TRNG I HC BCH KHOA H NI VIN K THUT HA HC B MN CNG NGH HU C HA DU

N TT NGHIP
ti: Nghin cu cc yu t nh hng ti qu trnh hydrodeclo ha tetracloetylen trn xc tc Pd-Ag/C*
GVHD: PGS.TS. Nguyn Hng Lin SVTH : Nguyn Vn Hon LP: Ha Du K52 QN

TNH CP THIT CA TI
Hp cht clo hu c/tetracloetylen c ng dng rng ri trong cng nghip do cc tnh cht rt u vit ca chng:

S dng trong quy trnh git l, lm sch b mt, ty du m

Lm dung mi, ph gia, nguyn liu cho qu trnh tng hp ha hc, sx nha, thuc tr su, thuc nhum,

Ngoi ra cn mt s ng dng khc nh trong nng nghip, dc hc,

8/21/2012 2

TNH CP THIT CA TI
Sau khi s dng a s cc hp cht ny thi trc tip vo mi trng, ha vo sng h, mch nc ngm v phn tn vo mi trng khng kh. Gy ra nhng hu qu nghim trng ti mi trng v sc khe con ngi, nh lm thng tn ozon, gy ra nhng cn bnh nan y nh ung th, c bit l nhng cn bnh di truyn sang th h sau.

V th vic gim thiu cc hp cht clo hu c thi ra mi trng ang l mt vn ht sc cp bch t ra hin nay.

NI DUNG TRNH BY

1. Tng quan l thuyt 2. Thc nghim 3. Kt qu v tho lun 4. Kt lun

4

TNG QUAN L THUYT

HP CHT CLO HU C

L nhng hp cht hu c m trong phn t c cha mt hay nhiu nguyn t clo gn vo phn t hp cht hu c, c cng thc chung:

RClx

R: gc hp cht hu c x: s nguyn t clo trong phn t

Mt s hp cht clo hu c tiu biu

Tetracloetylen

1,1,1-tricloetan

1,2,4-triclobenzen

Vinyl clorua

Hexaclobenzen
5

TNG QUAN L THUYT

CC PHNG PHP X L
Tc nhn u im Nhc im Khng thn thin vi mi trng. - Thi gian x l di. - Khng x l c cc hp cht c cha nhiu Clo. - Xc tc s dng l cc kim loi qu, c tin v nhanh mt hot tnh. SP khng ti s dng c.
6

Phng php Oxi ha

O2 (c hoc khng c xc tc)

- TB cu to n gin, d vn hnh. - Gi thnh re.

- Thn thin vi mi trng - Khng c hi i vi sc khe con ngi. - Hiu sut cao. - Sn phm ca qu trnh c gi tr kt Hiu sut cao.

Sinh hc

Vi khun

Hydrodeclo ha

H2 (xc tc, nhit ) H2, O2 (xc tc v nhit cao)

Oxy ha kh kt hp

TNG QUAN L THUYT

HNG NGHIN CU CA TI

Trong n ny em tp trung vo nghin cu cc yu t nh hng n qu trnh hydrodeclo ha tetracloetylen trn xc tc Pd-Ag/C*, nh: 1. Nhit hot ha xc tc

2. Thi gian hot ha xc tc

3. Nng dng hot ha xc tc 4. Lu lng dng hot ha xc tc 5. Nng dng phn ng 6. V lu lng dng phn ng

THC NGHIM

Tng hp xc tc. nh gi c trng xc tc.

nh gi hot tnh xc tc.

8/21/2012

2
Dung dch Pd(NO3)2, AgNO3

THC NGHIM
TNG HP XC TC
Ngm tm y np nhit phng 24h Bay hi nhit phng 24h Sy 120oC Qua m Nung 3000C trong 3h Hot ha Xc tc Cht mang C* 0,2 0,5 mm

8/21/2012

THC NGHIM

nh gi c trng xc tc bng phng php kh ha theo chng trnh nhit TPR H2

Phng php ny c tin hnh trong mt thit b phn ng vi
dng hnh ch U v c kt ni vi mt detector dn nhit (TCD). u tin cc mu xc tc c ra trong dng kh He 350oC

loi b vt nc.
Kh kh l hn hp H2/Ar10% c np vo thng qua mt b iu khin lu lng dng. Mu c gia nhit t 40oC n 800oC vi tc gia nhit l 10oC/pht, gi trong 45 pht. Qu trnh ny c thc hin trn my Autochem II ca hng Micromeritic, M.

2 THC NGHIM Hot tnh xc tc c nh gi trn s h vi dng HDC TTCE nh sau:

L phn ng

GC

1, 2. Thit b o & iu khin lu lng kh. 3. Thit b bay hi nguyn liu TTCE. 4. B trn. 5. L gia nhit. 6. Thit b phn ng. 7. B hp ph kh HCl bng NaOH khan. V1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 l h thng cc van iu chnh.

chuyn ha:

KT QU V THO LUN

Tng hp xc tc. nh gi c trng xc tc.

nh gi hot tnh xc tc.

8/21/2012

12

KT QU V THO LUN
TNG HP XC TC

tng hp c mu xc tc Pd-Ag/C*, vi tng hm lng hai kim loi l 1%, v t l mol ca Pd vi Ag l 1:1.

K hiu Pd-Ag/C*

Tng hm lng kim loi (% khi lng)

1

T l Pd/Ag (mol)
1:1

Cht mang C*

13

KT QU V THO LUN
Kt qu phn tch TPR H2 ca mu Pd-Ag/C*

Ag2O + H2 = 2Ag + H2O PdO +H2 = Pd +H2O

PdO3 +3H2 = Pd + 3H2O

PdO2 +2H2 = Pd + 2H2O

Trn gin ta thy c 3 peak kh nhit 272, 403 v 568oC. Mi peak ng vi qu trnh kh cc oxyt kl v dng kl hot ng.

KT QU V THO LUN
Kt qu phn tch TPR H2 ca mu Pd-Ag/C*

Kt qu lng H2 ng vi mi peak:
STT peak Nhit , oC Lng H2, ml/g

1
2 3

272
403 568

11,87
61,97 84,03

KT QU V THO LUN
65,7%, 3h
Dng kh Thi gian kh Lu lng dng kh 10% H2/Ar 3h 80ml/pht

nh hng ca nhit hot ha xc tc

72,3% ph48

Lu lng dng nguyn liu

Khi lng mu Nhit phn ng Dng v lu lng phn ng

120ml/pht
50mg

300oC 10%H2/Ar, 80ml/pht

Khi hot ha 300oC chuyn ha TTCE cao v n nh nht. Cn cc nhit khc chuyn ha c tng nhng kh thp.

KT QU V THO LUN
77,7%
Dng kh Nhit kh Lu lng dng kh Lu lng dng nguyn liu 10% H2/Ar 300oC 80ml/pht 120ml/pht 50mg

nh hng ca thi gian hot ha xc tc

55,6%

Khi lng mu Nhit phn ng Dng v lu lng phn ng

300oC 10%H2/Ar, 80ml/pht

T th ta thy hot tnh xc tc khi hot ha 4 gi > 3 gi > 5 gi

KT QU V THO LUN
Thi gian kh Nhit kh Lu lng dng kh Lu lng dng nguyn liu Khi lng mu Nhit phn ng Dng v lu lng phn ng 4h 300oC 80ml/pht 120ml/pht 50mg

nh hng ca nng dng hot ha

300oC 10%H2/Ar, 80ml/pht

Quan st trn th ta thy hot ha dng 10%H2/Ar cho hot tnh xc tc cao hn.

3
71,8%, ph12

KT QU V THO LUN
3h, 59,3%
Thi gian kh Nhit kh Nng dng kh Lu lng dng nguyn liu Khi lng mu Nhit phn ng Dng v lu lng phn ng 4h 300oC 35%H2/Ar 120ml/pht 50mg

nh hng ca lu lng dng hot ha

300oC 10%H2/Ar, 80ml/pht

T th ta thy chuyn ha ca xc tc tng theo th t: 40ml/ph > 30ml/ph > 80ml/ph

KT QU V THO LUN
Nhit hot ha Nng v lu lng dng hot ha Thi gian hot ha Nhit phn ng Nng dng phn ng Khi lng mu Lu lng dng nguyn liu 300oC 35%H2/Ar, 40ml/pht 4h 300oC 10%H2/Ar 50mg 120ml/pht

nh hng ca lu lng dng H2/Ar phn ng

chuyn ha TTCE cao hn v n nh hn khi phn ng vi lu lng dng H2/Ar 80ml/pht.

KT QU V THO LUN
Nhit hot ha Nng v lu lng dng hot ha Thi gian hot ha Nhit phn ng Lu lng dng phn ng Khi lng mu Lu lng dng nguyn liu 300oC 35%H2/Ar, 40ml/pht 4h 300oC 80 ml/pht 50mg 120ml/pht

nh hng ca nng dng H2/Ar phn ng

chuyn ha TTCE nng dng H2/Ar35% cao v n nh hn so vi mu phn ng nng dng H2/Ar10%.

KT LUN

Sau hn 3 thng nghin cu v tin hnh thc nghim v phn ng hydrodeclo ho tetracloetylen trn cc mu xc tc Pd-Ag/C* em thu c mt s kt qu nh sau:

1. Nghin cu c trng xc tc bng phng php

TPR H2 cho thy cc dng oxyt kim loi tn ti trong

mu xc tc Pd-Ag/C* c kh v kim loi 3 mc

khc nhau ti: 272oC, 403oC v 568oC. 2. iu kin tt nht xc tc c hot tnh cao l kh 3000C trong 4h vi lu lng dng H210% l 40ml/pht.

KT LUN

3. iu kin tt nht tin hnh phn ng HDC

TTCE l dng dng H2 35% lu lng 80ml/pht.

Tuy nhin y mi ch l nhng kt qu bc u,

cn phi c thi gian nghin cu, tm hiu v thc nghim nhiu hn na mi c th ng dng qu quy trnh ny vo thc t.

Knh chc cc Thy C hnh phc, sc khe v thnh t.

8/21/2012

24

THC NGHIM

nh gi c trng xc tc bng phng php kh ha theo chng trnh nhit TPR H2

Mc ch: Xc nh cc dng oxyt kim loi v iu kin kh v kim loi
trong xc tc Pd-Ag/C*. Nguyn tc:

- Hn hp kh kh (thng H2 pha long vi mt kh tr) c a qua b

mt mu oxyt cn phn tch, nhit ca mu c tng dn theo chng trnh nhit , khi qu trnh kh bt u lng hydro trong hn hp kh

gim i, lm thay i dn nhit ca hn hp kh. S thay i ny c

ghi li nh mt detector dn nhit TCD v chuyn thnh tn hiu in.

THC NGHIM

nh gi c trng xc tc bng phng php kh ha theo chng trnh nhit TPR H2

- Trog qu trnh kh cc oxyt kim loi trng thi ha tr cao s chuyn v trng thi ha tr thp.

- Mi mc chuyn trng thi ha tr ca kim loi s tng

ng vi mt peak kh. - Da vo din tch peak kh ny s xc nh c lng H2 tiu th v nhit kh cao hay thp hay mc kh kh hay d.

KT QU V THO LUN

nh hng ca nhit hot ha xc tc

Khi nhit hot ha tng qu cao c th xy ra hin tng thiu kt lm xc tc co cm li lm din tch b mt ca xt gim lm gim chuyn ha xt. nhng khi nhit hot ha thp, nng lng khng to ra cc tm hot tnh trit s lng tm hot tnh t CH gim. Theo kt qu TPR H2 phn tch phn trc, peak 272oC sc nhn v r nt nht, nn vng chn peak ny tc gn nhit 300oC lng tm kim loi to ra l ln nht chuyn ha ca xc tc ti nhit ny cao. Peak 568 cao nhng y l peak kh cui nn vng ny thng tp trung nhiu cc kim loi km hot ng. Nn chuyn ha ca xt khi hot ha nhit ny k cao.

KT QU V THO LUN
ph12, 81,3% 3h, 77,7%
Dng kh Nhit kh Lu lng dng kh Lu lng dng nguyn liu 10% H2/Ar 300oC 80ml/pht 120ml/pht 50mg

nh hng ca thi gian hot ha xc tc

3h, 55,6%

Khi lng mu Nhit phn ng Dng v lu lng phn ng

300oC 10%H2/Ar, 80ml/pht

Khi hot ha qu lu tm hot tnh xt b thu kt co cm li, lm gim din tch b mt xt, dn n chuyn ha ca xt gim. Khi hot ha trong thi gian ngn, nng lng k tm hot to ra hon ton CH xt gim.

KT QU V THO LUN

nh hng ca nng dng hot ha

C th lng hydro trong dng H2 35% cao dn n xy ra s cnh tranh gia cc phn t H2 khi tip cn cc tm hot tnh, gy cn tr khng gian b xt cc tm hot tnh chuyn ha TTCE ca phn ng gim.

KT QU V THO LUN
71,8%, ph12 Ph24, 63% 3h, 59,3%

nh hng ca lu lng dng hot ha

Khi hot ha lu lng 30ml/ph, trong cng mt khong thi gian lng H2 trong dng ny l t nht, khng s tm hot tnh to ra nhiu. Nhng vi lu lng 80ml/ph th qu nhanh qu trnh hot ha xt xy ra hon ton. Hot ha lu lng 40ml/pht l dng ph hp nht trong cc dng kho st qu trnh hot ha xy ra tt nht.

KT QU V THO LUN
Nhit phn ng Nng dng phn ng Nng v lu lng dng kh Thi gian kh 300oC 10%H2/Ar 35%H2/Ar, 40ml/pht 4h

nh hng ca lu lng dng phn ng

Nhit kh
Khi lng mu Lu lng dng nguyn liu

300oC
50mg 120ml/pht

Khi s dng lu lng dng 80ml/pht, cc phn t clo sinh ra trong pu HDC kt hp vi hydro to thnh HCl v nhanh chng c dng ny a ra ngoi, lm cho cn bng trong phn ng to kim loi hot ng chuyn sang chiu thun nn trnh gy ng c xt hot tnh xc tc cao v n nh.

KT QU V THO LUN

nh hng ca nng dng phn ng

Lng hydro trong dng H2/Ar 35% nhiu hn gp 3 ln so vi trong dng H2/Ar 10% nn qu trnh phn ct lin kt C Cl din ra nhanh v tt hn. Mt khc hm lng hydro trong dng H2/Ar 35% ln, cung cp lng hydro cho qu trnh kt hp gia hydro v clo gii phng ra to thnh HCl v nhanh chng c a ra ngoi, trnh gy ng c xc tc.

-Phn ng HDC thc hin trong mi trng kh. M trong mi trng kh th cht mang cacbon hot tnh l n nh nht. - u im ca C*: - din tch b mt ring ln, r, r, d ch to, kh nng mang ti xc tc ln, - khng c cu trc mao qun cho nn chng ta c th t c phn tn ln d thu hi c kim loi t xc tc phn ng Nhc im: B mt ring ln nhng kh a c kim loi ln cacbon hot tnh vi phn tn cao t mao qun ln v trung bnh,d b mt hot tnh trong thi gian ngn. Kim loi Pd: trong cc xc tc kim loi qu nh Pd, Pt, Rh, kt qu cho thy rng Pd l kim loi cho hot tnh xc tc v chn lc cao nht vi phn ng HDC nhc im l gi thnh cao, nhanh mt hot tnh.

Kim loi Ag: kh nng phn ct lin kt C-Cl tt hn cc kim loi thng khc. Qu trnh quan trng nht trong tng hp xc tc: ngm tm v ngm tm gip cc oxyt kL va phn tn tt trn b mt cht mang va phn tn vo bn trong l xp. To ra hot tnh cao cho xt. -ng dng trong dc hc: sn xut thuc v cc cc ha cht trong y hc. Nh: cacbon tetraclorua, d iu ch dc phm. -ng dng trong nng nghip: Hexaclobenzen sn xut thuc xt trng trong nng nghip. -Thuc tr su -Phn bn -ng dng trong ha du: 1,2-dicloetan dng lm dung mi trch ly, v loi b ch trong xng. -Tetracloetylen
- Lm cht tuyn kh - Lm cht lm sch kim loi v ty du m nhn - Tng hp ha hc

Vai tr ca Pd l gi hydro Ag: phn ct lin kt C-Cl L Th Nguyn: Nghin cu qu trnh x l hp cht clo hu c theo phng php hydrodeclo ha trn xc tc Pd-Ag/C* -im mi ca ti ny so vi cc ti khc l g -Mc ch pp TPR H2: Xc nh cc dng oxyt kim loi v iu kin kh v kim loi trong xc tc Pd-Ag/C*.