kỹ thuật xúc tác - hui - nguyễn Ánh nga
TRANSCRIPT
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
1/255
LOGO
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
2/255
www.themegallery.com
QUY NH V CCH NH GI IM
im gia hc k c tnh 20%.
im tiu lun c tnh 30%.
im thi kt thc mn c tnh 50%. Trng hp nhng sinh vin thi li (k c thi gia hc phn, kt
thc mn, tiu lun) Nu >4.5 th ch tnh phn thi bng 4.5,cc phn im khc c bo lu).
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
3/255
www.themegallery.com
GII THIU V NI DUNG MN HC
TT Ni dung Tit
1 Chng 1: Vai tr ca xc tc trong cng ngh ha hc 3
2 Chng 2: C s ca qu trnh xc tc 15
3 Chng 3: Xc tc cng nghip 7
4 Chng 4: Sn xut xc tc cng nghip 6
5 Chng 5: Cc phng php nh gi v nghin cu. 14Tng 45
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
4/255
www.themegallery.com
TI LIU THAM KHO
Charles N. Satterfields, Heterogeneous Catalysis in Industrial
Practice, McGraw-Hill, Inc., 1991.
Mukhlenov I.P., Dobkina E.I., Catalyst technology, Mir
Publishers, M. 1976.
Mai hu Khim, Bi ging K thut xc tc, NXB HQG TPHCM,2003
Imelik B.,Vedrine J.C., Les techniques physiques dtude decatalyseurs, Editions Technip-Paris, 1988.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
5/255
www.themegallery.com
Nguyn nh Hu, Trn Kim Thanh - ng ha hc v xc tc -NXB Gio dc, 1990.
Nguyn Hu Ph - Hp ph v xc tc trn b mt vt liu v c
mao qun -NXB Khoa hc v k thut, H Ni 1998. Phan Minh Tn - Tng hp hu c ha du tp 1,2 - Trng i
hc k thut TPHCM. 1992.
G.M - Chemical kindics and catalysic - Moscow. 1978.
Staley M. Walas - Reaction kinetics for chemical engineers - NewYorkToronto
TI LIU THAM KHO
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
6/255
www.themegallery.com
CHNG 1: VAI TR XC TCTRONG CNG NGH HA HC
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
7/255
www.themegallery.com
1.1 LCH S PHT TRIN XC TC.
. T 100 nm trc Phm nhumAntraquinon + acid sulfuric =
acid sulfonicHg
CH4+ O2= CO2+ H2O
Pt,Pd
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
8/255
www.themegallery.com
1.2 VAI TR CA XC TC .
1835 - Khi nim v cht xc tc v qu trnh xc tc c a ra lnu tin (Berzelius).
1875 - Cht xc tc bt u c s dng trong cng nghip (Platintrong mt lot cc qu trnh nh phn hy H2O2, oxy ho H2, CO, SO2,oxy ho hydrocacbon, ru...).
* ng dng hn ch do hot tnh Pt gim rt nhanh : b u c bi cccht nh As c trong nguyn liu cn tm bin php loi tr Cc qu trnh xc tc khc c a vo ng dng trong cng nghip :
- Oxy ha NH3thnh NO (xt Pt) iu ch axit nitric (1903 -Ostwald)
- Tng hp metanol t CO v H2(1923) ;- Tng hp hydrocacbon t CO v H2(Fischer-Tropsch1930)- Naphtalen thnh anhydride phtalic( 1920)
- Benzen thnh anhydride maleic (1928)
- Oxy ho tng phn etylen thnh oxyt etylen (Union Carbide- 1937
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
9/255
www.themegallery.com
1.1 LCH S PHT TRIN XC TC.
Trong t nhin lun tn ti cht xc tc ( xc tc men enzimtrong qu trnh iu ch dm n, ru etylic).
Th k 8 - Phn ng ester-ha xy ra nhanh hn nu H2SO4cthm vo mi trng phn ng:
Th k 18 Tc dng ca axit rn trong chuyn ha tinh btthnh ng, t st cho dehyrat ha ru, kim loi cho dehydratha.
Xc tc c s dng trong ch bin du m thnh nhin liu.Ngy nay xc tc cng nghip c tiu th nhiu: aluminosilicatv nh hnh v tinh th (zeolit).
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
10/255
www.themegallery.com
Tn phn ng Sn phm cui Cht xc tc rn
A. Cc phnngoxy ha kh
1. Oxy ha
SO2+ O2 SO3 H2SO4 Pt, V2O5, Fe2O3
CO + O2 CO2 Lm sch kh. kh v kh thi khi CO hh oxyt : Mn, Cu, Co, Ag, Pt, Pd.
H2, Hydrocacbon + O2 CO2, H2O Lm schkh thi Pt, Pd, CoO, CuO, V2O5, NiO...
mCH4+ nH2O mCO2 + nH2(st.reforming s cp)
CH4 + 3/2O2 CO + 2H2O (steam reform. th cp)
Kh tnghp Ni trn chtmang
CO + H2O H2 + CO2 (chuynha CO) H2 , CO2 Fe2O3+Cr2O3; ZnO+Cr2O3+CuO;..
2. Hydro ha
N2+ 3H22NH3 Amoniac Fe +cc cht xc tin ( K2O, Al2O3, SiO2 CaO..)
CH2=CH2+ H2CH3 -CH3 Lm schkhikh HC khng no Pt, Ni
C6H6+ H2 C6H12 hydrogen ha cc HC thm Ni, Co, Pb, Pt
RS + H2 RH2+ H2S ; RN + H2RH + NH3 lm schSP dumkhicc hpchtS,N
CoMo hocNiMo/Al2O3
CO + 3H2CH4 + H2O (metan ha) Lm schkh Ni + Cr2O3
mCO + nH2 CnH2n+1OH Rubccao Fe, cacbid Fe v cc cht xc tin
CO + 2 H2 CH3OH Metanol ZnO+Cr2O3 (+CuO+K2O)nCO + 2nH2 nH2O + CnH2n (P..F-T) Cc hydrocacbon Co+ThO2+ MgO ;
2nCO + nH2 nCO2+ CnH2n (F-T) ( lm xngtnghp Fe + Cu v ccphgia ;
CnH
2n+ H
2 CnH2n+2 (F-T) v cc chttyra.....) Fe ; Ni ; Cr2O3+ZnO
3. Dehydro ha
C4H10 H2 + C4H8 H2+ C4H6 Butadien Cr2O3; phosphat Ni+Cr2O3
C6H5C2H5 H2+ C6H5CH=CH2 Styren Cc hp cht Fe, Cr, K, Mg, Ca, CuC6H12 4H2+ C6H6 Benzen Pt, Ni
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
11/255
www.themegallery.com
B. Cc phnngaxit- baz:
1. Polymer ha
nC2H4 [ C2H4]n Polyetylen TiCl4+ AlR3 (xc tc Ziegler-Nata)
nC4H
6 [ C4H6]n Cao su butadien Na, TiCl4+ AlR3 (xc tc Ziegler-Nata)
nC4H
5CH
3[C
4H
5CH
3]
n Cao su isopren TiCl
4+ Al(C
2H
5)3(xc tc Ziegler-Nata)
2. Cracking hydrocacbon
Hydrocacbon (C20 -C25)HCC6 -C12 Nh. liucho ngc Zeolit, Aluminosilicat3. ngphn ha
butanisobutan isobutan AlCl3; AlSi; phosphat
Hydrocacbon n.C5n.C
6i.C
5-iC
6 xngisomer Pt mang trn Al
2O
3hoctrn zeolit Mordenit
4. Alkyl ha hydrocacbon
C6H6+ CH2=CH-CH3 C6H5-CH(CH3)2 Cumen cho snxutphenol H3PO4trn chtmang
C. Cc qu trnh phc tp trn xc tc a chc nng
1. Reforming
Hydrocacbon C7-C9 AromatC6-C9Xng c c.s octan cao; Cc HCthm, BTX cho ha du
Pt, Pt-Re hocPt-Sn trn Al2O3 cClo ha
2. Hydrocracking DuDO, xng Pt, Ni trn zeolit ; Ni-Mo trn Al2O3
Bng 1.1. Cc cht xc tc v qu trnh xc tc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
12/255
www.themegallery.com
1.3 ngha ca xc tc trong cngnghip v i sng
Sn xut axit sunfuric:SO2+ O2 = SO3
Hidrat ha to hnh sphm cui cng.
Cht xc tc hin nay l hn hp V2O5+ K2S2O7iu kin phn ng 450 5500C iu ch hir
Ngun nguyn liu r nht iu ch hir l kh thinnhin.CH4 + H2O= CO + 3H2(700-1000
0C, xt Ni)
CO+ H2O= CO2+ H2 (3450C, xt Fe3O4+ Cr2O3)
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
13/255
www.themegallery.com
Sn xut phn m v axit nitric:
N2 + 3H2 = NH3
Cht xc tc hin nay l Fe + hn hp K2O + Al2O3iu kin phn ng 450 5500C v 300-700 atm
Amoniac c sn xut trn th gii khong 70 triutn/nm, phn ln sn xut phn m, phn cn li
dng sn xut axit nitric bng cch oxi ha NH3
1.3 ngha ca xc tc trong cngnghip v i sng
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
14/255
www.themegallery.com
1.3 ngha ca xc tc trong cng nghipv i sng
Cracking xc tc:
L phn ng chuyn ha cc sn phm nng ca du m thnh xngc nhit si 38-2000C
Hiu sut xng cao hnCh s octan cao hnGim t l FO v kh trong sn phmCht xc tc hin nay 15% zeolit cha t him + 85%
aluminosilicat tng hp v nh hnh
Phng php hin i l tin hnh phn ng theo ch lp siFCC ( phn ng 475-5100C, 0,5-2 atm)
Cracking xtc l quy trnh xtc cng nghip c quy m ln nht. (M mi ngy c 1 triu tn du c ch bin)
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
15/255
www.themegallery.com
1.3 ngha ca xc tc trong cngnghip v i sng
Reforming xc tc:
L qu trnh thc hin mt s phn ng, trong dum chuyn ha thnh HC thm v mch nhnh, nhm
2 mc ch chnh l sn xut nhin liu xng c ch soctan cao v HC thm.
iu kin thc hin 480 - 5200C , 6- 20 atm
Phn ng chnh: ehiro ha naphten, ng phn hanaphten, ehidro vng ha, ng phn ha parafin.
Cht xc tc ph bin Pt/ Al2O3
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
16/255
www.themegallery.com
1.4. Lch s pht trin v xu hng citin ca xc tc lc ha du
Vai tr xc tc trong cng nghip ch bin du kh : Du th ban u ch cha khong 5 20% phn on nh (xng),
nh cc qu trnh ch bin c xc tc (cracking xc tc, reforming xc tc ngphn ha...) thu ti 75%xng c cht lng caohn ban u rt nhiu.
Nh c xc tc (kim loi v oxyt), t du m, than v kh t nhin thuc cc sn phm nh BTX, olefin nh...l cc nguyn liu quan trng cho ha du sn xut ra cc polymer, cht do, nha, cao su phc v cho kinh t v i sng
con ngi. Qu trnh xc tc cn ng vai tr quan trng trong sn xut cht ty ra,phm nhum v dc phm....
Chuyn ha xc tc metan vi hi nc thu c Kh tng hp (c thnh phn mCO+ nH2)vi hi nc To nguyn liu cho hng lot qu trnh sn xut khc(u l qu trnh xc tc) thu cc sn phm c gi tr s dng cao nh : metanol,hydrocacbon, amoniac, cht ty ra, ru bc cao.( Thay i cht xc tc v thay i cc iu kin cng ngh c th a dng ha cc
sn phm vi thnh phn v tnh cht khc nhau vi cc nh hng s dng khcnhau).
Xc tc hin i vi yu cu v mi trng : Cc qu trnh xc tc loi b chtc, lm sch kh thirt c quan tm. Cc qu trnh t cc thnh phn c hitrong kh thi nh hydrocacbon, CO, NOX, SO2...thnh CO2v H2O c s dngrng ri vi s c mt ca cc xc tc Pd, Pt...
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
17/255
www.themegallery.com
1.4. Lch s pht trin v xu hng ci tinca xc tc lc ha du
Xu hng ci tin ca xc tc lc du :
Cc cht xc tc cho cc qu trnh lc ha du ngy cng c ci tin theo hngp ng cc yu cu cng ngh mivyu cu v cht lng sn phm
Tin phong trong lnh vc ch to xc tc t vt liu mi (nano...)
p ng nhng i hi ngy cng kht khe hn v mi trng. C th :
- To ra nhiu th h xc tc khc nhau (i vi cc qu trnh c bn ca ch bindu nh cracking, rerorming, ng phn ha ), cng v sau cng t ra u vit hn vhot tnh xc tc(cho chuyn ha chung tng cao) hoc v la chntheohng sn phm mong mun (cho xng thnh phn c ch s octan cao hn) v bn ha hc.
- Mt khc, trong thnh phn xc tc ngi ta a thm ccph gia lm gimlng kh thi SOx, NOx ...
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
18/255
www.themegallery.com
Vai tr ca xc tc trong qu trnh lc ha du1.2. Mi tng quan gia cng ngh ch bin du kh v xc tc
Cho n ngy nay , hu ht cc qu trnh ch bin du (lc du vha du) u l qu trnh xc tc.
Mt qu trnh cng ngh c gi l qu trnh xc tc nu trong c mt hoc nhiu phn ng xy ra c s tham gia ca cht xctc.
Nu xt v tng th mt qui trnh cng ngh th cng on chuynha xc tc (qu trnh sn xut c xc tc) thc t khng chimnhiu khng gian, thit b khng phc tp, t nhn cng, chi phkhng ln.
Tuy nhin, y l cng on v cng quan trng, mang tnh quytnh cho c qu trnh.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
19/255
www.themegallery.com
Cng ngh lc du v xc tc gn b mt thit, hu c. Cngngh lun tm cch p ng trc nhng c th ring ca mith h xc tc ; ngc li, nhng i hi t pha cng nghthc y xc tc phi lun cn ci tin hoc i mi.
V d :- Cng ngh reforming xc tc loi bn ti sinh ph hp
vi h xc tc Pt-Re/Al2O3, trong khi cng ngh ti sinh lintc li c chn cho h xc tc Pt-Sn/Al2O3.
- Cng ngh cracking tng si i vi phn on cn du(cng ngh RFCC), i hi cht xc tc cha zeolit phi citin rt nhiu c pha hot tnh ln pha nn v c cht ph gianhm p ng yu cu kht khe ca cng ngh v c th canguyn liu nng.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
20/255
www.themegallery.com
CHNG 2: C S CA QUTRNH XC TC
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
21/255
www.themegallery.com
2.1 CC KHI NIM CHUNG V XC TC.
S xc tc: Xc tc l hin tng thay i tc do tc dng ca mt s cht. Hin tng bin i tc phn ng ha hc hay kch ng chng do
nhng cht m cui cng vn cphc higi l s xc tc.
c im quan trng nht ca chtxc tc l vi mt lng rt nhchtxc tc , ngi ta c th thc hin vic chuyn ho mt lng rtln cc cht phn ngTnh nng ca chtxc tc ng vai tr ht sc quan trng trong vicnng cao hiu sut phn ng, dn n gim gi thnh sn phm.
Tr cc nguyn t tr, hu ht cc nguyn t ho hc u c th lchtxc tc hoc mt thnh phn ca chtxc tc (dng kim loi, oxit,axit, baz, mui, cc phc cht ...).
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
22/255
www.themegallery.com
2.2 Phn loi phn ng xc tc:
C ch ca cht xc tc:
Xc tc dng (xc tc) lm tng tc phn ng.Xc tc m (cht c ch-inhibitor) lm gim tc phn ng.Trong thc t, ch s dng cht xc tc thun. Du hiu v pha trong phn ng:Xc tc ng th.(cht xt ha tan cng pha vi cc cht phn ng.)Xc tc d th.(xt tip xc).Xc tc chuyn pha. Cht xc tc to thun li cho s dch chuyn cc
tc cht khc pha c th tip cn nhau phn ng. Cht xc tc c sn trong h phn ng hay cho t bn ngoi vo:Phn ng t xc tc: Qu trnh xc tc xy ra bi cht xt l mt trong
cc sn phm phn ng.Phn ng c dng xc tc. Bn cht ca cht xc tc:Xc tc ha hc.Xc tc sinh hc (enzym).
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
23/255
www.themegallery.com
2.1 CC KHI NIM CHUNG V XC TC.
- khi phc hot tnh ban u sau mt thi gian s dng, cht xctc cn c ti sinh, hot ha li. Trong mt s trng hp cn bsung thm xc tc mi hoc thay th hon ton.
nh nghasau y phn no th hin ng thitnh c bn - ng dng: Cht xc tc l cht lmtng tc phn ng nhm t ti trng thi cn
bng m khng c s tiu tn ng k v lngtrong sut qu trnh.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
24/255
www.themegallery.com
2.3. Cc tc dng chnh ca cht xc tc
H2(kh) + I2(h) 2HI(kh)
Qua thc nghim, ngi ta thy rng:
C xc tc Au: Ehh= 25Kcal/mol C xc tc Pt: Ehh= 14Kcal/mol
Khng dng xc tc: Ehh= 44Kcal/mol
Lm tng tc phn ng nhng khng lm chuyn dch trng thicn bngca phn ng. Lm tng tc ca phn ng c kh nng xy ra(c th ht sc
chm) ch khng th gy nn c phn ng.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
25/255
www.themegallery.com
2.4. Cc c tnh ca cht xc tc
Tnh chn lc .( chn lc)
Hot ca xc tc.
Phn bit la chn v hiu sut.
Bo ton thnh phn ho hc, bo ton lng cht
Lm gim nng lng hot ho (Ehh).
nh hng ca iu kin bn ngoi ln s xc tc.
c trng nhit ng hc xc tc
c trng ng hc xc tc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
26/255
www.themegallery.com
2.4.1.Tnh chn lc .( chn lc)
chn lc ca xc tc: l t s tc to sn phm so vi tng tc bin i trn c s cht tham gia phn ng theo cc hng khcnhau.
la chn tch phn:
Ik= Gspchnh/ (Gspchnh+ Gspph)
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
27/255
www.themegallery.com
2.4.2.Hot ca xc tc.
Hot ca xc tc c o bngs bin i lng cht uthamgia phn ng ( hoc lng sn phm to thnh)trong mt n v thi
gianv trn mt n v ca lng cht xc tc.
Hot ca cht xc tc rn tng khi lm tng hot tnh cho mi nv b mt.
Hot thng b thay i trong qu trnh phn ng.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
28/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
29/255
www.themegallery.com
Lu : Cht xt c th s dng cho mc ch lm tng hot hoc la
chn, i khi c 2 mc ch.Trong trng hp c s a dng v snphm th yu t la chn tr nn quan trng hn.
Hot tnh xt c th c tng ln khi lm tng nhit . Tuy nhin t
tng cao d dn n: rt ngn thi gian sng ca xt, hoc tng thms lng cc phn ng(t,xt) khng mong mun. T cao s lm gim chuyn ha cc i ca cc qu trnh mang tnh ta nhit dokhng thun li v mt nhit ng hc.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
30/255
www.themegallery.com
2.4.3Bo ton thnh phn ho hc, bo ton lngcht
Cht xc tc khng b thay i vphng din ho hc cng nh vlng(mt s trng hp, cht xc tc c th b thay i v tnh chtvt l).
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
31/255
www.themegallery.com
2.4.4.Lm gim nng lng hot ho (Ehh).
Tc phn ng tngl do cht xc tc hng phn ng tin hnh theocon ng mi c nng lng hot ha nhhn
k= k0e-E/RTphng trnh Arrhenius
Phn ng xc tc ng th: k0c trng cho
tn s va chm ca phn t
entropy hat ha
s nh hng ca va chm
Phn ng xc tc d th: k0c trng cho
entropy hot ha
s lng cc trung tm hat ng dn n phn ng
)(. CfkW RTEekk /0.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
32/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
33/255
www.themegallery.com
Nng lng hot ha
A + B D
A + B AB
AB
D
A + [K] A[K]
A[K] + B AB[K]
AB[K]D + [K]
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
34/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
35/255
www.themegallery.com
Khng xc tc: A + BAB
AB D c k = k0e-E/RT
Khi c xc tc (theo thuyt hp cht trung gian):
A + [K] A[K]
A[K]+ B AB[K]
AB[K] [K] + D c kxt= k0xte-Ext/RT
So snh cc hng s tc phn ng:
Nu gi thit k0xt= k0th hng s tc phn ng thc t lnhn khi khng xc tc mt gi tr l eE/RTln, trong E = E Ext
/
0, 0, /
/
0 0
..
.
xtE RT
xt xt E RTxt
E RT
k e kke
k k e k
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
36/255
www.themegallery.com
Thc nghim cho thy:
Nu khng c CXTphnng c nng lng hot haEa= 44 Kcal/mol
CXT: AuEa= 25 Kcal/mol
CXT: Pt
Ea= 14 Kcal/mol
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
37/255
www.themegallery.com
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
38/255
www.themegallery.com
Nhit .Mi cht xc tc c mt khong nhit xc nh m khi n biu hin tc dng ti u gi l nhit thch hp(xc nh thng qua thc nghim).
p sut v nng .S lin quan gia p sut (nng ) vi hng s cn bngphn ng v mt nhit ng hc.
Dung mi.
nht. ho tan ca cc kh vo dung mi. Hng s in mi, axit v baz. S hnh thnh phc, s lin hp v s solvat ha.
nh hng ca iu kin bn ngoi ln s xc tc.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
39/255
www.themegallery.com
Tc th tch v thi gian lu.
Tc th tch l t s gia th tch kh chy qua cht xc tctrong thi gian mt gi v th tch cht xc tc: Vr= Vkh/gi/Vxt
Thi gian lu gi cht phn ng trn b mt cht xc tc t lnghch vi tc th tch (Vr): tr 1/Vr
Hiu sut th tch - thi gian: t s gia lng sn phm phnngtrong thi gian mt gitrn mt n v th tch cht xc tc.
nh hng ca iu kin bn ngoi ln s xc tc.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
40/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
41/255
www.themegallery.com
2.4.5 c trng nhit ng hc ca phn ng xctc
Phn ng thun nghch: CXT- khng lm thay i mc cn bng - lm cho phn ng mau
t ti trng thi cn bng- lm tng vn tc phn ng - tng vn tc phn ng thun bao
nhiu ln th cng lm tng vn tc phn ng nghch ln bynhiu ln
XT khng bao gi c th thay i iu kin nhit ng hc
ca qtrnh. N ch c th tc ng trong phm vi m nhitng hc cho php.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
42/255
www.themegallery.com
2.5.Phn ng xc tc ng th
c trng ca p xt ng th:
KN: Xt ng th l cht xt cng pha vi cc chttham gia phn ng.
P xt ng th ch xy ra trong pha kh v phalng, khng c xt ng th trong pha rn.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
43/255
www.themegallery.com
C ch phn ng xc tc ng th
Phn ng xc tc ng th trong pha kh.
Ly phn ng oxy ho SO2vi xc tc NO lm th d:2SO2+ O22SO3
S n gin ca phn ng nh sau:2NO + O2 2NO2
2SO2+ 2NO2 2SO3+ 2NO2SO2+ O2 2SO3
Phn ng ny c p dng trong phng php dng
phng v thp sn xut axit sunfuric trong cngnghip. Phn ng xc tc ng th trong pha lng.
Ph t th t h l
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
44/255
www.themegallery.com
Phn ng xc tc ng th trong pha lng.
Ly phn ng oxy ho ion thiosunfat bng H2O2vi xc tc lion I-lm th d:
2S2O32-+ H2O2+ 2H
+ S4O62-+ 2H2O
Phn ng xy ra theo 3 giai on v to thnh 2 hp cht trung
gian l IO-
v I2theo c ch sau:H2O2 + I
- IO-+ H2OI-+ IO-+ 2H+ I2+ H2O
I2+ 2S2O32- S4O62-+ 2I-
2S2O32- + H2O2 S4O62-+ 2H2O
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
45/255
www.themegallery.com
Nt c trng ca phn ng xc tc ng th.
Phn ng xc tc axit baz(axit v baz c tc dng xc tc).
Phn ng xc tc oxy ha - kh(xc tc l cc hp cht ca cckim loi c ha tr bin i).
Phn ng xc tc phc(xc tc l cc phc cht ca kim loichuyn tip).
Phn ng xc tc ng th trong pha khc xc tc bi cckh hot ng ha hc nh NO2, Br2
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
46/255
www.themegallery.com
Ni dung thuyt Hp cht trung gian
Xc tc tc dng vi cht phn ng to hpcht hp cht trung gian khng bn.
S to thnh hp cht trung gian l qu trnh
thun nghch xy ra nhanh. Hp cht trung gian khng bn, phn hy thnh
sn phm v cht xc tc. Tc ca qu trnht l vi nng sn phm trung gian.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
47/255
www.themegallery.com
Thuyt hp cht trung gian
Cht xc tc tng tc vi cht tham gia phnng hnh thnh sn phm trung gian km bn.
S hnh thnh sn phm trung gian l phn ng
thun nghch din ra nhanh. Sn phm trung gian phn hy chm, khng
thun nghch hnh thnh sn phm cui giiphng ra cht xc tc.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
48/255
www.themegallery.com
Thuyt hp cht trung gian
Tc chung ca phn ng t l vi nng casn phm trung gian ch khng t l vi nng cht phn ng.
Nng cht xc tc trng thi t do nm cnbng vi nng sn phm trung gian.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
49/255
www.themegallery.com
Thuyt hp cht trunggian
C th c nhiu cht phn ng cng nh nhiucht xc tc ng thi tham gia hnh thnh mtsn phm trung gian. Cc cht xc tc tng tc
nh hn hp xc tc. Mt cht xc tc c th to vi cht phn ng
ng thi nhiu sn phm trung gian.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
50/255
www.themegallery.com
Thuyt hp cht trung gian
Khi tc dng ng thi nhiu cht xc tc, tc chung ca phn ng bng tng tc ca ccphn ng thnh phn.
Cht lin hp ch yu l ion H+v OH-cng cth tham gia vo s hnh thnh hp cht trunggian.
Cht lin hp tham gia hnh thnh hp chttrung gian, lm thay i bn v tc phnhy.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
51/255
www.themegallery.com
Phn ng xc tc ng th vi xc tc axit-baz
1.N:Theo Bronsted-
Lowry:
Axit l cht cho proton. Dung dch axit trong nc l
h hai cp tn ti song songaxit-baz nh:
Baz l cht nhn proton. Baz trong dung dch nc
cng tn ti hai cp axit-baznh
bazoaxitbazoaxitAOHOHAH 32
bazoaxitaxitbazo
OHNHOHNH
423
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
52/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
53/255
www.themegallery.com
Miquan hnproton cthitlptheo l thuytcaLewis l do c stnticpintkhng cpi.
ycpin tcaH2O v NH3 cdng tophn tbn.
H3O+ + OH- H2O + OHH
H3O+ +
NHH
H
H2O + NHH
HH
+
axit
axit bazo
bazo
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
54/255
www.themegallery.com
Khi SO3 tc dngviH2O, th nc l bazov c in t t do, cn SO3 s dng trn
nn l axit.
OS
O
O
+ OOS
O
O
H
H
+ HOH OHOS
O
O
-
+ OH
H
H+
axit bazo
OH
H
+ HOH OHOS
O
O
2-
+ O
H
HH
+
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
55/255
www.themegallery.com
2. PHN LOI
Davo bnchtcacc chtxc tc, ngita phnchng thnh cc loixc tc axit-bazsau:
Xc tc axit ctrng
Xc tc axit tngqut (hotha ichtnhcht cho proton
btk,trH3O+), tcl tc dngbixc tc axit Bronsted. Xc tc electrofin khi chtxc tc l axit Lewis.
Xc tc nucleofin khi chtxc tc l bazo Lewis.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
56/255
www.themegallery.com
ng hc thuyt hpcht trung gian
Nu cn bng chuyn v pha to cht u, tcl Kc[A]
n
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
57/255
www.themegallery.com
ng hc thuyt hpcht trung gian
Phn ng lng phn t
1
2
3
4
*
*
( )
( )
k
kk
k
A K AK
AK B AKB
AKB X Y K
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
58/255
www.themegallery.com
ng hc thuyt hpcht trung gian
Ta s dng qui lut nng dng cho trnghp ny
T h phng trnh trn ta suy ra
1 2 3
**
3 4
[AK].[A][K]-k .[AK]-k .[AK][B]=0
d[(AKB) ].[AK][B]-k .[(AKB) ]=0
dt
dkdt
k
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
59/255
www.themegallery.com
ng hc thuyt hp cht trung gian
Nu k2>>k3[B] th k2+k3[B]k2
phn ng gi bc 2
* 1 3
4 2 3
* 1 34
2 3
k [A][B][(AKB) ]= [K]
k ( [B]
k [A][B]d[A]- [(AKB) ]= [K]dt [B]
k
k k
kk
k k
1 3
2
[A] [K][A][B]dt
k kdk
Tc phn ng xc tc ng th
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
60/255
www.themegallery.com
p g gt l thun vi nng CXT
k2>> k3 k2
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
61/255
www.themegallery.com
Cht kch ng
KN:Cht kch ng l cht m bn thn n khng c tcdng xt, khng lm tng tc phn ng, nhng nh cn m cht xc tc c th pht huy ti a kh nng xctc ca mnh.
Tc dng: Khi cho vo mt lng rt nh CK c th tng hot tnh
xt ln hng trm, hng ngn ln.
Lng CK ti u cho mi xt khc nhau th khc nhau.
CK lm gim iu kin khc nghit ca p.
CK lm tng bn ca xt: tng bn c hc, tng bn nhit, tng bn ha hc, gim ng c xt.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
62/255
www.themegallery.com
Phn loi cht kch ng:
Cht xc tin kt cu hoc hnh hc :a vo lm gims dnh kt ca cc vi tinh th cht xc tc, khng chochng t li vi nhau thnh cc tinh th ln, t gip
lm tng b mt hot ng ca cht xc tc Cht xc tin in t hoc cu trc : l cht m lm thay
i thnh phn ha hc ca xc tc, thay i c trngin t hoc lm bn cu trc, lm thay i bn cht cc
trung tm hot ng ca xc tc. Cht xc tin chng ng c:Bo v xc tc chng li s
u c bi tp cht hoc bi phn ng ph.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
63/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
64/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
65/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
66/255
www.themegallery.com
CHNG 2: C S CA QUTRNH XC TC
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
67/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
68/255
www.themegallery.com
2 M i b h d h
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
69/255
www.themegallery.com
2.Mt s c im c bn ca qu trnh xt d th:
1. Tnh c th: Hot tnh xt khng phi l mt tnh cht vn nng ca mt cht no m ch c th c xem xt i vi tng phn ng nht nh.
Vd: cc cht xt sinh hc-cc enzim, ch xt cho chuyn ha nhng hp cht c cuto ging nhau hoc cho chuyn ha ca mt trong s cc ng phn ca cc hpcht .
2. Tnh a nng:
Mt cht c th ng vai tr xt cho nhiu phn ng khc nhau. Vd: aluminosilicat c th hot ng xt cho mt lot cc qtrnh nh cracking, ngphn ha, bt cn i ha, ehirat ha ru. Xt Pt rt hot ng trong cc phnng reforming, ehiro ha, ..
3. Tnh a dng: Thnh phn ha hc ca cc cht rt a dng:
Rt nhiu cc nguyn t trong bng h thng tun hon c th l cht xt hoc thamgia vo thnh phn cht xt. Cht xt c th dng nguyn t, dng hp cht( cc oxit, hp kim, sunfua.,,4. Tnh khng thay i trng thi nhit ng: Xt khng t gy ra phn ng , khng lm dch chuyn cn bng m ch c tc dng
rt ngn thi gian t cn bng
2 Mt i b t h t d th
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
70/255
www.themegallery.com
2.Mt s c im c bn ca qu trnh xt d th:
5. Tnh cht nhiu giai on:
2 Mt i b t h t d th
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
71/255
www.themegallery.com
2.Mt s c im c bn ca qu trnh xt d th:
5. Tnh cht nhiu giai on: Thng chia lm 5 giai on: chuyn cht n b mt, hp ph hot
ha trn b mt, phn ng trn b mt, gii hp ph sn phm,chuyn sn phm ra khi b mt
Cc giai on hp ph cht, phn ng b mt, gii hp ph c bn
cht ha hc v xem nh cc giai on to nn phn ng xt. Giai on u( chuyn cht n b mt) v giai on cui(chuyn
sphm ra khi b mt ) khng lin quan n bin i ha hc, l qutrnh khuch tn, qu trnh chuyn khi.
Trong mt s trng hp, nu giai on u v cui l chm hn sovi cc giai on chnh ca p ha hc th tc ca qtrnh xt cquyt nh bi tc khuch tn hay chuyn cht.
Tc ton qu trnh b khng ch bi tc giai on chm nhtgi l giai on quyt nh tc .
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
72/255
www.themegallery.com
Cht xc tc d th
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
73/255
www.themegallery.com
Pha hot ng:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
74/255
www.themegallery.com
Cc tnh cht ca pha hot ng:
Hot tnh xc tc: hot tnh ng hc v hot tnhthc nghim.
Hot tnh ng hc: x da vo pt tc phn ng
Trung tm hot ng: L nhng trung tm c
ha tr t do ln nn c th hp ph cht phnng v tin hnh phn ng.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
75/255
www.themegallery.com
Thuyt Dankov
Mt phn t b hp ph ln b mt cn phi c nhiuTTH cng mt lc tc ng vo th khi mi ko dnc mi ni cc phn t b hp ph v to thnhHCTG, khi phn t mi c kh nng p vi cc phn
t b hp ph khc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
76/255
www.themegallery.com
V tr no cng c nhiu mt lm th cng cnhiu lin kt vi cht phn ng v kh nnghp ph dn n p cng cao
V tr hot ng mnh hay yu ty thuc votng loi p.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
77/255
www.themegallery.com
CHNG 3 : HP PH
1 h h
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
78/255
www.themegallery.com
1. nh ngha
Hin tnghpph l gia tngnng
mtschtnhtnh(kh, lng)trn bmt
chtxt so vitrong thtch .
Chtkh hay hicgil chtbhp
ph, cht rn xp dng ht kh hay hi
gi l chthpph v nhng kh khng b
hpphgil kh tr.
Bn cht qu trnh hp ph: L s tngtc gia c phn t vi b mt xc tc. Stng tc ny ng vai tr ch yu trong ccqu trnh xt d th.
2 Phn bit hp ph vt l v hp ph ha hc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
79/255
www.themegallery.com
2. Phn bit hp ph vt l v hp ph ha hc
Nhit hp ph Lc hp ph
S chn lc hp ph
Lng cht b hp ph
Tc hp ph
S ph thuc ca nhit
Trng thi cht b hp ph
Tnh cht ca cc mi ni hp ph Tnh thun nghch ca hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
80/255
www.themegallery.com
Qu trnh hp ph c ngha c bit trong phn ng
xc tc dth.
Trong qu trnh hpphc tora mtnhitlng,
gi l nhithpph (hoc q Kcal/mol). Bmtcnglntcxpcaxc tc cng cao th nhithpphto
ra cng ln.
Nhit hp ph
Nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
81/255
www.themegallery.com
Nhit hp ph
Trong qu trnh hp ph, nng lng t do b mt ca hgim, ngha l G < 0. ng thi hn n ca h gim(docc tiu phn ca cc cht b hp ph trn b mt cht hpph c sp xp mt cch c trt t) ngha l S < 0. Do t phng trnh nng lng ca cng thc GIBBS(Th ng
p ng tch). G = HT.S < 0. T suy ra: H < 0. Ngha l qu trnh hp ph l qu trnh ta nhit. iu ny
hon ton ph hp vi thc nghim. Hiu ng nhit ca qu
trnh hp ph c gi l nhit hp ph.
81
Nhit h h
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
82/255
www.themegallery.com
Nhit hp ph
HPVL v HPHH u to nhit Nhit to ra do HPVL nh khong t 0 5 Kcal/mol.
Nhit to ra do HPHH kh ln khong t 10 hng trmKcal/mol (tng ng nhit phn ng)..
Lc hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
83/255
www.themegallery.com
Lc hp ph
1.Hp ph vt l:
HPVL do lc Van-der waals gy ra gm cc lc:
Tng tc phn t
Lc tng tc tnh in.
2.Hpphha hc:
Trong HPHH lctngtc giachthpphv chtb
hpphl lctngtc ho hc
Lc hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
84/255
www.themegallery.com
HPHH: B mt vt rn khng bao gi bng phng l tng m c cc vt nt
gy, hoc to ra cc bc nhy hoc ch li lm
to ra cc ho tr t do trn b
Bmttinh th Bmtvtrn
Lc hp ph
Lc hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
85/255
www.themegallery.com
Lc hp ph
Hp ph ha hc
S khng cn bng lc cc nguyn t cht rn kim loi
S khng cn bng lc nguyn t trn b mt cht rn oxit
Lc hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
86/255
www.themegallery.com
Lc hp ph
Lc tng tc ho hc trong HPHH bn vng
hnrtnhiuso viHPVL.
Cu trc in t ca phn t b hp ph trongHPHH bin i su do lin kt ho hc hnh
thnh.
S chn lc hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
87/255
www.themegallery.com
S chn lc hp ph
HPHH c tnh chtchn lccao, ph thucvo
tnh chtbmtchtrnv tnh chtcachtb
hpph.
HPVL khng c s chn lc, ttc cc bmt
chtrnuc tnh chthpphl hc.
S lng cht b hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
88/255
www.themegallery.com
S lng cht b hp ph
HPHH xy ra rt t, khng hn mt lp trn b mt xc
tc (n lp).
HPVL ln bmtxc tc n lphay a lpphthuc
vo bnchthhpph,nhngthngxyra a lp,
nht l khi p sut cn bng gn vi p sut bo ho
(P/Ps1).
S lng cht b hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
89/255
www.themegallery.com
S lng cht b hp ph
Khi p sut P cn nh (P/Ps 0,1) xy ra hin tng hp ph n lp.Khi p sut tng ln s xy ra hp ph a lp
Sphthuclngchtbhpphvo P/Ps
Tc hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
90/255
www.themegallery.com
Tc hp ph
Tchpphvt l thngnhanh. Cn tchpphho hc
thngxychmdo skhc bitvnnglnghpph.
Khi xt v tc hp ph cn ch n nh hng ca tc
khuchtn, nhtl ivivtliuc mao qun,v trong mao quntckhuchtn c nhhngrtlnnqu trnh hpph.
Tccaqu trnh hpphho hccxc nhtheo phng
trnh
Khp= ko.Z.e-Ec/RT
S ph thuc ca nhit
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
91/255
www.themegallery.com
S ph thuc ca nhit
Nhittngchai qu trnh HPVL v HPHH ugim. HPVL tinhnh nhitthp(-1930C250C).
HPHH tinhnh nhitcao hn(354000C).
Nhittiucaqu trnh HPHH phthucvo cpchthpphv chtb
hpph.
V d: O2hp ph trn Ptv H2hp ph trn Cu. Ta c 2 ng biu din
Trng thi cht b hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
92/255
www.themegallery.com
Trng thi cht b hp ph
HPVL khng lm thay i trng thi cht b hp ph, vn gi nguyntrng thi ho hc ban u ca n.
HPHH xy ra lm thay i trng thi ban u ca cht b hp ph.
Cht b hp ph c th b phn ly trn b mt cht b hp ph
H2+ 2Me 2MeHCnH2n + 2+ 2Me CnH2n + 1Me + MeH
Cht b hp ph khng b phn ly
Tnh cht ca cc mi ni hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
93/255
www.themegallery.com
Tnh cht ca cc mi ni hp ph
HPHH to thnh minibnvngv tnh chtgngingnhminiha hc.
Chng c thl miniha tr,ion, ngha tr...
C sdi chuynin tgiachtbhpphv chthpph,
tcl c tc dngintphnthpphv bmtchtrn. HPVL khng hnh thnh mini.
Stngtc giaphn tbhpphvicc electron cachtrnrtyu.
Giachtrnv phn tbhpphccoi nhl 2 hthng,khng phil mthpchtthngnht.
Tnh thun nghch ca hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
94/255
www.themegallery.com
g p p
S gii hp: Hin tng ngc li vi qu trnh hp ph( xy ra khi gim p sut cht b hp ph hoc tng nhit)
Qu trnh hp ph (vt l hoc ha hc) thun nghch :
nu khi gii hp cht b hp ph c gii phng dngban u nh trc khi hp ph.
HPHH khng thun nghch: Nu lin kt gia cht HP vcht b HP tng i bn, qtrnh gii hp c th dn n
s gii phng vo th tch nhng nguyn t cht HP gnkt vi cht b hp ph.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
95/255
www.themegallery.com
HPVL bao gi cng l thun nghch: hp ph nh hp ph
HPHH khng phi bao gi cng l qu trnhthun nghch.
Tu theo c tnh mi ni lin kt ha hc mtnh cht thun nghch qu trnh hp ph khcnhau.
C nhng qu trnh HPHH kh bn vng, tothnh cc hp cht ha hc, V d nh s hpph Oxy ln kim loi to Oxyt kim loi, hoc khihp ph ln than cho CO2, CO
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
96/255
www.themegallery.com
Trng thi HPVL chuyn sang HPHH
HPVL c th l giai on ban u ca qu trnh HPHH v tng th
3.nh lut HPHH- Cc pt biu din HPHH
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
97/255
www.themegallery.com
p
Hpphngnhitcalangmuir. Trong qu trnh hpphnhngphn tkhbhpphslitrnbmt
htxc tc trong mtthigian nhtnhtipnhnnnglngv thchinqu trnh nhhpph. Qu trnh hpphv qu trnh nhhpphxyra ngthicho nkhi htphnngtctrngthi cnbng.
thitlpcphng trnh nghccho qu trnh hpph,Langmuir
ara mtsiukinsau(thuythpphngnhitcalangmuir). Ttccc tm hotha uc tnh chtnhnhau. Stm hotha khng thay itheo thigian.Mitm hotha chc thhpphmtphn tbhpph. Giacc phn tbhpphkhng c tc ngqua li.
NG HC QU TRNH HP PH L TNG
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
98/255
www.themegallery.com
NG HC QU TRNH HP PH L TNG
nghcqu trnh hpphcctrngbitc
qu trnh hpphv giihp
Phng trnh Langmuir m tcn bnghpph trn
b mt phng, c thit lp bng phng php l
thuytv c xy dng trn cc quan imvhp
phl tng
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
99/255
www.themegallery.com
Hp ph l tng
Cc tm hpph(HP) c mcnnglngnhnhau
NhitHP khng itheo gian: Q = const
Cc phn tcHP khng tngtc vinhau Mitrung tm hotngchHP 1 phn t
Trong qu trnh HP v nhhpstm HP khng i
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
100/255
www.themegallery.com
2.2 Hp ph n cht khng phn ly
A + R AR
Vn tc hp ph: vhA= kh. PA.(1 - A)
Vn tc nh hp ph : vnA
= kn. A Trong :
khs vn tc hp ph
kn: hng s vn tc nh hp ph
PA: p sut ring phn ca A
A: b mt b chim bi A
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
101/255
www.themegallery.com
trng thi cn bng: vh= vn
/(1 - )= kP
.
1
K P
KP
So snh hp ph phn ly v khng phn ly
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
102/255
www.themegallery.com
p p p y g p y
ng ng nhit hp ph khi b
phn ly vi gi tr b khc nhaung ng nhit hp ph khi khng
phn ly vi gi tr b khc nhau
Khi h t b h l
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
103/255
www.themegallery.com
Khi phn t b phn ly
C dng:
Khi bao ph b mtc xc nh:
nii
n
iii
PKPK
/1
/1
.1.
nAAn
.1
K PKP
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
104/255
www.themegallery.com
CHNG 3 : C TRNG XC TCBNG PHNG PHP HP PH
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
105/255
www.themegallery.com
3.1 Khi nim v cu trc xc tc rn xp
3.2 ng ng nhit hp ph
3.3 Cc phng trnh ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
106/255
www.themegallery.com
3.1 Khi nim v cu trc xc tc rn xp
Ccl
xp
Maoqun
3 1 Khi nim v cu trc xc tc rn xp
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
107/255
www.themegallery.com
3.1 Khi nim v cu trc xc tc rn xp
B mt ring ca vt liu (Sr); l tng din tch b mt trn mt gam cht hpph
(m2/g). ivichtkhng c lxpthbmtring khongvi chcm2/g. ivi
chtc lxpv mao mchth n khonghng ngn m2/g.
Th tch l xp ring; l khong khng gian rng tnh cho mt n v khi lng
(m3/g)
Phnbkch thcmao qun
Hnh dng mao qun: mao qunhnh tr,hnh cu,hnh khe, hnh cchai v.v
Phngphp hpphl cng ctm:bmtring, phnblxp,cc dngmao
qunv.v
Phnbkch thccacc mao qunhocphnblxpdatrn nhnggithitv
hnh dng mao qun. Sphnbcxc nhtheo sbinicathtch hoc
bmtcalxpvikch thcmao qun
Bngcc ilngctrngcutrc xpcamtsxc tc rn
Xc tc B mt ring Th tch ring ng knh
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
108/255
www.themegallery.com
Xc tc B mt ring(m2/g)
Th tch ringca mao qun
(cm3/g)
ng knhmao
qun, Ao
Than hot tnh 500 - 1500 0,6 - 0,8 10 - 20
Silicagel 200 - 600 0,4 15 - 100
Xc tc Ni cho hydro ha 200 - 250 0,3 15 - 200
Aluminosilicat xc tc cho
cracking
300 - 500 0,4 - 0,52 15 - 100
Oxyt Al hot tnh 150 - 200 0,4 20 - 100
Vanadium trn Ba -
Alumosilicat xt oxy
ha SO2
8 - 10 0,4 - 0,5 700 - 1000
Xt oxyt Fe tng hp NH3 7 - 10 0,3 200 - 1000
Xt oxyt Fe oxy ha SO2 3 - 5 0,3 - 0,4 2000 - 4000
Xt Cu nng chy 0,23 0
3 2 ng ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
109/255
www.themegallery.com
3.2 ng ng nhit hp ph
C 2 loi ng hp ph:
ng ng p hp ph: qu trnh hp ph t gi P khng i ch thay i T,
ta v c ng ng p hp ph
x = f(T)P
Dng ny t c gi tr thc t nn t c nghin cu ng ng nhit hp ph: qu trnh hp ph ta gi T khng i v ch thay
i P, ta s xy dng c ng ng nhit hp ph
x = f(P)T
Khi i lng x l hm ng bin vi p sut cn bng P
3 2 ng ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
110/255
www.themegallery.com
3.2 ng ng nhit hp ph
Khi ta tngp sutP tlP/Ps tng(P l p sut
cn bng ti thiim t, Ps l p sutbo ho ca
chtbhpph).
NuP/Ps tngt0 cho n1 th sphthucgiaxv P/Ps l ngngnhithpph.
Nu P/Ps gim t 1 cho n 0 ta c ng ng
nhitnhhpph.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
111/255
www.themegallery.com
3 3 Cc phng trnh ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
112/255
www.themegallery.com
3.3 Cc phng trnh ng nhit hp ph
C rt nhiu phng trnh m t mi quan h gia lng cht b hp ph (x)
v p sut cn bng ca pha b hp ph (x - P/Ps).
Phng trnh hp ph Henry: m t mi quan h x-P n gin nht
x = KP x- lng cht b hp ph, hp ph trn 1 gam xc tc (g/g).
P- p sut cn bng ca pha b hp ph (Torr, atm).
K- l hng s Henry.
Phng trnh Henry ch ng vng tuyn tnh nh, tc l vng c che
ph thp, ta gi l vng Henry; khng th p dng c khi nng cao, do
th tch hp ph c hn.
3 3 Cc phng trnh ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
113/255
www.themegallery.com
3.3 Cc phng trnh ng nhit hp ph
Phngtrnh ngnhithpphLangmuir: m t cn
bng hp ph trn b mt phng, c thit lp bngphngphp l thuyt; cxy dngtrn cc quan imvhpphl tng.
Cc qu trnh hpphm quan hgia1/v 1/P thomn quan h tuyn tnh l qu trnh hp ph tun theo
phngtrnh ngnhitLangmuir.Tphngtrnh trn ta suy ra cbmtbchim
3 3 Cc phng trnh ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
114/255
www.themegallery.com
3.3 Cc phng trnh ng nhit hp ph
Phng trnh Langmuir vit di dng tuyntnh:
KVOA
Vtg
m
m
.
1
1
TVmta xc nhcbmtring ca1g chthpph:
Sr= Vm.NA.Ao
NA: savodro (6,023.1023)
Ao: titdinngang ca1 phn thpph
3 3 Cc phng trnh ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
115/255
www.themegallery.com
3.3 Cc phng trnh ng nhit hp ph
Theo l thuyt th gia1/v 1/P l ng thng.
Nhng t nhng s liu
thc nghim cho phng
trnh l ng cong. iuny chng tphng trnh
khng chnh xc lm.
3 3 Cc phng trnh ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
116/255
www.themegallery.com
3.3 Cc phng trnh ng nhit hp ph
Nhng hn ch ca thuyt Langmuir
S hp ph c th xy ra theo lp a phn t
Bmtchthpphthngkhng ngnhtvnnglng,tccc vtr hpphc nhithpphkhc nhau.
C th c tng tc phn t ca cht b hp ph thuc cng mt
lp
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
117/255
www.themegallery.com
THUYT HP PH
A PHN TB.E.T
3.3 Cc phng trnh ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
118/255
www.themegallery.com
3.3 Cc phng trnh ng nhit hp ph
Phngtrnh ngnhithpphBET (Brunauer, Emnet, Tellernm1938) l mtthnh cng lnp dngcho hintnghppha
lp.Githitquan trngcaBET l:
Cc githitcaLangmuir cngcngdngvo BET.
Cc phn tbhpphutin c tngtc vinhau tora lc,lcny toiukincho lphpphth2,3...n
Tchpph(ra) trn lphpph th(i), bngvi tcnhhpph(ra) calp(i + 1).
Nhithppht lpth2 trln n lpngngtl bngnhauv bngnhitngngt
3.3 Cc phng trnh ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
119/255
www.themegallery.com
3.3 Cc phng trnh ng nhit hp ph
Phng trnh c bn ca BET l:
avdngtuyntnh
V: thtch chtbhpph
Vm: thtch chtbhpphlnnht
Tta xc nhcC v VmSr hpph
3.3 Cc phng trnh ng nhit hp ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
120/255
www.themegallery.com
3.3 Cc phng trnh ng nhit hp ph
ngngnhithpphv nhhpphtnlpsang alp
Cc dngngngnhithpphctrngcphn loibiIUPAC:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
121/255
www.themegallery.com
Cc dngvng trkhc nhau cho cc loivtliuc cutrc m ao qun
trung bnh khc nhau .
Cc phngtrnh hpphngnhit:
Phngtrnh BET
PCIP 1
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
122/255
www.themegallery.com
Nghin cucutrc xpcaVLMQ:Chnhngvtliuc cutrc v i mao qunv mao
quntrung bnh mithhinsphctptr ong qu trnh hpphvkhhpph. Do
chng ta snhg i 2 loivtliuny.
Cc phngtrnh hpphngnhit:
Vtliuv i mao qun(microp oros i ty ):
Cc zeo li t, t han hottnh, vtliukhong st vnhiuchtmang xc
tc ... c lxpbao gmchyul cc v i mao qun.
Kch thc ca chng xp x vi kch thc ca cc phn t b hpph. Do kch thc vi mao qun v qu trnh thc hin p suttng i nh nn khng c s ngng t hay hp ph a lp trongmao qun . Do khi nh hp ph khng c ng tr.
Vvyphngtrnh BET khng cn ygitrxc nhSr ing
cavtliu.
SmmS PP
CV
C
CV
I
PPV
P.
.
1
.
Cu trc xp trong s xc tc.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
123/255
www.themegallery.com
p g
Cutrc xp(lhng)lmttrong nhngctnhquan trngcaxc tc rn,thngchtxc tc rn
c bmtring rtln(hng trmm2/g), nhthan
hottnh 500 1500 m2/g . Cutrc xpphnnh
qua hng lotcc thng s: bn knh mao qun(r),
thtch mao qunvbmtring caxc tc.
Davo cutrc vm phn thnh hai loichnh:
xpvcutrc xp
http://images.google.com.vn/imgres?imgurl=http://www9.ttvnol.com/uploaded2/RatQuanTu/thanhoatinh.jpg&imgrefurl=http://www8.ttvnol.com/forum/SucKhoe/914513.ttvn&h=203&w=259&sz=14&hl=vi&start=13&sig2=NHKFdPk8VN_E9jo0TIr4kw&um=1&usg=__K884QNkt_TyJEnrxNdzOqCvun4E=&tbnid=TLqE8P12kGmkVM:&tbnh=88&tbnw=112&ei=M9HuSLHGDpr2swLLo8XnBA&prev=/images%3Fq%3D%2522THAN%2BXOP%2522%26um%3D1%26hl%3Dvihttp://images.google.com.vn/imgres?imgurl=http://www.tungvan.vn/Produce/asp-html/Anhnhom/fileanh/Impregnated_Activated_Carbon_and_Catalyst.summ.jpg&imgrefurl=http://www.tungvan.vn/Produce/asp-html/danhmuc.asp%3Fmbien1%3D19&h=100&w=100&sz=5&hl=vi&start=186&sig2=W68BmnBOa0J2rTUPJQj3JQ&um=1&usg=__5urIRUxZ0nHgZntxwr2BtuYtsuM=&tbnid=p9lDqOlbBwcLLM:&tbnh=82&tbnw=82&ei=CMzuSNuoKYGEtALM_4XtBA&prev=/images%3Fq%3D%2522than%2Bhoat%2Btinh%2522%26start%3D180%26ndsp%3D18%26um%3D1%26hl%3Dvi%26sa%3DNhttp://images.google.com.vn/imgres?imgurl=http://www.pvc.com.vn/images/stories/vatlieuloc/an.JPG&imgrefurl=http://www.pvc.com.vn/%3Fmodule%3Dcontent%26id%3D31&h=408&w=408&sz=59&hl=vi&start=376&sig2=5VBQcJ4Gbb1GxnO4egcqiQ&um=1&usg=__z-KE_hgvJjTSEFIB4UdQDThfn8w=&tbnid=sycamncpE5XMAM:&tbnh=125&tbnw=125&ei=rMvuSNjQDI6EsgK28MzpBA&prev=/images%3Fq%3D%2522than%2Bhoat%2Btinh%2522%26start%3D360%26ndsp%3D18%26um%3D1%26hl%3Dvi%26sa%3DN -
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
124/255
www.themegallery.com
Zeolit Than anthraxt Than hot tnh
L xp
Vtliumao quntrun g bnh (mesopo ros ity)
Sngngtmao qunvnhlutKelv in
i i VLMQ t b h t t h h h kh i t h
http://images.google.com.vn/imgres?imgurl=http://www.ciren.gov.vn/newsimg/Sanphamcongnghe240106.jpg&imgrefurl=http://www.ciren.gov.vn/index.php%3Fnre_site%3DNews%26nth_go%3Dsave%26sid%3D4217&h=80&w=120&sz=6&hl=vi&start=310&sig2=P9Ib5sfuOP4kGqR_6d6hyQ&um=1&usg=__P33FU-8_XoahgFd21VpWBbBp6YU=&tbnid=VNJg2FRNapQL0M:&tbnh=59&tbnw=88&ei=asvuSL3eH6aeswLkuI3VBA&prev=/images%3Fq%3D%2522than%2Bhoat%2Btinh%2522%26start%3D306%26ndsp%3D18%26um%3D1%26hl%3Dvi%26sa%3DNhttp://images.google.com.vn/imgres?imgurl=http://www.hoahocvietnam.com/Home/images/stories/photos/The-gioi-vat-lieu/a.jpg&imgrefurl=http://congnghehoahoc.org/forum/showthread.php%3Fp%3D6149&h=238&w=350&sz=15&hl=vi&start=3&sig2=14tjqQoPzV5aesh9gXn5OA&um=1&usg=__nak5gpM6UViNSjHfNNKTiX0fJ7o=&tbnid=TrGVPAh6hDpWzM:&tbnh=82&tbnw=120&ei=2dDuSKGPOaPUswLytczZBA&prev=/images%3Fq%3D%2522LO%2BXOP%2522%26um%3D1%26hl%3Dvihttp://images.google.com.vn/imgres?imgurl=http://www.dost-dongnai.gov.vn:8181/portals/0/tinkhcn/200805/20080507/080506111917.jpg&imgrefurl=http://www.dost-dongnai.gov.vn:8181/Th%25C3%25B4ngtinKHCN/Tinn%25C6%25B0%25E1%25BB%259Bcngo%25C3%25A0i/tabid/849/isd_news_news/33413/Default.aspx&h=200&w=300&sz=27&hl=vi&start=128&sig2=4vam6f0W1rpDdcMSudeL7w&um=1&usg=__d-TGGcFPQ4cPGUP2Fj_nbobAhwA=&tbnid=zAHX3W-Tn5Hq3M:&tbnh=77&tbnw=116&ei=rczuSMNEpp6zAuS4jdUE&prev=/images%3Fq%3D%2522lo%2Bxop%2522%26start%3D126%26ndsp%3D18%26um%3D1%26hl%3Dvi%26sa%3DNhttp://images.google.com.vn/imgres?imgurl=http://www9.ttvnol.com/uploaded2/RatQuanTu/thanhoatinh.jpg&imgrefurl=http://www8.ttvnol.com/forum/SucKhoe/914513.ttvn&h=203&w=259&sz=14&hl=vi&start=13&sig2=NHKFdPk8VN_E9jo0TIr4kw&um=1&usg=__K884QNkt_TyJEnrxNdzOqCvun4E=&tbnid=TLqE8P12kGmkVM:&tbnh=88&tbnw=112&ei=M9HuSLHGDpr2swLLo8XnBA&prev=/images%3Fq%3D%2522THAN%2BXOP%2522%26um%3D1%26hl%3Dvihttp://images.google.com.vn/imgres?imgurl=http://www.tungvan.vn/Produce/asp-html/Anhnhom/fileanh/Impregnated_Activated_Carbon_and_Catalyst.summ.jpg&imgrefurl=http://www.tungvan.vn/Produce/asp-html/danhmuc.asp%3Fmbien1%3D19&h=100&w=100&sz=5&hl=vi&start=186&sig2=W68BmnBOa0J2rTUPJQj3JQ&um=1&usg=__5urIRUxZ0nHgZntxwr2BtuYtsuM=&tbnid=p9lDqOlbBwcLLM:&tbnh=82&tbnw=82&ei=CMzuSNuoKYGEtALM_4XtBA&prev=/images%3Fq%3D%2522than%2Bhoat%2Btinh%2522%26start%3D180%26ndsp%3D18%26um%3D1%26hl%3Dvi%26sa%3DNhttp://images.google.com.vn/imgres?imgurl=http://www.pvc.com.vn/images/stories/vatlieuloc/an.JPG&imgrefurl=http://www.pvc.com.vn/%3Fmodule%3Dcontent%26id%3D31&h=408&w=408&sz=59&hl=vi&start=376&sig2=5VBQcJ4Gbb1GxnO4egcqiQ&um=1&usg=__z-KE_hgvJjTSEFIB4UdQDThfn8w=&tbnid=sycamncpE5XMAM:&tbnh=125&tbnw=125&ei=rMvuSNjQDI6EsgK28MzpBA&prev=/images%3Fq%3D%2522than%2Bhoat%2Btinh%2522%26start%3D360%26ndsp%3D18%26um%3D1%26hl%3Dvi%26sa%3DN -
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
125/255
www.themegallery.com
iviVLMQ trung bnh, trong qu trnh hpph,kh i p sutcn nh
hnp suthibo ha Ps th c xyra hintngchtbhpph
ngngt.
Phngt rnh Kelv in xc nhmiquan hgiatsP/Ps v rk l
bn knh cagitlnghnh thnh bn tro ng mao qun.
Hnnakh i khhpph,sbay hichtlngtmao qunthng
xyra p sutthphnPs . V do ngkhhpphkhng
trng vinghpph. Ssai khc l do p sutmao qun
cntrskhhpphcahingngngnhp suthpph.
TRr
VgfPP
k
L
S ..cos...ln
Tphngtrnh Kelv in c ththyrng: P/Ps caqu trnh thot hi
tmao qunngngtlun l un nhhnP/Ps caqu trnh hpph.
Sphn bkch thctro ng VLMQ t run g bnh
Phngphp cngdngnhiunhtlphngphp caBarrett,
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
126/255
www.themegallery.com
Joyn er v Halenda, gittlphngphp BJH. N p dngcho nhnh
khhp
ph
trnng
ng
nhit
.
Cscaphngphp lcncvo phngt rnh Kelv in viiukin
cho rng,sau khi b ay hichtlngngngt,chtlngcn lulitrn
thnh mao qunmtmng hpphalpc chiudy t. Chiudy t
cxc nhtheo cng thcsau:
Bn knh camao qunrp ctnh theo biuthc:
r
L
S
Vxt
.
trr kp
Xc nhbmtring caxc tc.
Khng mtqu trnh ngh in cuxc tc dthno hon thnh m khng
h i t b t i h b
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
127/255
www.themegallery.com
nhgixpcaxc tc, bmtr ing vmcphn bmao qunca
xc tc. nhg i cc ilngt rn phngphp ttnhtl dng
phngphp hpph.
Cng thctnh bmtring caxc tc : mmr SNnS ..
Chtbhpphthngdng didnglng- kh. GitrSm cachtb
hpphkhng phililngtuyti. Hinnay thngdng nhtl kh
trnhN2, Ar, He, Kr...
Mtkhc cngcnhtscthntrngivinhngtrnghpmchtb
hpphc tngtc ha hcvibmtchthpph. Chnh v l do
ngita thnglachncc khtrvnhitthpxc nhbmt
ring. N2 lchtkhcsdngnhiunht. Trong mtstrnghpcn
c skhuchtn tttro ng cc v i mao qun,A r lngcv in smt,sau
l He hocH2. Tuy nh in H2 c thhpphha hc,cn He th kh thao
tcthc
nghim,
do
vic
ng
dng
chngbhn
ch
.
Vicngdngphngtrnh BET tnh bmtring trthnh mt
phngphp tiu chuntro ng n gh in cuVLMQ.
T cc s liu thc nghim xy dng c biu m P/V(P P) ph
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
128/255
www.themegallery.com
T cc s liu thc nghim, xy dng c biu m P/V(Ps-P) phthuc vo P/Ps s nhn c 1 on thng nh trn hnh v
Phngtrnh BET ni chun g uc thp dngxc nhSr cattcmi
chtrnt rong phmv i g itrP/Ps cachtbhpph= 0,05 0,35 vhng
sC >1.
Xc nhxpcaxc tc.
nhg ixpcaxc tc vchtmang , cbitl xc tc vcht
mang c xpkm, ngita dng phngphp gnng. Dng phng
php ny c thnhg icxpmbngshpphnc. xp
mlilngphnxpso vibmtchung
LnghpphncW tnh th eo cng thc: %100.0
01
g
ggW
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
129/255
www.themegallery.com
xpmcxc nhtheo cng thc: %100.02
01
gg
ggB
Xc nhxpcaxc tc.
Sphn bmao quntheo kch thcngvai tr qu an trngtrong qu
trnh khuchtn bn trong caphnngha hcxc tc. xc nhphn
bmao qunxc tc theo kch thcthtrchtcnphixc nhkch
thcmao quncaxc tc.
Theo phngphp BJH p dngcho nhnh khhpphtrn ngng
nhit,ta c cng thc: trr k
Trong ,xc nhrk:
khpS
Lk
P
PTR
Vgfr
ln..
cos...
Hai thsau ybiudinsphn bthtch mao quncaA l2O3 v
SiO2
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
130/255
www.themegallery.com
TrnghpiviAl2O3 c 2 ccitngngvingknh mao qun
l 22 Ao v 41 Ao. iviSiO2 c 1 ccitngngvingknh mao
qunl 50 Ao.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
131/255
www.themegallery.com
CHNG 4: XC TC CNGNGHIP
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
132/255
www.themegallery.com
4.1. Cc yu cu c bn i vi xc tc vn hnh trongcng ngh.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
133/255
www.themegallery.com
1/ Hot tnh cao, n nh 2/ chn lc cao. 3/ Thi gian sng ca xc tc phi di 4/ bn ha, bn c, bn nhit cao 5/ Xc tc phi d iu ch v c kh nng ti
sinh c . 6/ Gi thnh hp l .
7/ Xc tc t c vi ngi
4.2. Thnh phn xc tc cng nghip.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
134/255
www.themegallery.com
Xc tc cng nghip thng bao gm 2 hocnhiu hp phn i khi rt nhiu hp phn .
Cc vai tr:
cht hot ng xc tc cht kch ng xc tc
cht mang.
Cht mang ( pha nn)
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
135/255
www.themegallery.com
L phn mang cc pha hot ng xt v xtin,gip tng cng ti a din tch b mt ca phahot tnh nh bn thn c b mt ring ln, gipqu trnh trao i nhit thun li v tng bn
c hc cho xt.
Vai tr v tnh cht chung ca cht mang:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
136/255
www.themegallery.com
Mt s tnh nng vt l v ho hc quan trng cn quan tm khi la chncht mang cho xt:
C b mt ring thun li nhm lm tng din tch b mt pha hotng(bao gm xt v xtin), gip cc tiu phn xt c th phn tn v c nhtrn mt cch tt nht.
C xp cao( gm kch thc l xp trung bnh v s phn b l xp) Gip qu trnh trao i nhit thun li, trnh gy qu nhit cc b, ngn cn
s hnh thnh cc tiu phn xt c kch thc ln. Tnh bn trong iu kin phn ng v iu kin ti sinh xt. Tnh cht c hc thun li: chng mi mn, c cng tt, chu lc nn
thch hp. Th hin Tnh tr i vi cc phn ng khng mong mun (ngc li c
th bin tnh thm tnh nng xt thun li cho phn ng mong mun).
Vd: cht mang nhm oxit trong xt reforming, ng phn ho, c x lthm vi axit tng cng chc nng axit-baz ca xt(gip chuyn ha ttcc phn ng mong mun nh ng phn , ng vng ho).
Cht mang cng c th lm thay i hng phn ng.
PHN LOI CHT MANG
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
137/255
www.themegallery.com
Cht mang c b mt ring nh: diatomit, amian, bt t vi m2/g n vi chc m2/g. Vd: thnh phn v tnh cht bt:
SiO2 60 - 70%
K2O. Na2O 2 - 4%
Fe2O3 13% Al2O3 15 -20%
CaO 23% % l xp 60%
B mt ring 10 m2/g
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
138/255
www.themegallery.com
Cht mang c b mt ring ln: oxit nhm, silicagel, tst , aluminosilicat, than hot tnhC b mt ring t vitrm n hng nghn m2/g
Cht mang B mt ringm2/g
xp(%)
Than hot tnh 500 - 1500 60-70
Silicagel 200 - 800 20-60
Aluminosilicat 300 - 500 -
Oxit nhm 150 - 200 50-70
Cc ch vn hnh xc tc trong cng nghip
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
139/255
www.themegallery.com
Lp xc tc tng tnh: c im c bn: Cc lp xt c nh, c sp xp theo dy vi h thng gia nhit
hoc lm lnh trung gian. Kim tra cht ch s thay i nhit t vng tm xt ra ngoi. Dng nguyn liu c np lin tc vo h thng l phn ng (
cha xt) v dng sn phm c ly ra lin tc. Ngng hot ng ton b h thng ti sinh xt ti ch ( i khi a
ra ti sinh ngoi h thng) khi hot tnh xt gim n mt gi tr nhtnh ( hoc t mt trng lng nht nh ca cc bm trn b mtxt)
Cng ngh ny c p dng trong trng hp xt c hnh dng ph
hp, hn ch s mt mt nguyn liu v loi tr s khuch tn hnlon. Xt thng c dng vin bi hoc dng ht n. V d : cc cng ngh hydrogen ha, hydrocracking, ng phn
ha
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
140/255
www.themegallery.com
Lp xc tc tng ng: p dng trong trng hp xt b gim hot tnh rt
nhanh( bi cc che ph) c im c bn: Lp xt chuyn ng nh nhng, lin tc trong h
thng thit b phn ng. Ton b h thng c vn hnh lin tc.
Lp xt sau khi ra khi h thng phn ng cra ngoi ti sinh ring. Sau c bm trli vo h thng ( t pha u l phn ng).
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
141/255
www.themegallery.com
Lp xt tng si: p dung trong trng hp khng gii quyt c vn truyn nhitnu s dng lp c nh.
c im: Cht xt dng bt mn (dng vi cu).
Cht xt nng c a vo l phn ng vi tc cao (60 cm/s),c pha trn vi dng nguyn liu ( gia nhit s b) ti ngnng (riser). Ti y, trong vng nhit ha hi ca nguyn liu,bi xt chuyn ng t di ln trn nh mt lp si.
S tn tht p sut nh hn, s truyn nhit tt hn so vi xt tngc nh.
lm vic c tng si cn c s kt hp gia c tnh c hcvi hnh dng xt.
Vd: Cng ngh cracking xt u s dng kiu vn hnh xt tng si.
S gim hot tnh xt:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
142/255
www.themegallery.com
Trong qtrnh lm vic thng xy ra hin tng mt hottnh xt tng phn hoc hon ton. Nguyn nhn gy ras mt hot tnh xt:
Do ng c:
S hnh thnh cc: Hin tng thiu kt, s bin tnh thnh phn v cu trc
ca xt v cht mang di tc dng ca nhit hi nc (xt axit, zeolit)
Do to thnh cc hp cht bay hi Do xt b mi mn, tht thot ca cu t hot ng d bay
hi.
Cc cht u c xc tc rn ca mt s qu trnh ha du
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
143/255
www.themegallery.com
Cht c Cht xc tc
Hp cht cha lu hunh Hydrogen ha, dehydrogen ha, reforming, ng phnha, tng hp methanol, ammoniac, methan ha
Hp cht cha oxi Xt reforming, ng phn ha, polymer ha, alkyl ha
Hp cht cha nit hu c Tt c cc xt axit hoc xt lng chc nng.
Cc hp cht thm a vng Xt axit hoc lng chc
Cc hp cht dng keo ca asphalten Xt HDS i vi cc phn on nng v cn du, cracking
Cc kim P, As
Cc halogen
Xt reforming, hydrogel ha
Xt chuyn ha CO nhit thp, tng hp metanol
Kim loi Ni,V, Na Xt HDS i vi phn on du, xt cracking, xt reforming.
Cc bin php ngn nga:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
144/255
www.themegallery.com
Cc phng php ngn nga s ng c xt: Phng php hp ph: Cho hn hp phn ng
i qua ct cha cc cht hp ph mnh.
PP ha hc: Bin cht c thnh cht khngc, ta dng phn ng oxi ha.
Bin php ngn nga s to thnh cc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
145/255
www.themegallery.com
Phn tch nguyn nhn, ngun gc to ra cc vcacbon.
S dng cc nguyn t c th ph v gc t do,hoc bng cch a vo cc kh nh hiro , hinc.
La chn cht mang c mao qun ln lmgim thiu hin tng lp kn cc mao qun do
cc v cacbon. Gim lng tm axit mnh bng cch thm cc
ph gia nh MgO, K2O
Bin php ngn nga qu trnh thiu kt do nhit :
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
146/255
www.themegallery.com
La chn cc iu kin ti u nh nhit , mitrng phn ngNhit cn khng chnghim ngt trnh xy ra hin tng qunhit sinh ra thiu kt cc b.
Gim lng hi nc trong qu trnh p.
B sung vo xt cc cht ph tr c tnh n nhcao.
Qu trnh ti sinh xc tc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
147/255
www.themegallery.com
Xc tc c th c ti sinh nhiu ln, nhng khng cxt no c tui th v hn.
Trong qu trnh ti sinh nhng thay i kt cu c- ldn n s suy gim hot tnh xt.
Vic tch t cc kim loi nng As,Pb,Cutrn b mtcht xt l qu trnh bt thun nghch
S mt mt thun ty c hc ( do va p, ri vi trongqu trnh lun chuyn) cng lm tn tht mt lng cht
xt nht nh Xtc mt hot tnh b thi ra nu cha kim loi qu(Pt,Au),
c a vo qu trnh thu hi kl qu sn xut xt mi
4.3. iu ch xc tc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
148/255
www.themegallery.com
1/ Xc tc khng c cht mang
1.1/ Xc tc kim loi
1.2/ Xc tc oxyt
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
149/255
www.themegallery.com
1.1/ Xc tc kim loi
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
150/255
www.themegallery.com
Phng php kh cc oxyt kim loi
o Tc nhn kh : H2
o Kim loi thu c c hot tnh cao
o Kch thc ht kim loi ph thuc vo iu kin kh
o i vi mi mt loi xc tc th iu kin kh c th khc nhau
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
151/255
www.themegallery.com
Phng php in ha: tc l iu ch kim loi bng
cch in phn dung dch mui.
1.2/ Xc tc oxyt
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
152/255
www.themegallery.com
t mui ban u cho kt ta bng baz thuc hydroxyt rn em nung thnh oxyt : iu ch Al2O3 dng Al2(SO4)3 v NH4OH: Al2(SO4)3 + 6 NH4OH = 2 Al(OH)3 + 3
(NH4)2SO4
2 Al(OH)3 = Al2O3 + 3 H2O
Cc yu cu c bn i vi xc tc vn hnh trongcng nghip
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
153/255
www.themegallery.com
C tnh nng xc tc cao (hot tnh xt cao) Tnh la chn ca xc tc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
154/255
www.themegallery.com
CHNG 5: PHNG PHP NGHINCU V NH GI XC TC
1. Phng php tnh:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
155/255
www.themegallery.com
Nguyn tc: L phng php tin hnh trong th tchkn cho n khi t c cn bng nhit ng hay nkhi chuyn ha hon ton mt trong s cc cht phnng ban u.
c im : Thng p dng trong iu kin c sbin i s phn t . Phng php cho php theo dinh hng ca p sut n tin trnh phn ng.
u im : Kh nng lm vic vi lng nh cht tham
gia phn ng vi cht xc tc bt k dng no v thuc ton ng ng hc trong mt th nghim viphp o c th t nhy v chnh xc cao.
Phng php tnh
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
156/255
www.themegallery.com
Khuyt im : Kt qu thc nghim thu c dngtch phn, mun nghin cu s bin i cc thng scn phi tin hnh vi phn.
Do nhc im trn, phng php t c s dngtrong nghin cu xt cng nghip.
2. Phng php dng:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
157/255
www.themegallery.com
L phng php ph bin nht nh gi hot tnh xctc.
Nguyn tc: Dng cc cht phn ng c np lin tc(vi vn tc c xc nh vo h thng phn ng ccha lp xt. C th o c v theo di s bin i ca
nng cht phn ng v cc sn phm phn ng theothi gian. c im: L phng php tch phn v lin tc, cho php thc
hin qu trnh gi cc iu kin t ra nh nhit ,nng , p sut, tc di v tc th tch ca dngvo thit b phn ng.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
158/255
Phng php dng
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
159/255
www.themegallery.com
u im:l c th xc nh c hot ca xc tc trng thi n nh ca cht xc tc, cu trc ngin, lm vic lin tc, c th kim tra cht xc tctrong cc iu kin gn vi sn xut
Nhcim:caphngphp l khng c khnngo trc tip tcphnng v kh thchin trongcc iukinl tngcachchyl tng.
3.Phng php dng vi lng:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
160/255
www.themegallery.com
L phng php n gin kho st cc phn ng xtd th, c s dng kh rng ri do tit kim xtc vcht phn ng m vn bo m qui lut ng hc caqu trnh.
Dng cht mang tr c sc qua bnh cha cht phnng v mang hi bo ha cht phn ng vo l phnng c lp xc tc. Nng ca tc cht c kim sotbng cch iu chnh p sut hi bo ha ca n trongdng kh mang hoc bng mt phng thc thch hpkhc.
Vi tc dng ln thnh phn ca hn hp phn. ngc th c coi l rt gn vi ch trn l tng
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
161/255
www.themegallery.com
Nhng u khuyt im rt ra tphng php dng vi lng:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
162/255
www.themegallery.com
L phng php tm loi xc tc mi nhanh nhtv t tn km nht (xtc kim loi qu Pt, Pd)
Lng xt dng mi ln th nghim rt nh vlng cc cht phn ng cng rt t.
Phng php ch nghin cu trong phng thnghim khng th p dng vo cng ngh c.
Ptrnh ng hc rt ra t phng php vi lng
l ptrnh vi phn cho s liu chnh xc. Thit b n gin.
4. Phng php dng tun hon
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
163/255
www.themegallery.com
Nguyn tc: C s tun hon mnh ( nh bm tunhon) hn hp phn ng qua lp xtc. Lng kh tunhon ln hn lng kh tham gia phn ng. Kh phnng c nhp vo v ly ra lin tc.
c im: o c trc tip tc phn ng.
Nh cng tun hon ln loi tr c s thay inhit trong l phn ng.
C kh nng lm vic vi lng xc tc ti thiu. Nhc im: H thng thit b phc tp. Cn lng cht
phn ng ln tun hon. Thi gian phn ng cn lu t trng thi n nh, do d dn ti phnng ph.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
164/255
www.themegallery.com
5.Phng php xung vi lng:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
165/255
www.themegallery.com
c ph bin nhm sng lc nhanh cc cht xt. Thun tin trong kho st ng hc v c ch
cc phn ng trong trng thi khng n nh. c im : Tc cht c a vo bnh phn
ng khng lin tc m bng cch np nhngxung vo dng kh mang ( kh tr) lin tc thiqua lp xt, ging nh trong phn tch sc k kh.
Sn phm p sau khi ra khi bnh p b gi li
trong by t trong bnh cha nit lng trc khic gia nhit dng kh mang a vo ctphn tch sc k.
PHNG PHP XUNG VI LNG
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
166/255
www.themegallery.com
Xc nh tnh cht l- ha ca xc tc.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
167/255
www.themegallery.com
Tnh cht c hc: Th nghim va p
Th nghim mi mn
Phn b ht.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
168/255
www.themegallery.com
CHNG 5: SN XUT CHT XCTC
Mt s cht xc tc s dng trong cng nghip
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
169/255
www.themegallery.com
NR-2- xuc tac reforming thu kh qua s chuyen hoa metan vi hinc.
Thanh phan: NiO20%; Na2O 0.15%; SO30.5% tren chat mang.
Be mat rieng 18 m2/g, dang khoi tru 12.7 12mm
Thi gian lam viec 4-5 nam.
Toc o the tch toi thieu 200 l/h; nhiet o 838oC; ap suat 1 atm.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
170/255
www.themegallery.com
HI-3- xuc tac chuyen hoa CObang hi nc. Thanh phan: Fe2O3-95%; Cr2O3-4%; SiO2-0.2%.
Dang tru, ng knh 6.91, dai 12.7mm
Thi gian lam viec 7 nam.
Toc o the tch 600 l/h; nhiet o 455oC.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
171/255
www.themegallery.com
FM-1- xuc tac tong hp amoniac. Thanh phan: 64,6% Fe2O3; 31%FeO; 1,4% K2O; 2.5%Al2O3; 0,5% SiO2.
Dang vien khong qui tac thu c theo phng phap nong chay;96% co kch thc nho hn 10mm va 4% co kch thc nho hn
4mm. Thi gian s dung 7 nam.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
172/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
173/255
www.themegallery.com
Kim loai nhom Ptdung oxy hoa, hydro hoa va dehydro hoa,
dehalogen hoa.
1. 5% Pt, Pd, Ruva Rdtren phien than hoat tnh, oxyt nhom choat hoa va CaCO3.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
174/255
www.themegallery.com
Cac xuc tac dang hat nho va vien (vien thuoc): 0,3% Pt tren
oxytAlhoat tnh co kch thc 3.2mm; 1% Pttren than go cochoa, kch thc 2.4-4.7mm; 0.3% Pttren silicagel.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
175/255
www.themegallery.com
Xuc tac dang keo 0.5g Pd/l; li kim loai thanh phan 90 - 10% Pt
- Ph ; muoi en Pt.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
176/255
www.themegallery.com
Code-902- xuc tac oxy hoa naphtalen, thanh phan 10% V2O5, 33%K2SO4; 55% SiO2 dang phien, 85% qua ray 1,147mm; 45% qua ray0,074mm.
dang vien (nh vien thuoc) 3.2 3.2; toc o the tch 1400gi1, nhiet o 455oC
Code-904- xuc tac thu vinylclorua t acetylen va HCl. Than hoat tnh (91%); kch thc 1,7 4,7mm tam thuy ngan clorua
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
177/255
Xuc tac co cac dang hat khac nhau: phien, hat nho, vien, tru, vong, cau
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
178/255
www.themegallery.com
Chat mang va chat xuc tac tron vao nhau dang ran, sau o
em ep vien thanh hnh dang can thiet.
Chat hoat ong xuc tac c phan bo bang phng phap kettua len tren chat mang a c tao hnh xac nh.
Phng phap ket tua
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
179/255
www.themegallery.com
Phng phap ket tua c dung nhieu trong cong nghiep. Co
nhieu cach ket tua:
1- Tam t chat mang bang dung dch cha loai muoi cua chat
xuc tac lam kho chuyen xuc tac sang dang hoat ong
Nhc iem: trong qua trnh lam kho, muoi chuyen dch ra be
mat ngoai mot phan be mat trong khong c phu chatxuc tac.
Phng phap ket tua
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
180/255
www.themegallery.com
2- Tam chat mang bang dung dch, sau o x ly hoa hoc.
3- Ket tua ong thi chat mang va chat xuc tac, tao vien va lam
kho.
4- Tron hai cau t dang kem nhao, tao hnh va lam kho.
Phng phap ket tua
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
181/255
www.themegallery.com
5- Phun chat xuc tac len be mat chat mang (phng phap nay thch
hp cho chat mang khong xop).
6- ien di ket tua, hay hap phu cac ket tua xuc tac t dung dch
long, hi len chat mang.
Phng phap ket tua
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
182/255
www.themegallery.com
Cac phng phap khac:
TachAl khoi hp kim 50%Al, 20% Ni bang dung dch thuxuc tac Ni
Tach loai cac chat khong co li cho xuc tac khoi at set
thien nhien xuc tac alumosilicat.
Ngng tu hi tren si thuy tinh (chat mang)
Hoat hoa be mat xuc tac
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
183/255
www.themegallery.com
La giai oan can thiet trong qua trnh ieu che xuc tac: tachchat b hap phu, ket tua v.v ra khoi be mat chat xuc tac(a lam bien oi tnh chat hoa hoc va ly hoc cua chat xuctac).
Co the tien hanh ngay trong qua trnh s dung.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
184/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
185/255
www.themegallery.com
Xuc tac b au occo the t phuc hoi trong qua trnh lamviec, hay phuc hoi theo chu ky trong thiet b phan ng hay trongthiet b rieng.
Tranh xuc tac b ngo ocbang cach thay oi qui trnh kythuat e co li cho xuc tac.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
186/255
www.themegallery.com
Phan loai xuc tac theo phng phap chuan b va ban chat hoa hoccua chat xuc tac
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
187/255
www.themegallery.com
ket tua
ket tua tren chat mang
tron c hoc cac cau t
nong chay
khoang thien nhien, zeolite...
Quy trnh ky thuat chung
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
188/255
www.themegallery.com
Giai oan 1: Thu nguyen lieu ran ban au: (Cac chat tham gia
vao thanh phan cua chat xuc tac cuoi cung + cac chat can
phai c loai bo)
Giai oan 2: Phan huy hp chat co cha cau t xuc tac (nhiet
phan hay phan huy) san pham.
Giai oan 3: Bien oi thanh phan cua chat xuc tac
Yeu cau ve nguyen lieu au
hS ong nhat
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
189/255
www.themegallery.com
thanh phan hoa hocxac nh co kch thctheo yeu cau o amcan thiet khong co chat oc
gia ca thap, v.v
S ong nhat
ve thanhphan hoa
hoc cua chat
xuc tac
Phng phap troncac thanh phanban au, ieu kien van chuyen, baoquannguyen lieu
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
190/255
www.themegallery.com
Thanh phan pha nguyen lieucau truc xop cua chat xuctac
Tap chatco t nguyen lieu au giam hoat tnh, o chonloc cua chat xuc tac.
Tap chat gia thanh.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
191/255
www.themegallery.com
Ncdung e hoa tan, pha loang va ra cac chat trong quatrnh san xuat chat xuc tac
Vat lieu lam thiet btrong san xuat. Thiet b phai c lambang vat lieu khong an mon, khong tao vay oxyt, v.v
Cac qua trnh c ban trong san xuat chat xuc tac
C h h h kh l l
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
192/255
www.themegallery.com
Cac qua trnh thuy ong hoc: khuay tron, lang, loc.
Cac qua trnh nhiet: gia nhiet, lam lanh, bay hi, ngng tu hi.
Cac qua trnh khuech tan (chuyen chat): trch ly, hoa tan, kettinh, hap phu. lam kho
Cac qua trnh c hoc: tron cac phan t ran, nghien, phan
loai, nh hnh va cac qua trnh khac.
Cac qua trnh hoa hoc: ong the, d the.
Cac qua trnh hoa hoc
R i h l d h d h
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
193/255
www.themegallery.com
Rong rai nhat la s dung cac qua trnh d the, trong o cac
qua trnh hoa hocdien ra kem theo s khuech tanva chuyencac cau t t pha nay sang pha khac.
Kh - long: s hap phu hoat hoa va giai hap
Kh ran: s hap phu hoat hoa va giai hap
Long - ran va long long: s trch ly chon loc, tao chat mitrong phan trch ly.
nh hnh hat xuc tac va chat mang
k i h
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
194/255
www.themegallery.com
ket tu trong giot phun
ong vien nen, ep un
say phun paste
Cac chat ket dnh: bot talk, grafit, thuy tinh long, mot so axithu c va cac chat khac.
nh hnh hat xuc tac va chat mang
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
195/255
www.themegallery.com
Phng phap tao hnh anh hng en:
be mat rieng
cau truc xop cua khoi tiep xuc
o ben c cua hat
THU KHOI TIEP XUC TREN C S KET TUA
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
196/255
www.themegallery.com
ay la phng phap san xuat 80% cac chat xuc tac va chatmang xuc tac cong nghiep
u iem: gii han rong bien oi cau truc xop va be mattrong cua cac chat xuc tac va chat mang.
Nhc iem: tieu hao ang ke ca lng nguyen lieu lan lngnc.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
197/255
Cac giai oan quan trong theo phng phap ket tua
l h h h d l
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
198/255
www.themegallery.com
1- Hoa tanla qua trnh chuyen pha ran vao dang long trangthai phan tan phan t hoat tnh hoa hoc cua cac phan t
tang len tang toc o phan ng cua cac cau t vi nhau
Toc o cua qua trnh c xac nh bi lng chat hoa tan
trong mot n v thi gian.
Hoa tan
Hai yeu to anh hng trc tiep en s hoa tan la:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
199/255
www.themegallery.com
Hai yeu to anh hng trc tiep en s hoa tan la:
Khuay tron giup lam tang s san bang cau t trong pha long, giam xuong lam cho qua trnh hoa tan tang len.
Nhiet o tang th he so khuech tan, s chuyen chat tang (doo nht giam); nhiet o tang cung lam cho o bao hoa tang
len. (Vi cac muoi Na2SO4, K2SO4, Na2CO3, Na3PO4, MgSO4thkhi nhiet o tang lam o hoa tan giam cho en khong).
Ket tuah h h h h k l
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
200/255
www.themegallery.com
2 - Ket tua:chuyen cac chat hoa tan thanh ket tua la tong cuahai qua trnh: tao mampha ran va s ln len cua cac mamtinh the, ket tua.
So lng mam tinh the xuat hien ban au phu thuoc: nong o
Ket tua
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
201/255
www.themegallery.com
So lng mam tinh the xuat hien ban au phu thuoc: nong o
dung dch ban au, nhiet o,pH,lc ion
S tach chat ran t dung dch dien ra vi s ln len cua tinhthe - qua trnh d the
Qua trnh ket tua tao he a phan tan, tai ket tinh (theo Kelvin -Thomson)
Tnh chat cua ket tua (o phan tan o xop hnh dang hat) c
Ket tua
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
202/255
www.themegallery.com
Tnh chat cua ket tua (o phan tan, o xop, hnh dang hat) c
cac nh bi cac yeu to:
nhiet o ket tinh
pH
thanh phan ban au cua dung dch
nong o cua dung dch
cng o khuay tron
th t o dung dch vao nhau
Ket tua
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
203/255
www.themegallery.com
Phng phap tien hanh ket tua anh hng nhieu en tnh chat cuasan pham:
Ket tua chu ky se cho san pham khong ong nhat ve thanhphan.
Ket tua lien tuc (suot thi gian nong o chat phan ng,pHmoitrng bao am khong oi) cho xuc tac kha ong nhat.
e thu khoi tiep xuc n cau t n pha co dang vi ong nhat
Ket tua
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
204/255
www.themegallery.com
e thu khoi tiep xuc n cau t, n pha co dang vi ong nhat
th yeu cau ieu kien tien hanh cang phc tap hn v o hoatan cua hp chat ket tua, thanh phan pha ran luc bat au vacuoi la khac nhau.
Loc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
205/255
www.themegallery.com
3- Loc: Trong qua trnh loc cac cau t hoa tan thng hap phu tren be
mat ket tua.
Ra ket tua loc
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
206/255
www.themegallery.com
4- Ra ket tua locco the thc hien ngay trong qua trnh loc, nocho phep s dung lng ln dung dch ra e lam sach themket tua, ong thi cung tao ranh tren ket tua.
Say
5- Say:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
207/255
www.themegallery.com
Say kho trc tiep, la phng phap cho phep tiep xuc khongngng cua ket tua vi chat lam kho.
Say tiep xuc la qua trnh say c truyen nhiet t tng chatlam kho en vat lieu do s truyen nhiet.
Phng phap ien: s dung dong ien cao tan hay nhiet Jun.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
208/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
209/255
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
210/255
Aluminosi l icat
dang vien, hnh cau, bot mn
Al2O3: 7 30%
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
211/255
www.themegallery.com
2 3
La xuc tac axit-baz, ng dung:cracking, alkyl hoa, polyme hoa, ongphan hoa
Trong qua trnh ieu che xay rangng tu gelAl2O3va SiO2do tao
lien ket SiOAl, trong o coca lien ket SiOSihay AlOAl
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
212/255
www.themegallery.com
S TNG HP ALUMINOSILICAT silicate, nc
Dd Na2O nSiO2
Al(OH)3, nc
Dd H2SO4
Dd Al2(SO4)3
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
213/255
www.themegallery.com
Sy kh
Nung
Sn bi v ht khng t tiu chun
Thnh phm xc tc
Giac
ng
t
Tch nc (co gel)
Hot ho htRa
Kt ta v nh hnh
Dd Na2O.nSiO2 Dd Al2(SO4)3
H thng thit b chun b thy tinh lng
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
214/255
www.themegallery.com
Dy chuyn h thng chun b dung dch Al2(SO4)3
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
215/255
www.themegallery.com
CAC CHAT XUC TAC TREN CHAT MANG
(PHNG PHAP TAM)
Cau t hoat ong nh tren chat mang co nhieu lo xop, trong o chat
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
216/255
www.themegallery.com
mang la vat lieu tr hoac t hoat ong. Tng tac vi chat mang co the lam thay oi kch thc gia cac
phan t trong xuc tac hay hoa tr trong lien ket do co lien quan entng tinh the.
Tuy thuoc vao loai thiet b phan ng, chat xuc tac tren chat mang
co the la vien vi hnh dang bat ky: cau, vi cau, hnh tru, vay...
CAC CHAT XUC TAC TREN CHAT MANG
(THEO PHNG PHAP TAM)
Tam cau t hoat ong xuc tac len chat mang xop bang dung dch
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
217/255
www.themegallery.com
g g p g g
cha cau t hoat ong xuc tac.
Cac chat hoat ong xuc tac c chon dang cac muoi nitrat,
cacbonat, acetat cua anion de b phan huy khi nung
Xuc tac kim loai thng thu dang hydroxyt tren chat mang, sau o
chuyen sang dang oxyt va kh (bang kh H2). en kim loai
CAC CHAT XUC TAC TREN CHAT MANG
(PHNG PHAP TAM)
Muoi kho tan: tam 2 giai oan:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
218/255
www.themegallery.com
g
1. tam cau t th nhat
2. tam cau t th hai (la chat tao muoi kho tan vi cau tva tam giai oan 1)
ket tua c tao ra trc tiep tren chat mang xop.
CAC CHAT XUC TAC TREN CHAT MANG
(PHNG PHAP TAM)
Cac bc:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
219/255
www.themegallery.com
Hut chan khong, tach kh t lo xop cua chat mang
X ly chat mang bang dung dch
Tach dung dch tha
Say va nung.
CAC CHAT XUC TAC TREN CHAT MANG
(PHNG PHAP TAM)
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
220/255
www.themegallery.com
Tam theo chu ky hay tam lien tuc.
Tam lien tuc cho san pham ong nhat hn ve thanh phan va hoattnh xuc tac.
Tam co the tien hanh mot lan hay nhieu lan (tuy ieu kien xem coat yeu cau chat hoat ong xuc tac cha).
Sau moi lan tam chuyen qua giai oan gia cong nhiet.
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
221/255
www.themegallery.com
So lan tam phu thuoc nhieu vao cau truc lo xop cua chat mang echuyen van chat en tan ben trong mao quan.
Mao quan nho, tang so lan tamlam bt cac mao quanco the
lam mat tac dung xuc tac phai tm so lan tam toi u.
ac tnh va qui trnh san xuat cac chatmang quan trong
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
222/255
www.themegallery.com
Chat mang vi be mat rieng nho (diatomit, amian, a bot)
Chat co be mat rieng ln (gamma oxid nhom, silicagel, at set,
alumosilicat)
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
223/255
www.themegallery.com
1, 2- Thiet b phan ng co gia nhiet va khuay tron; 3- Loc; 4- May ep; 5- May nghien truc - tron;
6- Tao vien; 7- Lam kho; 8- Lo nung
He thong san xuat silicagel vien nen)
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
224/255
www.themegallery.com
1, 13- Bnh cha dung dch; 2- Bm; 3- Thung cao v; 4- Ap ke; 5- Thung em; 6- Van chnh;7- He thong lanh; 8- Lu lng ke; 9- Mang dan chat xuc tac; 10- Cot nh hnh hat xuc
tac; 11- Bo phan phoi; 12- Dau hon hp
He thong san xuat silicagel dang vien cau
KHOI TIEP XUC TREN C S TRON C HOC CAC CAU T VAO NHAU
Cac qua trnh c ban:tron cac cau t vao nhau e co the tao dung dch
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
225/255
www.themegallery.com
ran, hp chat hoa hoc, he nhieu pha.Phng phap t:Tron huyen phu cac loai cau t vao nhau ket tualoc
saynh hnh.
Ham lng cac cau t trong xuc tac phu thuoc:
nong o trong dung dch
kha nang hap phu huyen phu o am con lai cua ket tua
u iem: o ong eu tot.
Nhc iem: ieu kien tien hanh nghiem ngatkho khan trong sx cong nghiep
KHOI TIEP XUC TREN C S TRON C HOC CAC CAU T VAO NHAU
Phng phap kho:tron cac cau t ran ong thi vi viec
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
226/255
www.themegallery.com
lam am hon hp tao ra (can cho viec tao hat).
- Nhc iem: kho thu c khoi cac cau t ong nhat
Cac chat xuc tac san xuat theo phng phap nong
chay
Cac giai oan:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
227/255
www.themegallery.com
1. chuan b mang li vi thanh phan can thiet2. phan bo cac cau t
3. nh hnh hay lam nguoi hp kim
4. nghien en kch thc can thiet.
Chat xuc tac tren bo khung (Skeleton catalysts)
Cac chat xuc tac tren bo khung c dung trong cac qua trnh:
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
228/255
www.themegallery.com
hydro hoa ng, dau, furfurol, quinon a nhan, v.v
la thanh phan cua cac ien cc cua pin nhien lieu nhiet o thap.
Chat xuc tac tren bo khung (Skeleton catalysts)
1. Vat lieu e thu cac khoi tiep xuc tren bo khung la cac hp kim lng
-
8/13/2019 K thut xc tc - HUI - Nguyn nh Nga
229/255
www.themegallery.com
hay a cau t cua cac kim loai hoat ong xuc tac.
2. Cac thanh phan cua hp kim nay b tach loai ra khi x ly bang cac
dung dch cac chat ien ly manh, chng cat trong chan khong
3. Khi tach