch vn hnh ny lm cho mt phn nha tng c vn chuyn ng
thi xung tng pha di. Khi dng chy t di ln c bt u tr li, lot tng si
c ti thit lp. C nhiu tng khc c a ra, v d nh ngh ca McNeill
v ng nghip khi s dng xung thp to ra dng nha chy, v Levin (nm 1995,
Vin thu luyn quc gia Johannesburg, Nam Phi) ngh dng cht lng dng
to dng nha ngc chiu bng sa lng. Nguyn l ca Cloete-Streat c m t
hnh 13.3-6.

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51

Trn nguyn tc ny, uranium c thu hi t nc thi long. Dch cp vo
cha 200ppm uranium chy ngc qua ct c ng knh 4,85m, tc 332m
3
/h,
khong thi gian chy trc l 4,5h. Cui mi chu k, dng cp vo c dng li
lng trong 5 min v sau li chuyn ngc tr li trong 5 min, trong thi gian ny,
mc nh gim xung 400mm v khong 6,3 m
3
nha c vn chuyn xung pha
di gia mi tng trong tng s 12 tng. Dng chy trc li c bt u v 6,3m
3

bn nha trong y hnh cn ca ct c vn chuyn qua ct ti sinh bng bm. V
vy, dng chy trung bnh ca dch r (leach) l 320m
3
/h v nha l 1,35 m
3
/h. Mi
khay cha 9,25 m
3
nha tng si, gin gp i so vi mc lng ca n do vn tc
dng cp b mt l 18m/h, c phn b qua 1945 l ng knh 12mm nm trong
khay, to ra mt din tch m bng 1,2% din tch khay.
Nh my u tin c xy dng Germiston, Nam phi tch Zn v Fe t HCl
dng cho ty ra. Nhiu thit b ln hn c xy dng Nam phi thu hi
uranium cc m: Randfontein Estates, Blyvouitzicht, Chemwes, Harmony v Vaal
Reefs. Cng loi thit b vi ng knh ct l 3m c th thu hi vng vt t 528m3/h
nc thi m ti m vng Welkom Nam Phi, s dng than hot tnh thay cho nha
trao i ion. Dng cp vo cha 30ppb vng, thu hi khong 5kg vng mi thng.
Cc nghin cu nguyn l c bn v cng ngh c tin hnh i hc Hong
Gia, Anh (Imperial College). Hnh 13.3.7 th hin nguyn tc c bn ca nh my

___________________________________________________________________________

52

Dng lng chy lin tc t di ln qua nhiu tng trong ct. Mt trong cc tng
l tng nha si. Cc m nha c chuyn ni tip nhau t trn xung bng o
nghch dng chy t tng ny sang tng khc mt cch chn lc. Tng c la chn
vn chuyn b tt xung do chuyn dng chy, v sau thay th nha i xung
trong tng trng pha di. Mi m nha trong y ct chuyn ln nh ct ca ti
sinh. Khay c thit k khc thng v ch c 1 loi phn b nh hnh 13.3-7. S
chuyn ngc dng t tng ny sang tng khc cn cc c cc van vi bm m cng
sut ca n ln hn bm cp. Cc mng chn hay cc phn phi mi tng ngn s
tc nght qua bm vn chuyn.
Porter thit k c bit vi tc dng rt ln, hot ng ngoi tri l cc thng
ln c np m c sp xp theo tng. Vi cc thit k c, dung dch chy t tng ny
sang tng khc bng bm, cc thng lm bng xi mng, hnh ch nht. Cc thng loi
mi l thp c lt cao su, cc thng c t thp dn nn dng chy s theo trong
lng. Dng lng chy lin tc, vo thng ng phn phi c l, t v tr thp ,
dng chy trn qua cc chn trn nh v cui cng chy qua mng chn thu li
mt t nha vo. Nha c chuyn gin on t tng nay sang tng k tip t di
ln, khi trng, bng cch s dng khng kh, n s ko xung gn cui mi tng v
tun hon bn nha, v dung dch vo trong tng t di ln. Nha cho vo gin on
tng cp liu, m t hnh 13.3-8.

___________________________________________________________________________

53

Thit k ln nht c thc hin nh may uranium Rossing, Ty nam chu phi
(Namibia). Cc tng l cc thng hnh ch nht lm bng b tng lt cao su, cao 3,8m
vi kch thc d tr l 6,2m. C 4 dng song song, vi tng nng sut 3600m
3
/h, i
qua 5 tng t so le nhau, tc b mt l 23m/h. Nha trong mi tng l 26m
3
, tng
lng nha s dng l 914m
3
.
3.3.4. Loi thng khuy (stirred tank)
Phn ng ca nha vi dung dch trong mt ci cc c khuy trn hay c thc
hin trong phng th nghim kho st ng hc ca phn ng. Khi p dng trong
quy m ca mt nh my, s gp nhng rc ri sau:
-Khuy vi tc va phi trnh mi mn nha
-Thng trong dy chuyn phi c hiu sut chuyn ho cao
-Nng nha trong huyn ph phi thp
Vi k thut ny, ng dng chnh l trong h m dng lng cp vo cha cht
rn nh mn c th lm tt tng c nh hay c th y nha ni ra khi tng si do
khi lng ring hay nht ca cht lng. Cng ngh ny c s dng thu hi
uranium t qung c thnh phn khong st cao. Cc khong ny to ra mt khi nho
lm chi ph lc cao ln v v vy ny sinh ra bi ton tch kim loi ho tan trc tip t
dch r (leach pulp). Cc nh my M trong nhng nm 50, hot ng trn nguyn l
ny v c gi l kiu nha trong bn (resin-in-pulp-RIP). Phng php khuy trn
c l n gin nht l sc kh vo y thng trn.
Mt v d in hnh th hin trn hnh 13.3-9.

___________________________________________________________________________

54
Kh s nng bn ln n mt sng rung, tng trn v dng kh hot ng lin
tc to lm cho dng nha chuyn ng ngc chiu vi dng dch qung (pulp:
qung nghin nh trong nc). Thit b n gin ny s dng thu hi vng t nc
qung sau khi chit (leach pulp) bng than hot tnh kch thc 2-4mm. Cng ngh
ny c a thch tch vng mt s nh my mi ca M, Canada, c, Nam phi.
S cng ngh n gin trong nh my tinh ch vng gm nhng thit b n
gin s dng RIP, nhng thit b c im khc bit c bn l gii hp vng di p
sut v ti sinh than trong l nung 600-700
o
C.
Vn chnh trong thit k hot ng theo nguyn l RIP l phi c nhng mng
c th tch nha (hoc than hot tnh) trong dung dich qung chy trn ca mi
thng v cui cng n dng thi.iu ny khng ch gy tt do cn m cn lm hng
thit b v mi mn ht nha khi rung ng. Carman v Read th nghim trn mt thit
b pilot c gng lm ni cc ht nha trong dung dch qung vi mong mun pht trin
cng ngh RIP khng c li lc thu hi vng v uranium.
tng mi pht trin: chuyn tng si ca nha ni trong thit b nc r, gi l
nha trong nc r (resin-in-leach) RELIX. tung mi ny khng thnh cng khi p
dng trn quy m ln do vy, pht trin ch tp trung vo t c nng sut cao
vi mi mn thp nht bng cc tm li.
Mt dng li c p dng rng ri Nam Phi trong cc nh my trao i ion
la DSM (Dutch Sate Mines), li vi dy c tit din hnh ch nht. Cc thit b ny
i hi p sut tnh thp, khng di chuyn, gn chc chn. Mt loi khc do Laxen v
ng nghip ngh, cng tng t vi kiu ca Shoemaker. C hai thit k li chy
trn t chm di b mt ca dung dch qung v dng chy tip tuyn vi mng lc.
Laxen v cng s t c hiu ng ny bng cch bm kh qua mng, vi tm chn
sau mng dng chy rung ng c to ra bi cc bng kh; trong kiu ca
Shoemaker cc nh hng tng t cng c to ra khi a xung khuy trn. Tc
dng dung dch qung qua mng vi tc b mt l 120m/h c th t c trong
thc t trong thit k ca Laxen v ng s. Arden v ng s s dng xung thp
lm sch mng trong thit k kiu RIP.S dng kh khuy trn trong dung dch
qung c p dng trong cng nghip khong sn. Nng lng dng cho khuy trn
gim so vi khuy c hc - thng hiu qu hn nhng chi ph tng. Hnh 13.3-10,
___________________________________________________________________________

55
mt kiu nh my thu hi vng t nc r ca dung dch qung Nh my s dng thit
b khuy trn ng c d tr khi ng sau khi tt.

The slots cut into the draft tube follow a suggestion from Australia. Cnh khuy
c hn vao phn trn ca ng m bo mc trn ca dch qung sa lng.
Thit k khuy c hc da trn tinh ton nng lng cn thit lm l lng cc
ht rn trong thng. Cc gi tr ny c sn i vi mi loi cnh khuy song khng
my tin cy, i khi cho kt qu tri ngc nhau. Cc nh hng ca khuy trn ln
tc mi mn ca nha hay carbon phi c xem xt cn thn.

___________________________________________________________________________

56
Ph lc

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57

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58
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59

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