I HC QUC GIA TP.

HCM
TRNG I HC BCH KHOA

THUYT MINH NG K
TI NGHIN CU KHOA HC SINH VIN NM 2018
(Thuc chng trnh: Chnh quy/KSTN/PFIEV)

1. TN TI 2. M S

Ch to mng phng composite GO/MA-PVA lm khan nc dung dch

furfural-nc bng cng ngh thm thu bc hi.

3. THI GIAN THC HIN thng

T thng nm n thng nm

4. CH NHIM TI (Trng nhm sinh vin)

H v tn: Trn Minh Mn MSSV: 1511952
Khoa: Khoa K Thut Ha Hc Nm hc: 2017 2018
a ch nh: p Hiu Minh B, x Hiu Nhn, huyn Vng Lim, tnh Vnh Long.
Di ng: 01882091217 Email: manhoahoc2015@gmail.com

5. THY/C HNG DN
H v tn: NGUYN HU HIU Hc v: Tin s M s cn b:
001986
Chc danh khoa hc: CBGD
Khoa, BM: K Thut Ha Hc, BM Qu Trnh v Thit B in thoi BM:
a ch nh: in thoi nh:
in thoi D: 0918498117 Fax: Email: nhhieubk@hcmut.edu.vn

6. C QUAN CH TR
Tn c quan: Trng i hc Bch Khoa i hc Quc gia Tp. HCM
a ch: 268 L Thng Kit, Q.10, Tp. H Ch Minh
in thoi: 8-8652442 Fax: 8-8653823 Email: khcn@hcmut.edu.vn
7. SINH VIN THC HIN TI

Ni dung nghin
H v tn MSSV Ch k
cu d kin c
giao
1 TRN MINH MN 1511952 Tng hp
RHA- silica
Ch to mng
ng RHA-
silica/MA- PVA
trn nn ceramic

2 TRN TH BCH 1514013 Tng hp

VN RHA- silica
Ch to mng
ng RHA-
silica/MA- PVA
trn nn ceramic

3 Kho st c tnh
v kh nng lm
khan dung dch
cn ca mng
ng
4 Kho st c tnh
v kh nng lm
khan dung dch
cn ca mng
ng

8. C QUAN PHI HP TRONG, NGOI NC V NI DUNG PHI

HP

Tn n v trong v Ni dung phi hp nghin cu H v tn ngi

ngoi nc i din n v

1 Phng TN Trng Hong Minh

im CNHH v DK Nam

2 Phng th nghim
Hunh K
chuyn ngnh V c
Phng H
213 B2
9. TNG QUAN V FURFURAL & CNG NGH THM THU BC HI
9.1 Furfural v tnh hnh sn xut
9.1.1. S lc v furfural:
Cc sn phm c sn xut c ngun gc t biomass, c bit l t ph phm
nng nghip , ang tr thnh nhng cht thay th hiu qu v y tim nng cho cc
sn phm t du m (Than , du FO,...) do qu trnh sn xut khng ch bn
vng m cn thn thin vi mi trng.
Furfural l mt aldehyde ca furan, mt loi ha cht in hnh c ngun gc t
biomass. y cng l mt loi ha cht nn quan trng trong vic to ra hn 1600
loi sn phm ha hc khc. N c nhiu ng dng quan trng trong i sng nh:
dung mi; cht trung gian tham gia vo qu trnh tng hp dc liu, ha hc,
polymer sinh hc;...
9.1.2. Sn xut furfural:
Furfural ch yu c sn sut bng qu trnh thy phn biomass c ngun gc
t cc ch phm thin nhin cha nhiu hemicellulose (nh ng, b ma, rm la,
m v ph thi sn, bao gm c cht thi t bt giy v giy, v cc ngnh cng
nghip xenluloza ethanol).

Hnh 1: S chuyn ha Hemicellulose thnh Furfural,

s dng mt cht xc tc axit rn. Ngun: (Bhaumik v Dhepe 2014).
Vi s hin din ca cht xc tc, hemicellulose b thy phn thnh pentose v
sau pentose c cyclodehydrate ha thnh furfural. Nhiu nghin cu c
cng b v vic tm ra cc cht xc tc mi v iu kin ti u ha cho qu trinh
thy phn, iu gp phn ng k trong vic ci thin hiu sut ca qu trnh
sn sut furfural bng phng php ny. Tuy nhin, vic trin khai cc phng
n cho qu trnh phn tch nc t sn phm sau khi thc hin qu trnh thy phn
vn cn nhiu hn ch.
9.1.3. Phn tch nc t dung dch ng ph furfural-nc

Chng ct thng thng: Qu trnh phn tch thng c thc hin bng
phng php chng ct dung dch sau khi thy phn, phng php ny thng ph
hp cc nh my sn xut c quy m nh. Yu cu thc t l ton b lng nhp
liu cn phi bc hi, trong khi ch c khong 3-6% trng lng ca furfural phi
c tch ra (Do h furfural-nc tn ti im ng ph), iu ny cho thy rng,
phng php ny khng tit kim hiu qu c v mt nng lng v kinh t.

Hnh 2: Gin thnh phn cn bng lng-hi ca h furfural-nc.

Ngoi ra, cn lu rng phn ng ph din ra trong sut qu trnh thy phn v
dn ti s gim sn lng furfural. Furfural to thnh c th c trng hp vi
cc ng C5 khc v chnh n; trong khi n c th b phn hy mt phn trong
dung dch axit. Kt qu l, nng sut furfural thng thng ch khong 50-70%
Nh vy, Mt yu t quan trng cn lu trong vic loi b furfural ra khi hn
hp l gim tc ng ca cc phn ng ph.

Chng ct li cun hi nc: Chng ct li cun bng hi nc, c thc

hin bng cch sc hi nc vo hn hp sn phm thu phn, tch furfural ra
khi hn hp.

u im: phng php ny c p dng rng ri v tnh n gin v d

tip cn.

Nhcim:

- Tiu th mt lng ln hi nc (khong 20 tn hi/tn furfural).

- Tiu th nhiu nng lng.
- To ra mt lng ng k nc thi cha furfural.
Nhng hn ch ny cho thy, phng php chng ct thng thng khng phi
l mt s la chn tt, cn phi c mt phng php tit kim nng lng v thn
thin vi mi trng.

Trch ly h lng-lng: Phng php trch ly h lng-lng thu ht c s

quan tm ca cc nh nghin cu. Phng php ny c thc hin bng cch thm
mt hoc nhiu loi dung mi, trong furfural c ha tan cao hn so vi trong
nc, vi hydrolysate. Furfural c tch ra khi nc, ng nht vi cc dung mi
trch ly khng ha nhp vi nc trc khi t c cn bng pha. Cui cng,
furfural c tch ra t dch chit bng cch chng ct, v dung mi trch ly c thu
hi v ti s dng.

Hnh 3: Gin pha biu din trch ly h ba cu t

ethylene glycol-furfural-nc.
 u im: Qu trnh ny gip trnh s dng hi nc, ngn chn cc vn tiu
cc ca n, ng thi, cng cho thy tnh chn lc cao i vi furfural.
Nhc im:
- Dung mi trch ly c s dng a phn l c hi, tn km v c s
dng cc t l ln hn 1.0.
- Sau khi trch ly, dung mi trch ly cn c tch ra khi furfural ti s
dng vn ny ch yu c tin hnh bng chng ct, iu ny khin qu
trnh phn tch phc tp hn nhiu.
Trch ly CO2 siu ti hn: Trch ly bng CO2 siu ti hn l qu trnh tch mt
cu t (furfural) t hn hp (furfural-nc) bng vic s dng lu cht siu ti hn
(CO2 trn nhit v p sut ti hn ln lt l 31oC v 74bar) nh dung mi trch
ly.

Hnh 4: Gin pha T-P ca CO2

u im: Ngc li vi cc cht chit sut dung mi hu c thng thng

- CO2 d dng c ch bin v ti s dng.

- Khng gy nhim mi trng.
- Hiu qu trch ly cao hn trng thi lng.
Nhc im: Tuy nhin, vic p dng k thut ny cng hn ch ch yu do i
hi cao v thit b.

S dng cht hp ph: l qu trnh s dng cc cht hp ph chn lc phn

ring hn hp c nng thp. Khi cho mt hn hp cu t c kch thc khc nhau
i qua cht hp ph th cu t c kch thc nh hn kch thc mao qun, cht hp
ph s c gi li. Cn cu t c kch thc ln hn s i ra ngoi v ta s thu c
dng vt cht c nng cao hn. Li dng tnh cht ny ca cc cht hp ph,
ngi ta s dng tch furfural ra khi hn hp furfural-nc.

Cc cht hp th thng dng l zeolite, than hot tnh, silicagelVic loi b

furfural thng c s dng cht hp th nh than hot tnh v organobentonit
 cng c p dng, nhng gp phi mt s vn nh bo ha v ti sinh cht
hp th.

Hnh 5: Minh ha c ch hot ng ca than hot tnh.

Cng ngh thm thu bc hi

C ch:
Di tc dng ca p sut chn khng hay dng kh thi qua vi tc cao,
nc t trong dung dch s thm thu qua mng. Di iu kin chn khng, nc
qua mng s tn ti di dng hi v c ngng t thu hi. Dung dch cn li s t
nng furfural cao hn. ng lc ca qu trnh ny l s chnh lch p sut ring
phn ca cc cu t gia hai b mt mng. Phng php ny l mt hng i mi v
cng hp dn bi kh nng tch khng ch c furfural-nc m cn nhiu h cht
khc nhau, s dng nhiu cht n khc nhau thay i tnh cht ca mng,...
u im:
Tit kim nng lng, dung dch khng b nhim bn nh chng ct ,trch ly,...
Nhc im:
Vic ch to v lp t mng kh phc tp v khng h r. Tuy pht trin
kh nhiu nc ngoi nhng li t c quan tm nghin cu Vit Nam v hin ti
vn cha c cng ngh hon thin cho hng i ny.
Sau khi phn tch cc phng php phn tch h furfural-nc, ta thy rng:
Vic tm ra mt phng php n gin , hiu qu, tit kim nng lng v thn thin
vi mi trng cho vic phn tch furfural t hn hp sn phm ca qu trnh thy
phn l c bit cn thit. Trong bi bo co ny chng ti xin chn phng php thm
thu bc hi cho vic nghin cu kh nng phn tch furfural-nc.

9.2. Cng ngh thm thu bc hi (Pervaporation_PV):

9.2.1. C ch thm thu bc hi:

Thm thu bc hi (PV) l qu trnh tch hn hp lng bng cch thm thu v
ha hi cc cu t khi qua mng lc. Tn ca phng php ny bt ngun t hai bc
c bn ca qu trnh: l s thm thu qua mng (permeation) v ha hi
(evaporation).

Hn hp lng p sut kh quyn tip xc vi b mt mng, cc cu t s thm

thu v bc hi qua mng. ng lc ca qu trnh ny l do s chnh lch p sut
ring phn ca cc cu t gia hai bn b mt mng, nh m dng nhp liu tng
dn nng . p sut chn khng ln dng thm thu qua mng c th c to ra bi
bm chn khng hoc dng dng kh qut.

Hnh 6: S c ch thm thu bc hi s dng(a) p sut chn khng, (b) kh qut

Kh nng phn tch ca mng c nh gi qua ba thng s c bn: thng

lng J (kg/m2.h), chn lc v ch s phn tch thm thu bc hi (pervaporation
separation index-PSI) (kg/m2.h).

1 W
J .
A t
yH 2O / yFurfural

xH 2O / xFurfural
PSI J .( 1)

Trong :

Thng lng thm thu J c nh ngha l khi lng dng thm thu
W (kg) qua 1 n v din tch mng A (m2) trong khong thi gian t (h).
chn lc c tnh ton vi x v y ln lt l nng khi lng ca nc
hoc Furfural trong dng nhp liu v dng thm thu.
PSI c trng cho hiu qu phn tch ca mng.
V mt l thuyt, mng c thng lng v chn lc ln s c hiu qu phn
tch cao hn.
Trong qu trnh thm thu bc hi, hai thng s J v c xu hng t l nghch
vi nhau v mi quan h ny c biu th qua ch s PSI. Khi PSI = 0, qu trnh
phn tch khng xy ra. l trng hp khi = 1 (mng khng c tnh chn
lc) hoc J = 0 (khng c dng thm thu qua mng).

9.2.2 u im chnh:
Sn phm to ra c tinh khit rt cao v khng gy nhim mi trng.
Cc hn hp a cu t vi chnh lch nhit si tng i nh cng c kh nng
tch ra mt cch hiu qu.
Tiu th lng nng lng nh cho qu trnh vn hnh.
C th p dng cho cc quy m khc nhau ty vo thit k phc v yu cu, mc ch
khc nhau.
H thng d dng khi ng, vn hnh v dng mt cch linh hot v ch ng.
 Trong quy m cng nghip, h thng c thit k gn gng, lp rp mt cch n
gin ti nh my.

9.2.3 ng dng ph bin:

Tch nc t hp cht hu c.
Tch hp cht hu c t nc.
Tch cc hn hp hu c.
Tng nng dung dch.

9.3. Mng Polymer cho qu trnh phn tch furfural t dung dch furfural

long:

9.3.1. Tnh hnh nghin cu v pht trin

c th ng dng vo vic tch nhiu hn hp khc nhau, nhiu loi polymer,

cht n, tc nhn to lin kt ngang c nghin cu v pht trin .
Cc loi polymer thng dng: PVA, PDMS, PVP, PVAc, PVDF, PVC
Cc cht n: graphene (GE), graphene oxide (GO), silica, chitosan
Cc loi tc nhn lin kt ngang: glutaraldehyde (GA), axit malic (MA), axit maleic
(MAE), axit furic (FA)

Trn th gii, cng ngh thm thu bc hi c xut v pht trin t

nhng nm 1950 nhng phi n tn cui th k XX cho ti nhng nm gn y mi
bt u c quan tm v nghin cu rng ri v y l hng i c nhiu u im so
vi cng ngh truyn thng. Tuy nhin, nc ta th cng ngh ny vn cn kh mi
m nn s pht trin vn cn rt hn ch. Bn cnh , nhng tr ngi v cng ngh v
vn u t cng l nhng nguyn nhn cn tr s ng dng rng ri cng ngh ngy
nc ta.

9.3.2. Poly(vinyl alcohol) (PVA):

Poly(vinyl acohol) (PVA) c cng thc ha hc l [CH2CH(OH)]n l mt
polymer dng bt mu trng, khng mi, tan nhiu trong nc. PVA c tng hp
u tin bi Hermann v Haelnel (c) vo nm 1924 bng phn ng thy phn
poly(vinyl acetate) trong cn vi kali hydroxide v cho n ngy nay vn c sn xut
t PVAc trong cng nghip.

Hnh 7: Cu trc PVA

 PVA c nhiu ng dng trong cng nghip:

X si tng hp: dng lm vi nn cho cc sn phm thu, ch thu, lp lt trong

v bnh xe cao su.
Keo dn: bn ko cao v c tnh keo dn khin chng c ng dng rng ri
trong lnh vc keo dn.
H v ph giy trong cng nghip in giy.
Cht kt dnh trong cng nghip gm: ch mt lng nh PVA cng c th lm
cho gm d dng gia cng hn rt nhiu.
Tc nhn to nh
i vi cng ngh sn xut mng thm thu bc hi cho vic tch nc t
furfural, PVA th hin mt s u im ni tri sau:

Nhn chung y l mt trong nhng polymer nn tt nht cho vic sn xut mng
thm thu bc hi tch nc t dung dch cn, tch nc t dung dch axit
axetic/nc,...
Nhng vic p dng cho h furfural-nc l cha c nghin cu no s dng phng
php ny. Nhm nghin cu ca chng ti p dng loi mng ny da trn cc tnh
cht ca n kho st kh nng phn tch ca loi polymer thng dng ny cho h
dung dch furfural-nc.
9.3.3. Graphene Oxide (GO)
GO l mt n lp graphite oxit. GO c tng hp thnh cng trong phng
th nghim trong hn mt th k trc. C ba hng tip cn chnh tng hp oxit
graphite. GO c tng hp bng cch tch lp oxy ha cc vt liu graphite, xut
hin trong nhng nm gn y l mt trong nhng vt liu nano c nghin cu
nhiu nht. Mt khc, GO l mt nguyn liu th quan trng sn xut i tr
graphene thng qua vic loi b cc nhm cha oxy, ngha l kh GO. Trong s cc
phng php kh, vic kh bng ha hc c th xy ra nhit thp hoc trung bnh
vi s tham gia ca tc nhn kh, y l mt trong nhng cch ph bin nht bin
i GO thnh graphene.
 Hnh 8: Cu trc ca grapheme oxide
Cc nhm chc cha oxy phn cc, bao gm cc nhm epoxit, hydroxy, v
cacboxy, to cho vt liu c nhiu tim nng ng dng trong cc lnh vc khc nhau
nh quang hc, cm bin kh, vt liu composite, ro cn kh v cng ngh nano sinh
hc. Hin nay, mng n GO c chng minh l ro chn hiu qu i vi vic
tch kh v cht lng. Mt s bc t ph lin quan n mng GO t c.

Nghin cu ca Geim et al. chng minh mng GO cho nc thm thu qua
nhng gi li cc phn t khc.
Nghin cu ca Kim v cc ng nghip tng hp thnh cng cc mng GO
mng nh polyme vi chn lc CO2/N2 cao.
Nghin cu ca Yu et al. mng GO siu mng c tng hp (c dy gn 1,8
nm) vi kh nng phn tch H2 c chn lc cao trong qu trnh lc n gin.
....
Kt lun: Nhng cng trnh ny chng minh rng GO l mt vt liu mng c trin
vng tch kh v cht lng. y, chng ti trnh by v mng GO tinh ch cc
dung dch nc hu c thng qua qu trnh pervaporation (PV).
Cc phng php tng hp GO
Nguyn tc: GO thu c t cc phng php oxy ha graphite (Gi) sau c
tch lp [6].
Mc d lng oxy c trong GO kh khc bit qua cc phng php iu ch khc
nhau, t l C:O khong 2:1 l gii hn trn ca mc oxy ha, d l cc phng php
oxy ha qua mt hay nhiu bc (Brodie 1859, Hummers & Offeman 1958,
Dresselhaus & Dresselhaus 2002, Duquesne 2003) [9-12].
Cc phng php tng hp:
Phng php Brodie:
Phng php Brodie cng b vo nm 1859 l phng php tin phong s dng
axit bc khi HNO3 v KClO3 l tc nhn xen k v tc nhn oxy ha. Tuy nhin,
phng php ny c nhng nhc im nh:
- Phn ng ko di trong khong bn ngy.
- Cn c bn chu k oxy ha, ra v sy t c GiO c mc oxy ha
cao.
- S bay hi axit c hi v hn hp kh NO2/N2O4 t axit bc khi HNO3.
- Kh ClO2 d gy n sinh ra khi mui clorat trn vi cc axit mnh.
Thc t, c vi v n xy ra trong phng th nghim c ghi nhn khi thc
hin phng php Brodie [13].
Phng php Staudenmaier
Nm 1898, Staudenmaier ngh s dng hn hp hai phn H2SO4 v mt phn
HNO3 kt hp vi tc nhn oxy ha KClO3. Trong trng hp ny, mt bc oxy ha
 oxy ha hon ton Gi thnh GiO. Tuy nhin, kh d n ClO2 vn cn v thi gian
phn ng vn l bn ngy.
Nhn xt: C hai phng php trn u nguy him v tn nhiu thi gian, khng thch
hp p dng trong quy m cng nghip [13].
Phng php Hummers & Offeman
Nm 1958, Hummers v Offeman pht trin mt phng php tng hp GO
v ang c s dng rng ri cho ti nay. H s dng H2SO4 vi s h tr ca
NaNO3 v KMnO4 oxy ha Gi. Phng php Hummers c nhiu u im so vi
phng php Brodie v Staudenmaier:
- Vic s dng tc nhn oxy ha KMnO4 nhm m bo phn ng hon thnh trong
vng vi gi.
- Khng c kh d n ClO2 v khng dng mui clorat.
- Vic thay th HNO3 bng NaNO3 loi b hin tng bc khi axit.
V vy, y c xem l phng php ha hn cho vic sn xut GO vi s
lng ln. Tuy nhin, y cha phi l phng php ti u v c t nht ba hn ch:
- S hnh thnh hn hp kh NO2/N2O4 do c mt NaNO3.
- Kh loi b ion Na+ v NO3- khi nc thi trong qu trnh tng hp GO v cc qu
trnh lc.
- Oxy ha khng hon ton dn n hnh thnh hn hp Gi/GO [13].
Phng php Hummers ci tin

Nm 2010, phng php Hummers ci tin loi b NaNO3, tng lng KMnO4 v
s dng hn hp axit vi t l 9:1 H2SO4/H3PO4 c cng b [14]. Tc nhn oxy
ha chnh l ion MnO4- sinh ra khi KMnO4 phn ng vi H2SO4. MnO4- tn cng
vo ni i ca alkene, hnh thnh nn diol. Nu khng c H3PO4, diol tip tc b
oxy ha thnh dione, to ra khuyt tt trong mng cacbon m sau qu trnh kh
khng th phc hi li c. Ngc li, nu c H3PO4, cu trc vng s c hnh
thnh, qua bo v nhm diol, gim thiu vic oxy ha qu mc to ra dione
[14,15].

Hnh 9: C ch phn ng oxy ha khi khng c v c H PO

3 4 [15].
 Kt lun: Bi nghin cu s dng phng php Hummers ci tin ny v c nhiu
u im ng k so vi phng php Hummers truyn thng tng hp GO v:

- Qu trnh phn ng khng ta nhit ln v sinh kh c.

- T l cacbon b oxy ha cao hn (nhiu gc OH hn).

- rGO thu c t b khuyt tt hn, dn n dn in cao hn.

9.3.4. Mng PVA s dng GO lm cht n trn nn mng phng:

Hnh 10: Cu trc mng thm thu bc hi phng GO/MA-PVA

Nh cp pha trn, mng PVA tuy c tnh cht a nc tt nhng cng th hin nhiu nhiu
nhc im v vy vic b sung GO, tc nhn to lin kt ngang v nn gm l v cng cn thit.Bi:

Do dung dch furfural nguyn liu c gia nhit 50oC nn trng n ca mng
PVA cng ln tuy tng c thng lng nh chn lc khng cao, cht lng sn
phm km.

Khi mng trng n ln, mng li polymer khng cht dn n c tnh yu, c bit h
thng lm vic di p sut chn khng kh ln nn kh nng rch mng l rt cao.

GO th hin vai tr v cng quan trng trong kh nng nh hng ti tnh cht mng:
9.3.4 Mng PVA s dng RHA-silica lm cht n trn nn gm:

Hnh 7: Cu trc ca mng ng composite trn nn gm

Nh cp pha trn, mng PVA tuy c tnh cht a nc tt nhng cng th
hin nhiu nhiu nhc im v vy vic b sung RHA- silica, tc nhn to lin kt
ngang v nn gm l v cng cn thit. Bi:
Do dung dch ethnol nguyn liu c gia nhit 50oC nn trng n ca mng
PVA cng ln tuy tng c thng lng nh chn lc khng cao, cht lng
sn phm km.
Khi mng trng n ln, mng li polymer khng cht dn n c tnh yu, c
bit h thng lm vic di p sut chn khng kh ln nn kh nng rch mng l
rt cao.
RHA-silica th hin vai tr v cng quan trng trong kh nng nh hng ti tnh cht
mng:
Cha nhiu gc silanol OH trn b mt tng tc vi cc gc OH trong mng
polymer bng cc lin kt hydro iu ny lm cho mng li polymer tr nn cht
hn gim trng n.
Cc gc silanol a nc gp phn vo vic tng kh nng tng tc vi dung dch
cn nh tng kh nng chn lc, gim bt lu lng thm thu.
Tuy nhin, khi nng silica cng ln, chng c xu hng t li vi nhau. T
dn n s xm ln ca silica vo cc lin kt ca PVA, lm tng tc gia RHA-
silica v PVA yu dn i, ph v lin kt dn ti tng lu lng thm thu v gim
chn lc ca mng, v vy vic nghin cu, la chn lng RHA-silica thm vo
l rt quan trng.
 Hnh 8: Gc silanol trn b mt silica
phn tn ca RHA-silica cng nh cc silica thng thng khc dng nh kh
km, chng c xu hng t li vi nhau khi nng ln. gii quyt vn ny,
vic thm tc nhn to lin kt ngang chng hn nh axit malic (MA) c p
dng. MA s to cc lin kt ester ni cc chui polymer li vi nhau nh mng s
cht hn, lm tng chn lc, gim lu lng thm thu v RHA-silica kh t li
vi nhau hn.
So snh vi nhng m-un mng ang c s dng rng ri, m-un mng ng
c nhiu u im vt tri nh: d ch to, v sinh, tr lc thp, kh nng chng bm
cn rt tt, din tch tip xc cao, tn tht p sut thp V vy, d chi ph u t c
phn ln hn nhng nh nhng u im vt tri, m-un mng ng vn l mt trong
nhng loi m-un ph bin nht trong ngnh cng nghip mng.

Ngy nay, m-un mng ng lun c nghin cu ci thin kh nng vn hnh,

mt trong s chnh l vic s dng vt liu gm ch to. Vi nhng c im
ni tri nh c tnh tt, bn ha, bn nhit, xp ln nn dng hi thm thu d
dng khuch tn qua, ng thi p sut chn khng d dng tip cn vi mt bn ca
mng. Chnh v vy, vic s dng m-un mng ng composite RHA-silica/MA-PVA
trn nn gm s khc phc hu ht cc nhc im cn tn ti ca mng PVA. Bn
cnh , tim nng p dng vo quy m cng nghip ca cng ngh ny rt kh thi
nu c ch trng u t nghin cu v pht trin.
9.4 ngha ca ti
T nhng tnh cht v c im nu trn, vic nghin cu v pht trin ti
ny l ht sc quan trng trong bi cnh s dng nhin liu sinh hc, tit kim nng
lng, gim pht thi ra mi trng ang c t ln hng u nc ta hin nay
ni ring v trn th gii ni chung.
Ti Vit Nam, vic sn xut RHA-silica t tro tru c ngha rt ln, ng dng
RHA-silica vo vic ch to mng lc cn nhin liu li cng c ngha hn rt nhiu.
Tuy nhin, lnh vc ny cha c quan tm nghin cu nhiu, v vy vic ch to
mng composite RHA-silica/MA-PVA trn nn gm ceramic lm khan dung dch
bng cng ngh thm thu bc hi l mt ti thit thc v y ha hn.
Hin ti, nhm nghin cu bc u c gng pht trin hng i bng cch ch to
mng composite RHA-silica/MA-PVA trn nn gm quy m phng th nghim vi
mc ch nghin cu ci thin tnh cht ca mng ng, nng cao nng sut ca mng
v hng ti c th a nghin cu ny vo quy m cng nghip trong tng lai.
Danh mc ti liu tham kho:
[1] H.N. Njenga, Dept. of Chemistry, University of Nairobi, Box 30197, Nairobi, Kenya -
Estimation of azeotropic compositions of the ethanol-water system below 760mm Hg pressure,
International Journal of BioChemiPhysics, Vol. 13, No.2, December 2004.
[2] V. Udeye*, S. Mopoung, A. Vorasingha and P. Amornsakchai, Department of Chemistry,
Faculty of Science, Naresuan University, Phitsanulok 65000, Thailand, Ethanol
heterogeneous azeotropic distillation design and construction, International Journal of
Physical Sciences Vol. 4 (3), pp. 101-106, March, 2009.
[3] P. Pruksathorn, T. Vitidsant, Production of Pure Ethanol from Azeotropic Solution by
Pressure Swing Adsorption, American J. of Engineering and Applied Sciences 2 (1): 1-7,
2009.
[4] Ghoshna Jyoti, Amit Keshav, and J. Anandkumar; Department of Chemical Engineering,
National Institute of Technology, Raipur 492010, India; Review on Pervaporation: Theory,
Membrane Performance, and Application to Intensification of Esterification Reaction,
Hindawi Publishing Corporation Journal of Engineering Volume 2015, Article ID 927068, 24
pages
[5] P. Shao , R.Y.M. Huang; Polymeric membrane pervaporation; Journal of Membrane
Science 287 (2007) 162179.
[6] Elizabeth Fonseca dos Reis , Fbia S.Campos , Andrey Pereira Lage , Romulo Cerqueira
Leitea , Luiz Guilherme Heneineb , Wander Luiz Vasconcelosc , Zelia Ines Portela Lobatoa ,
Herman Sander Mansurc; Synthesis and Characterization of Poly (Vinyl Alcohol) Hydrogels
and Hybrids for rMPB70 Protein Adsorption; Materials Research, Vol. 9, No. 2, 185-191,
2006.
[7] K.Bogeshwaran* , R.Kalaivani, Shifna Ashraf, G.N.Manikandan, George Edwin Prabhu;
Production of Silica from Rice husk; International Journal of ChemTech Research, CODEN
(USA): IJCRGG, ISSN : 0974-4290 Vol.6, No.9, pp 4337-4345, September 2014.
[8] V.P. Della et al, Rice husk ash as an alternate source for active silica production,
Materials Letters , vol. 57, p. 818 821, 2002.
[9] S. P. A. Kamath, Silica gel from rice hull ash:preparation and characterization, Cereal
Chemistry, vol. 75, pp. 484-487, 1998
[10] Majid Monshizadeh et al, Synthesis and characterization of nano SiO2 from rice husk
ash by Precipitation method, in 3 th National Conference on Modern Researches in Chemistry
and Chemiscal Engineering.

10. MC TIU CA TI
Tng hp thnh cng silica t tro tru;
Ch to thnh cng mng ng composite RHA-silica/MA-PVA trn nn
gm;
nh gi hiu qu lm khan nc dung dch cn ca mng ng ch to
c.

11. TM TT NI DUNG CA TI V QU TRNH THC HIN (ghi r

rng thnh mc)

11.1 Ni dung nghin cu

Ni dung nghin cu 1: Tng hp tin cht v ch to mng ng

- Tng hp RHA-silica t tro tru bng phng php axit-baz-axit, kho st hm

lng RHA-silica ti u.
- Ch to mng ng composite RHA-silica/MA-PVA trn nn gm.
Ni dung nghin cu 2: Kho st kh nng vn hnh v c tnh ca mng
 - Kho st kh nng lm khan nc dung dch cn ca mng ng composite RHA-
silica/MA-PVA vi s ln ph khc nhau, o cc thng s c trng J, v PSI
tm ra s ln ph ti u.
- Kho st hnh thi-cu trc-c tnh ca mng ng composite RHA-silica/MA-PVA
bng: ph hng ngoi bin i Fourier (Fourier Transform Infrared Spectroscopy -
FTIR), nhit qut vi sai (Differential Scanning Calorimetry - DSC), phn tch nhit
trng lng (Thermal gravimetric analysis - TGA), knh hin vi in t truyn qua
(Transmission Electron Microscopy - TEM), gin nhiu x tia X (X-ray
Diffraction XRD) v th nghim trng n, bn ko v gc thm t

11.2 Thc nghim

Dng c th nghim

C t, bp t, a khuy, nhit k, becker chng loi 100 mL, 250 mL, 500
mL; ng ong 50 mL, b siu m Sonic 410 (40 kHz), my ly tm (2000 rpm), cn
phn tch bn s, t sy, a petri, my khc x k,

Ha cht
Bng 4: Cc ha cht s dng

Trng
TT Ha cht K hiu ha hc c tnh Ngun gc
thi

1 Tro tru Rn Dh < 20 m Sigma Aldrich

2 Axit clohidric HCl Lng 36,46% Trung Quc

3 Natri hidroxit NaOH Rn 96% Trung Quc

4 Kali permaganate KMnO4 Rn >9% Vit Nam

6 Ethanol C2H5OH Lng 99,7% Trung Quc

7 Poly(vinyl alcohol) (C2H4O)n Rn 99,9% Vit Nam

8 Axit maleic C4H2O3 Rn 98% Vit Nam

12 ng ceramic Rn Vit Nam

11.3 Tng hp Silica

Thuyt minh quy trnh:

 RHA-silica c tng hp bng phng php axit-baz-axit. Quy trnh ny c
thc hin nh sau: cn 10 gam tro tru em nung 700 oC trong vng 4 gi. Sau ,
tin x l phn tro bng cch ra trong 50 ml dung dch HCl 3N, khuy u trn bp
80oC. Sau 2 gi, em i lc chn khng v ra tht sch bng nc ct, ly phn
cht rn cho phn ng to natri silicate vi 200 ml dung dch NaOH 1N 90oC trong
90 pht. Sau khi phn ng kt thc, i nhit h xung 30oC ri em lc chn
khng v ra vi nc ct ly phn dch. Dng dung dch HCl 1N cho t t vo
phn dch lc n khi pH= 7. Lc, ra phn cht rn v em sy 105oC trong 12
gi thu c RHA-silica.
Tro tru

Nung
HCl 3N

Tin x l

Dch
Lc chn
khng
NaOH 1N

Axit ha

Kt ta

Dch
Lc chn
khng

Sy 105oC,
12 gi

RHA-silica

Hnh 9: Quy trnh tng hp RHA-silica theo phng php axit-baz-axit

Kt qu nghin cu s b:
Thnh phn SiO2 trong sn phm RHA-silica l 99,28% trong khi hm
lng SiO2 ban u trong tro tru l 95,59%, loi b hu nhu hon ton
cc oxit kim loi khc.
Hiu sut ca qu trnh H = 73,1% (10g tro tru c x l v cho ra 7,31g
Silica)
Kch thc trung bnh ca ht 20 50 nm
Din tch b mt ring 333,918 m2/g
Gin XRD, ph FTIR, TEM

Hnh 11: Gin XRD ca RHA-silica Hnh 12: Ph FTIR ca RHA-

silica

Hnh 13: nh TEM ca RHA-silica

Gin XRD cho thy mt nh dao ng trong khong 20o n 30o c trng
c cu trc v nh hnh ca RHA-silica.
Ph FTIR nh cc ph xut hin ln lt ti bc sng 3466 cm-1, 1654cm-1,
1091cm-1 v 467 cm-1 l do s hin ca cc nhm Silanol , hydroxyl (-OH), lin
kt Si-O-Si, lin kt Si-O.
 nh TEM cho thy s kt t ca cc ht RHA-silica trong cu trc mng, iu
ny l do khi sy dung mi bay hi lin kt hydro gia nc v nhm Silanol b
ph hy hnh thnh lin kt Si-O-Si.
11.3 Kho st nng thch hp ca MA v RHA-silica

Sau khi c tng hp thnh cng, RHA-silica s c tin hnh kho st nng
thch hp bng cch tin hnh th nghim vi nng MA v RHA-silica khc nhau
vi m-un mng phng. u tin mng phng RHA-silica/MA-PVA c ch to
bng phng php bay hi dung mi. Quy trnh ny c thc hin nh sau: chun
b h huyn ph cha 2 gam PVA v SiO2 ln lt 0%, 5%, 10%, 15% v 20% khi
lng (SiO2/PVA) trong 100 ml nc ct, em khuy v gia nhit hn hp trn bp
t 80oC trong 1 gi. Sau , hm lng MA ti u (c kho st trn mng phng
MA-PVA vi nng ln lt 0%, 5%, 10%, 20%, 30%, 40% khi lng PVA
tm c hm lng ti u) c thm vo t t vo dung dch PVA v tip tc
khuy cho n khi dung dch cn khong 40 ml. Cho 20 ml dung dch ny vo a
petri (ng knh 100 mm) v bay hi t nhin trong vng 48 gi. Mng
SiO2/MA-PVA c ly ra t a petri s c sy 80oC trong 4 gi n nh
nn polyme. Mng phng sau khi c ch to s c kho st bng h thng Thm
thu bc hi vi m-un mng phng tm ra nng ti u.

Hnh 14: Cu trc v nguyn l vn hnh ca m-un mng phng

11.4 Ch to ng gm:

ng gm (kch thc di: 30cm, ng knh: 1,5 cm, b dy: 2 mm) c tng
hp ti Khoa Vt Liu- i hc Bch Khoa Tp.HCM. Trc tin ng s to ra t
phi liu gm cao lanh, oxit nhm v bt alc vi t l thch hp. Sau khi nh lng,
phi liu c nghin mn. H phi liu c sy kh, ti to ht ri trn m thch
hp to hnh bng phng php rt trong khun thch cao. Sau khi to hnh,
mc c sy 110oC trong 24 gi ri em nung non 900oC. Bn thnh phm ny
c mi li c bn t kch thc yu cu, sau c nung 1200oC. Cui cng
mi tinh c ng ng kch thc mong mun. ng gm c l xp trn b mt
chim khong 5% din tch b mt.

11.5 Ch to mng ng:

Sau khi chn c nng MA v hm lng RHA-Silica thch hp, ta tin hnh
ph dung dch c chun b ln ng gm. Trc khi tin hnh ph ng, ng gm
c sy kh trong l 100oC trong vng 30 pht. Sau ng gm c nhng ngp
bng dung dch RHA-Silica/MA-PVA chun b trc trong vng 15 pht sau tip
tc c em sy 100oC trong vng 30 pht trong l sy vi trc quay lin tc. Qu
trnh ny c lp i lp li n khi t c s ln ph theo yu cu. Sau ng s
c x l nhit 120oC trong vng 3 gi. Cui cng, ta c ng sn sng cho
th nghim kh nng lm khan cn bng cng ngh thm thu bc hi.

Hnh 15: Quy trnh ch to mng ng composite polymer trn nn gm

nh hng ca s ln ph mng

Qua th nghim thm thu bc hi, nh hng ca s ln ph mng c kho st

tm ra s ln ph ti u. Mng ng composite RHA-silica/MA-PVA vi s ln
ph ln lt l 1, 2, 3 v 4 ln c ch to v a vo h thng thm thu bc hi
 vn hnh nhm tm ra cc thng s J, v PSI tng ng vi mi ln ph. Da
vo xu hng tng gim ca thng lng, chn lc, c bit l da vo ch s PSI
ta s tm ra mng c b dy thch hp vn hnh.

11.6 Kho st hnh thi-cu trc-c tnh ca mng ng composite RHA-

silica/MA-PVA

Ph hng ngoi bin i Fourier (Fourier Transform Infrared Spectroscopy -

FTIR), nhit qut vi sai (Differential Scanning Calorimetry - DSC), phn tch nhit
trng lng (Thermal gravimetric analysis - TGA), knh hin vi in t truyn qua
(Transmission Electron Microscopy - TEM), gin nhiu x tia X (X-ray
Diffraction XRD) v th nghim trng n, bn ko v gc thm t c
kho st a ra kt lun v hnh thi, cu trc v c tnh ca mng. T kt qu
c th khng nh mng ng composite RHA-silica/MA-PVA trn nn gm c
ch to thnh cng hay cha.

11.7 Th nghim lm khan nc bng h thng thm thu bc hi:

Hnh 16: S nguyn l ca m-un mng ng

 Hnh 17: S h thng thm thu bc hi

1. Bn nhp liu 6. Van ly mu 11. Van x p

2. Bc cch nhit 7. Bm nhp liu 12. By lnh
3. Van tho liu 8. Van chnh lu lng 13. p k
4. Nhit k 9. Van lu lng bc hi 14. Bng iu khin
5. Van nhp liu 10. M-un mng ng 15. Bm chn khng

Khi ng b iu nhit

Lp mng vo m-un v kim

tra kn ca m-un

Cho dung dch cn vo bnh

nhp liu, gia nhit nhp liu.

iu chnh lu lng, bm
nhp liu vo m-un mng

Khi ng bm chn khng

Ly mu nh k

Kt thc th nghim

Hnh 18: S quy trnh th nghim thm thu bc hi

 Bng 5: Thng s k thut vn hnh h thng thm thu bc hi.

Nhit Lu lng qua Nng cn

p sut chn Thi gian vn
m-un m-un mng dng nhp liu
khng hnh (h)
mng (oC) (l/h) (% khi lng)

50 100 60 2 95

Hnh 17 v hnh 18 th hin s v quy trnh vn hnh th nghim thm thu bc

hi. Theo , by lnh c khi ng trc h nhit dn xung -20oC. Tin
hnh lp mng ng vo m-un (4) v kim tra cc v tr c th xy ra r r. Tip tc
cho cn nguyn liu vo bn nhp liu (1) v tin hnh gia nhit n 50oC. Bm nhp
liu (7) bm dung dch cn vo m-un mng v sau tun hon v li bn nhp
liu. Ti v tr m-un mng, di tc dng ca p sut chn khng -100 kPa gy ra
bi bm chn khng (15), hn hp lng s thm thu qua mng v thnh ceramic v
chuyn thnh pha hi. Dng hi tip tc c dn n by lnh (12) v c ngng
t hon ton . Dng tun hon s mang nng cao hn v tr v li bn nhp
liu. Qu trnh vn hnh trong khong thi gian l 2h. Dung dch thm thu thu c
by lnh v mu sn phm ti bn nhp liu s c em i cn v phn tch thnh
phn.

12. SN PHM CA TI (ghi r rng thnh mc)

Mng ng composite RHA-silica/MA-PVA trn nn gm vi hm lng ti u ca

cc tin cht v y cc thng s v:

- Kch thc mng ng, b dy lp ph.

- Cu trc v c tnh ca mng ng.
- Kh nng lm khan nc dung dch cn.
- Bo co trong Hi ngh Sinh vin/ Tham gia Gii thng Sinh vin
NCKH Eurka
13. KINH PH THC HIN TI
Tng kinh ph thc hin ti: 8.000.000 ng
Trong t:
Ngun trng 8.000.000 ng
Cc ngun kinh ph khc 0 ng

Ngy thng nm 2017 Ngy thng nm 2017

Ch nhim ti Thy/c hng dn

(K v ghi r h tn) (K v ghi r h tn)

Trn Minh Ngc TS. Nguyn Hu Hiu

Ngy thng nm 20 Ngy thng nm 20

Ban ch nhim khoa KT. HIU TRNG

(K v ghi r h tn) PH HIU TRNG

PGS.TS.Mai Thanh Phong