bao cao semina sfe dlieu 3
TRANSCRIPT
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Ni dung :
S lc v cht lng siu ti hn v SFE
Qu trnh xy ra trong SFE
CHT LNG SIU TI HN
1. Gii thiu:
Khi nhit v p sut ca cht lng trn im ti hn ca n, cht lng
c xem l trong vng ti hn v c g l cht lng siu ti hn, ni
m khng c s khc bit giu pha lng v kh.
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Nhit ti hn ca cht lng c xc nh nh l nhit cao nht m
cht kh c th ha lng khi tng p sut ca h thng. Tng t th, p sut
ti hn l p sut cao nht ca cht m cht lng c th chuyn thnh cht
kh khi tng nhit ca h thng.
Cht lng siu ti hn c th to ra t cht kh hoc lng, khng th t
cht rn c. Khi cht lng trong trng thi siu ti hn n s mang nhiu
c tnh ca c cht kh v cht lng.
Trong sut 10 nm va qua, ng dng ca k thut siu ti hn c
c nhng bc tin nhy vt v kh nng c th s dng cho nhiu
nguyn liu ha hc khc nhau v thay th dung mi hu c trong nhng
qu trnh ha hc khng nhng trong lnh vc cng nghip dc phm m
cn trong nhng ngnh cng nghip ha hc khc.
2. Nhng u im ca vic s dng cht lng siu ti hn so vi nhng
phng php khc:
- Cht chit xut c tinh khit cao hn.
- Khng tn ng dung mi chit trong sn phm.
- Gim gi thnh ca qu trnh sn xut.
- Chn lc.
- Phn tch tt hn.
- Thn thin vi mi trng.
- Gim s bin cht hay phn hy ca sn phm nhy cm vi nhit(v
s dng nhit khng cao).
3. S lt v lch s:
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L phng php khng c hi, thn thin vi mi trng, chi ph hp
l v vn hnh vi iu kin nhit v p sut khng cao lm cho
phng php ny tr nn cun ht trong vic nghin cu dc phm.
S tn ti ca cht lng trng thi siu ti hn ln u tin c ch
ra bi Cagniard de la Tour vo nm 1822. T vic quan st mt chai cha
kn bng thy tinh khi tng nhit , ng quan st c s mt i s phn
pha ca cht kh v cht lng.
Tip theo sau vo nm 1879, Hannay v Hogarth bo co v
vic tng kh nng ha tan ca cloride kim loi trong cht lng siu ti
hn(Ethanol siu ti hn) p sut thp. Sau Villard chng minh rng
nhng cht kh nh Methan, Ethylen, CO2 v Nito oxid c th ha tan rt
nhiu nhng hp cht rn v lng nh comphor, acid stearic v parafin sp
ong. K t , mt s tc gi khc cng m t kh nng ha tan nguyn
liu ca cht lng siu ti hn.
Nm 1948 Diepen v Scherffer nghic cu kh nng ha tan
Napthalene trong Ethylen siu ti hn, mt s nghin cu theo sau xem xt tan ca napthalen khi s dng cht lng siu ti hn khc nhau.
Sut t nhng nm u n gia th k 20 phng php ny c
ch n nhiu. Nm 1936, Welson et al thc hin trn propan bng qu
trnh kh asphalt khi h s dng propan c tng kh nng ha tan
trng thi siu ti hn v phn tch c nhng phn khc nhau nh
parrafin sp ong, asphalt, tinh khit ha du nh t du nhn nguyn liu.Qu trnh ny cng to ra s pht trin ca qu trnh Solexol(loi kh c tnh
acid) cho vic tinh khit ha v chit xut vitamin A t du c v nhng
triglicerid khng bo ha t rau qu s dng propan siu ti hn.
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Sau vo nm 1971 qua trnh ny c s dng tch cafein t ht
caf m n tr thnh mt ng dng quan trng ca cht lng siu ti hn
trong mc nh thng mi trong giai on ny. Trong cng nghip dc
phm s dng cht lng siu ti hn ln u tin c s dng trong qutrnh lm gim v ng nht kch thc tiu phn v v th lm tng sinh kh
dng. V vic s dng n rng ri trong cng nghip dc phm bt u
sut nhng nm 1980-1990.
4. c tnh ca cht lng siu ti hn.
Ni chung, cht lng siu ti hn nhng tnh cht trung gian ca cht
kh v cht lng. Bng vic thay i nhit v p sut ca cht lng, nhng
c tnh ca cht lng siu ti hn c th tr nn ging cht kh hoc ging
cht lng. Cht lng trng thi siu ti hn c th khuych tn xuyn qua
cht rn ging nh kh v ha tan nguyn liu ging nh cht lng. Thm
vo , khi gn ti im ti hn mt s thay i nh v p sut hay nhit
cng to nn mt s thay i ln v mt , lm bin i nhiu c tnh ca
cht lng siu ti hn trong c kh nng ha tan cc cht. S thay i khnng ha tan ny xy ra ch vi mt s thay i nh nhit v p sut cho
chng ta t do chn la cht lng siu ti hn thch hp cho mt mc ch
c th no . V th cht lng siu ti hn rt thch hp cho vic thay th
cc dung mi hu c trong lnh vc cng nghip v trong phng th nghim.
V k thut ng dng cht lng siu ti hn c gi l cng ngh siu ti
hn.
Trong Bng 1 l nhng iu kin ti hn ca mt s phn t c s
dng ph bin nh nhng cht lng siu ti hn.
Bng 1. Critical properties of various solvents (Reid et al., 1987)
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Dung mi
Khi lng
phn t
Nhit
ti hn
p sut ti
hn
Khi lng
ring ti hn
g/mol K MPa (atm) g/cm3
Carbon dioxide (CO2) 44.01 304.1 7.38 (72.8) 0.469
Water(H2O)
(acc. IAPWS)18.015 647.096
22.064
(217.755)0.322
Methane (CH4) 16.04 190.4 4.60 (45.4) 0.162
Ethane (C2H6) 30.07 305.3 4.87 (48.1) 0.203
Propane (C3H8) 44.09 369.8 4.25 (41.9) 0.217
Ethylene (C2H4) 28.05 282.4 5.04 (49.7) 0.215
Propylene (C3H6) 42.08 364.9 4.60 (45.4) 0.232
Methanol (CH3OH) 32.04 512.6 8.09 (79.8) 0.272
Ethanol (C2H5OH) 46.07 513.9 6.14 (60.6) 0.276
Acetone (C3H6O) 58.08 508.1 4.70 (46.4) 0.278
Bng 2 Ch ra s khc nhau v mt , khuych tn v nht ca cht
lng , kh, cht lng siu ti hn in hnh.
S so snh gia Kh, Lng v Cht lng siu ti hn
T trng nht khuych tn
http://en.wikipedia.org/wiki/Kelvinhttp://en.wikipedia.org/wiki/Pascal_(unit)http://en.wikipedia.org/wiki/Atmosphere_(unit)http://en.wikipedia.org/wiki/Carbon_dioxidehttp://en.wikipedia.org/wiki/Water_(molecule)http://en.wikipedia.org/wiki/IAPWShttp://en.wikipedia.org/wiki/Methanehttp://en.wikipedia.org/wiki/Ethanehttp://en.wikipedia.org/wiki/Propanehttp://en.wikipedia.org/wiki/Ethylenehttp://en.wikipedia.org/wiki/Propylenehttp://en.wikipedia.org/wiki/Methanolhttp://en.wikipedia.org/wiki/Ethanolhttp://en.wikipedia.org/wiki/Acetonehttp://en.wikipedia.org/wiki/Pascal_(unit)http://en.wikipedia.org/wiki/Atmosphere_(unit)http://en.wikipedia.org/wiki/Carbon_dioxidehttp://en.wikipedia.org/wiki/Water_(molecule)http://en.wikipedia.org/wiki/IAPWShttp://en.wikipedia.org/wiki/Methanehttp://en.wikipedia.org/wiki/Ethanehttp://en.wikipedia.org/wiki/Propanehttp://en.wikipedia.org/wiki/Ethylenehttp://en.wikipedia.org/wiki/Propylenehttp://en.wikipedia.org/wiki/Methanolhttp://en.wikipedia.org/wiki/Ethanolhttp://en.wikipedia.org/wiki/Acetonehttp://en.wikipedia.org/wiki/Kelvin -
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(kg/m3) (Pas) (mm/s)
Kh 1 10 110
Cht lng siu ti
hn1001000 50100 0.010.1
Cht lng 1000 5001000 0.001
Thm vo , khng c sc cng b mt cht lng siu ti hn cng
nh khng c mt phn cch lng-kh nn lm tng c tnh di ng cadung mi siu ti hn n c th thm nhp vo trong cht rn c l xp nh
hiu qu hn cht lng dn n s chuyn khi v chit xut s nhanh hn.
S chuyn sang pha siu ti hn ca CO2
hnh ny chng ta c th thy c s
phn cch 2 pha d dng ca CO2
Khi tng nhit b ng phn
m dn.
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Tng nhit cao hn na s lm cho t
trng ca cht kh v cht lng gn nhau hn,
ng phn cch pha vn tn ti nhng kh
quan st.
Khi t n nhit v p sut ti hn
th khng cn phn bit c 2 pha na,
ng phn cch cng khng cn to thnh
mt pha ng nht gi l pha siu ti hn.
Mt trong nhng c tnh quan trng ca cht lng siu ti hn l ha
tan c nguyn liu trong cht lng. Kh nng ha tan ca cht lng siu
ti hn c xu hng tng theo s tng ca t trng ca cht lng( nhit
hng nh). V t trng tng theo p sut nn kh nng ha tan cng c xu
hng tng theo p sut. Trong khi mi quan h vi nhit t phc tp
hn. Vi mt mt hng nh, kh nng ha tan tng theo nhit . Tuy
nhin, khi gn vi im ti hn, mt c th gim mnh khi nhit tng.
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Chnh v th, khi gn vi nhit ti hn, kh nng ha tan thng gim khi
tng nhit , sau tng tr li.
Tt c nhng cht lng siu ti hn u hn ha vi nhau to thnh
hn hp mt pha iu ny c m bo nu im ti hn ca hn hp c
vt qu. im ti hn ca hn hp 2 thnh phn c th c tnh ton bng
phng php s hc ca nhit ti hn v p sut ti hn ca 2 cht lng.
Tc(hh) = (t l mol ca A) x TcA + (t l mol ca B) x TcB.
chnh xc hn, im ti hn c th c tnh ton da vo phng
trnh trng thi nh ca Peng Robinson, hoc bng phng php cng cc
thnh phn tham gia( group contribution methods).
Biu cc pha ca vt cht
http://en.wikipedia.org/w/index.php?title=Group_contribution&action=edit&redlink=1http://en.wikipedia.org/w/index.php?title=Group_contribution&action=edit&redlink=1 -
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Figure 1. Biu m t CO2 theo nhit v p sut
Figure 2.
Biu ca CO2 theo t trng v p sut
Hnh 1 v 2 m t cc pha ca vt cht. Trong s ca p sut-
nhit (hnh 1) im si l ni tch bit ra pha kh v pha lng v kt thc
im ti hn, ni m pha kh v pha lng bin mt v tr thnh mt phasiu ti hn. iu ny c th c quan st trong biu m t theo t
trng-p sut ca CO2, nh c m t trong hnh 2. di nhit ti
hn v d nh 280k, khi p sut tng, kh nn li v cui cng( khong trn
40bar) c c li thnh cht lng c hn, to nn s ngt qung ca
ng thng(ng chm dc). H thng gm 2 pha trng thi cn bng,
1 cht lng c c v 1 cht kh c khi lng ring thp, Khi n gn nhit
ti hn(300K), mt ca kh trng thi cn bng tr nn c hn, v
mt ca cht lng th thp hn. Ti im ti hn(304.1K v
7.38Mpa(73.8 bar)) khng c s khc bit no v t trng v 2 pha tr thnh
1 pha lng. V vy, trn nhit ti hn 1 cht kh khng th c ha
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lng bi p sut. nhit trn nhit ti hn 1 cht(310K), khi ln cn
vi p sut ti hn, ng thng gn nh thng ng. Mt s thay i nh
v p sut cng gy ra mt s thay i ln v t trng ca pha lng siu ti
hn. Nhng tnh cht vt l khc cng thay i ln khi p sut gn vi imti hn v d nh nht, tnh thm tng i v mnh ca dung mi,
m tt c u lin quan n t trng. nhit cao hn, cht lng tr nn
ging kh nh theo hnh 2 khi CO2 400K, t trng tng gn nh tuyn tnh
vi p sut.
Cht lng siu ti hn khng nhng c nht trung bnh n cao m
cn c kh nng nn cao khi vng ti hn. iu ny c ngha, thm ch chmt thay i nh v p sut cng gy ra s thay i v t trng v v vy lm
thay i kh nng ha tan. C th so snh hiu lc ha tan ca cht lng siu
ti hn vi cht kh v lng trn cn bn v t trng v nht.
Khi la chn cht lng siu ti hn cho nhng sn phm khng bn
vi nhit nh nhng protein v peptides, nhit ti hn c xem l rt
quan trng. CO2 l cht lng siu ti hn c s dng ph bin nht v nc nhit ti hn(310C) v p sut ti hn(73.8 bar) thp lm cho n tr
thnh dung mi rt hu dng cho nhng thuc v nguyn liu nhy cm vi
nhit.
5. CO2 siu ti hn:
C nhiu cht c th c s dng nh dung mi siu ti hn nhng
CO2 c s dng nhiu trong cng ngh siu ti hn trong lnh vc thcphm v thuc v tnh tr, tng i khng c, r, d kim, khng mi,
khng v, khng gy chy n v c th t trng thi ti hn d
dng(T=31.10C, P=73.8 bar), c bit l d dng thu hi li v ch cn thay
i nhit v p sut l CO2 s chuyn thnh kh v c ht ra ngoi nn
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dung mi c s dng l cht lng trng thi siu ti hn. SFE ny c th
c s dng chun b mu cho mt phn tch no , hay quy m ln
hn l loi b nhng cht tp khng mong mun cho sn phm(loi
cafein trong ht caf) hoc thu c mt sn phm mong mun. CO2 trng thi siu ti hn c s dng nhiu nht. i khi ngi ta thm
nhng cht iu chnh nh Ethanol hay Methanol. iu kin c c
CO2 trng thi sieu ti hn l trn nhit ti hn(310C) v trn p sut
ti hn(73.8 bar), v s thm nhng cht iu chnh ny vo vn khng lm
thay i iu kin to trng thi siu ti hn ca CO2.
2. Quan im v kha cnh mi trng v cht lng sn phmc iu ch bng SFE: chtlng siu ti hn l mt dung mi thay th
cho vic chit cht cn tch ra khi hn hp lng bng nhng dung mi nh
hexan, diclomethan v dung mi c th tn d li trong sn phm lm nh
hng n sc khe ngi dng. Trong khi c CO2 d dng c loi ra
khi sn phm sau qu trnh ch bin n gin bng vic gim p sut, CO2
s bay hi hon ton.
3. Tnh chn lc ca SCF: Nhng tnh cht ca SCF c th thay i
khi nhit v p sut thay i to nn chn lc ca SCF. V d nh
nhng tinh du d bay hi c th c chit xut t thc vt p sut
thp(100bar).
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4. Tc : Qu trnh chit xut da trn s khuych tn v vy dung
mi i hi phi khuych tn vo trong hn hp nn(lng hay rn) v
cht(nguyn liu) c chit xut phi khuych tn ra khi cht nn vo cht
lng. Kh nng khuych tn ca SCF nhanh hn so vi cht lng bnhthng v th qu trnh chit xut din ra nhanh hn. V v khng c sc
cng b mt v nht thp hn nhiu so vi cht lng thng thng nn
dung mi c th thm nhp vo trong tng l nh trong cht nn m qu
trnh khng th xy ra c nu l cht lng bnh thng. C hai yu t
khuych tn cao v nht thp lm tng ng k tc ca qu trnh
chit xut(mt s chit xut bng dung mi hu c c th mt vi gi trong
khi SFE ch mt khong 10-60 pht).
5. Hn ch SFE: Vic i hi p sut cao lm tng gi thnh so vi
chit xut bng phng php thng thng v th SFE ch c s dng khi
c nhng li ch ng k. CO2 c bn cht l khng phn cc v v th gii
hn kh nng ha tang mt phn no v khng th s dng chit tch
nhng cht phn cc. V th ngi ta s dng thm nhng cht ph tr
lm tng thm kh nng chit nhng c bn cht phn cc.
QU TRNH CHIT SIU TI HN
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Chit lng siu ti hn thng dng chit mt cht no trong
mt hn hp cht. Nhng thng s chnh trong qu trnh l nhit , p sut
v tc dng. Figure 2 m t s ca nhng qu trnh trong chit siu ti
hn. Bn bc chnh ca qu trnh l: chit xut, trin khai, phn tch v thu
hi dung mi.
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Mu np liu thng l cht nn rn c cho vo b phn chit xutcng vi CO2(c np vo b phn chit xut bi mt bm p sut cao).
Dng CO2 cha cht c chit xut s a n b phn phn tch thng
qua mt van gim p. Khi nhit v p sut c gim c cht chit
xut s ngng t li trong b phn phn tch trong khi CO2 s c thu hi
ti s dng li cho gian on chit xut.
Gn y ngi ta ch vo vic phn tch tng giai on ni mnguyn liu u s c chit xut vi nhng b phn chit xut ring bit
c iu kin nhit v p sut khc nhau to nn tnh chon lc khc
nhau nhm tch c hon ton nhng phn t mong mun. V dng
cht CO2 siu ti hn mang cht chit xut s c a ti nhng b phn
phn tch c iu kin nhit v p sut khc nhau ngng kt mt cch
chn lc thnh phn ring bit m h quan tm.
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S liu chit xut tiu biu t nguyn liu rn(h thng gm mt b
phn chit xut v mt b phn phn tch) c thy Figure 8, trong
lng cht chit xut c so vi lng trong mu np vo ban u cxem xt vi thi gian chit xut. Theo s liu th nhit cng cao th
ng thng s cng dc v c 2 phn: phn ng thng l lng chit xut
c trong CO2 siu ti hn v ng cong t khong l lng chit xut
gn kt vi nn rn. Trong giai on u vic chit xut b gii hn bi kh
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nng ha tan, trong giai on sau s chit xut b nh hng bi s khuych
tn v c tnh khuych tn c vai tr quan trng trong s thnh cng ca
chit siu ti hn.
Figure 8 cng cho thy nh hng ca nhit trong qu trnh chit
xut. Mt s yu t khc cng c vai tr kh quan rng trong qu trnh chit
xut l p sut, tc dng CO2 v m ca nguyn liu em chit xut.
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TI LIU THAM KHO
1. Jounal A OVERVIEW OF SUPERCRITICAL FLUIDEXTRACTION FOR HERBAL DRUGSby Karale Chandrakant K.*1,
Dere Pravin J.1, Honde Bharat S. 1,Kothule Sachin1,Kote Amol P (in
Department of Pharmacognosy, S.V._.H.TS College of B.Pharmacy,
Shrishivajinagar
(Rahuri factory), Tal-Rahuri, Dist-Ahmednagar, MS, India-413706.)
2. Jounal A review on methodology and application of supercriticalfluid technology in pharmaceutical industry by Lovenish Bhardwaj*,
Pramod Kumar Sharma, Sharad Visht, Vipin Kumar Garg, Nitin
Kumar(Department of Pharmaceutical Technology, Meerut institute of
Engineering and Technology Meerut, Uttar Pradesh, India)
3. Jounal Supercritical fluid extraction: An upcoming green
technology
4. http://en.wikipedia.org
5. Jounal Supercritical fluid extraction of organic compounds fromsolids and aqueous solutions by technical research centre of finlandespoo 1999
6. JounalIntroduction to supercriticalfluidsby Muslim Dvoyashkin
http://en.wikipedia.org/http://en.wikipedia.org/