DAI HOC 01 OC GIA IIA NOI
IRIJONC DAI HOC KlIOA HOC I i M l l K N
xvivfxWKyrxxwxJfTCKXXXX^rx

Dfi lAI NGIIIKN Cl'j'U KIlOA HOC CAP DAI HOC QIJOC GIA IIA NOI

c m - : TAG VA DAC TRUNC HE VAT LIKIJ MAO QUAN
rRllN(; BiNH ( IIIIA KIM LOAI CHUYKN TIKP (V,Ti, Pt) LAM
XIJC lAC C l i O PI IAN IJN(; OXI HOA MOT SO HOP CHAT H C U CO

Ma so
: QT-07-22
Clui tri cle tai : ThS.Nguyen Tlii Minli T/nr

OAI HOC QUOC GIA HA NOI
TRUNG TAM THONG TIN THU VIEN

Df/ HT
Ha N'oi-IOO?


DAI HOC QUOC GIA HA NOI
IRLONC DAI HOC KIIOA HOC IL NHIKN

BAO CAO TOM T A T
KKT QUA NC.IHKN CIJU 1)E TAI NCIHEN CUU KHOA HOC
CAP DAI HOC: QUOC CIA IIA NOI

JEN DETAI:
ClJi-; TAO VA DAC I RUNG HE VAT I.IHU MAO QUAN TRUNG BINH
CIIUA KIM I,OAI CIIUYHN ill-;]' (V.Ti. Pi) LAM XUC lAC CHO PIIAN

/^G;----

B^.i^i^;i,^^,C.^Lj^

2007


SUMMARI/.E KKPORT OF THE PROJECT
OF VIETNAM NATIONAL UNIVERSFI Y HANOI

1. Title: Synthesis

and

charactirization

mesoporoiis

materials

transitive metals (V, Ti, Pt). Stiidyin}> catalytic properties
oxidation some ort^anic

containin};

of those materials

in

compounds.


science:

I Ihe suppor malerials i\'lCM-41. ri-MCM-41 were s\nlhcsi/ed 'and
characleri/ed.
\ Dispered nano si/e \anadiun oxide on ri-MCM-41 and plalinium on
MC^M-41. eharaeleri/ed b\ chemi-pii\sieo techniques: XRD. Raman. 1 HI PR, I I M . ...
i SUidied llie ealaixlie properlies of ihe malerials sxslems in oxidalion
some organic ei)mpounds: t/-pinen. melh) loleale and glucose. Ihe results


showed thai the V20s/'ri-MCM-41 is effective catahst for oxidalion cxpincn and melh> loleale. Pt-MCM-41 is cffeeli\e catal\sl for oxidalion
ulucose.
CI?

Results in trainin};:
1 wo bachelors have been trained.
Publication:
Two reseaeh papers ha\ e been publiched.
Hanoi, December

2007

Person of project

Nguyen Thi Minh Thu


DAI HOC 01 OC CIA HA NOI
IRIJONC DAI HOC KIIOA HOC TU NHIEN

^
NOI D U N G NGIIIKN C U U C U A

III. PlIUONG PHAP

DK lAI

NGIIIAN C U U

3
16
16

IV. CAC KHI QUA NGIIIHN CUU VA THAO LUAN

17

4.1. lonj^ hop vat lieu

17

4.1.1. long hop vat lieu mao quan Irung binh MCIVI-4I

17

4.1.2. long hop vat lieu ri-MCM-41

18

4.1.3. long hop vat lieu V20s/Ti-MCM-41

Hien nay nhu'ng cong nghe sach (il chal thai \'a khong doc hai) ha\ con goi la
cong nghe than ihien moi truang vai cac xiic lac "xanh'' dang ngay cang phal Irien
nham dap li'ng ycu cau cua ncn cong nghiep hoa chat hien dai. Da co nhifiu nghien
cu'u cai lien cong nghe, giam san phAm phu nang cao hieu sual cua qua Irlnh,
nghien cii'u nhu'ng ca scV khoa hoc cho vice xii If cac chat thai rdn
lao ihanh cong nhu'ng val lieu xuc lac moi co hieu qua kinh Ic

long

khi. Che

ky ihual cao du'Oc

ung dung rong rai khong chi Irong ITnh \'u'c moi Iru'ong ma con Irong nhieu ITnh \uc
khac nhu chat hoal dong bC mat, duoc phaim, my phalm, Huong lieu, thuoc bao ve
ihu'c vat, polime....
I km 40 nam qua, eac vat lieu /eolit va vat lieu tuang ty zcolit voi eac tinh
chat axit, ba/o', oxi hoa khu, krong chue, ... da dong mot \ai iro v6 cung quan
trong voi nhieu irng dung ti'ong cong nghe hap phu va xuc lac, su dung Irong nhieu
eac qua trinh hoa hoe khac nhau. \u\ nhien, duong kinh mao quan va eac hoe rong
eua he vat lieu iia\ nho, khoanu 5,3 den 5,6 A chi thich ho'p cho viee ehuvcMi hoa
eac phan tu nho khong the dap ung cho cae qua Irinh gom co nhieu phan lu Ian,
eonu kenh.
Dau thap nicMi 90, mot phat minh mang tinh dot pha cua hang Mobil la long
hop ducK vat lieu mao quan trung binh (MQTIi) M41S. He vat lieu nay voi kich
thu'oe mao quan 20 - 500A, be mat rieng Ion 1000

1400m"/g va rat dong deu, co

kha nang tao eac nhom ehue be mat khac nhau. Thanh cong na\ da mo' ra co hoi
en lieu tho: xu hirong tha\ the parafm bang olcHn hay eac
hgp chat tho'm. (\ie iiua trinh dieu ehe anhidrie maleie tir butan ha\ pentan duac
tha\ the banu nuuxen lieu dau la ben/en, de san xuat acrylonitrin neuai la
khong su dung propan ma dung propilen. Cac nguycn lieu dau nay giup don
gian hoa qui trinh cong nghe\ cho hieu sual cao \ a san pham tinh khict ho'n.

-

I loan thien eac he xiic tae eo san vai xu huong tha\' the eac he xuc lac dong the
bang xiie tae di the. d i a n g han tha\ he xuc tae PdCk/CuCk bang Pd'7Mo-V-P
irong cae qua irinh ehu\ en hoa olefm thanh xelon.


d6ng phan alpha \ a beta pinen la hai monotecpen chfnh. Con trong cac linh dau
khac nhu cam, chanh...chua nhieu lecpen cung dong vai Iro quan Irong trong cong
nghiep tao huong va nuoc hoa...
Cac san phfim lu' monotecpen, hay cac hgp chat chua noi doi noi chung co
gia Iri cao trong cong nghiep tao huong lieu va hucrng vi, la cac thanh phan Irong
cong nghiep che lao dung moi, chat lay rua, hoa hoc nong nghiep xa trong nganh
duoc lieu. I l x p e n andehil, ancol \'a este thuong la nhu'ng chat quan Irong trong
nhom thanh phan lao mui Iho'm Ion nhal | 8 | . Trong hoa hoc lecpen, su epoxi hoa
chon loe la rai ciuan trong. Cac chal oxi hoa theo ti le hgp ihu'c dung cho phan ung
nay ihudng la cac pcaxit hu'u eo. phu'o'ng phap nay lao ra nhieu san phclm phe thai
va khong chon loe \o'i \iec dieu che epoxi nhay axil. Tranh hien lugng nay, nhieu
nizhien cuu sir ditiiu he

XL'IC

Uic bao izom eac ho'p chat cua x'onlVam, xuc tae nhom

silieat mang lilan. peroxolungslophotphat. mt)l}'pden. phu'c xanadi. mangan

da

duoc sir dung cho nhieu muc do thanh cong cung nhu la han che khac nhau.
Patricia cung cong su da thu'c hien phan ting oxi hoa limone. 3-carcn,...dijng lac
nhan lUO. tren he xiic lac (\)/SiO. khac nhau cho siin phixm rat phii'c tap 118|. Vf
du nhir khi dinig he xuc lac (AVSiO.. limonen ta(^ ra 3 san phAm chfnh: limoncn
oxil, earxeon, CcU\eol. li'ong khi do caren lao ra hon hop san pham \a'\ dtVchon loe
ihap, nhu 3-caren 5 on \a 3 earen-2.5-dion. khong eo san pham epoxi hoa....nhu
sau:
4



MF

M^
.-O

Mt^ •

H

CHv
i' *j

o
M^

-X
CH,

.. O

Me-/^"
o

C n'''..'on

Trong thoi gian gan day, da co mot so nghien cu'u rat ihii vi vC phan ung oxi
hoa chon loe cac anken noi chung cung nhu cac monotecpen noi rieng tren cac xiic
lac sinh hoc, xuc lac en/ym. braces Arnold cung cac cong su da nghien cuu phan
li'ng epoxi hoa cac anken C^-C^ hoac cac axil beo mach dai trcn xiic Uic
pho
bien o Viet Nam. Sir oxi hoa alpha pinen dirge quan tam Ian bo'i cae san pham eua
no CO nhieu ung dung quan trong irong cong nghiep cung nhu trong doi song, \ i du
nhu \erbenon. diing de long hgp taxol. la mot lac nhiin duge ly. Con eac san pham


lecpcnie andeh} I, rirgii. esle va epoxi duge xem nhu cac chat dau dc long hgp duge
pham, chal lao miii Irong ehe lao my pham, nuoc hoa, chal lao huong \\ ... Dae
bicl la cae chal epoxi duge dung rong rai nhu* la cae nguycn lieu tho cho cac loai
nhua epoxi, so'n, chal hoal dong be mal, eac chal trung gian Irong ITnh vue long
hgp hu'u CO linh khict. Tren the giai, vice nghien cii'u, che tao cac chal hoal dong
be mat dang chira nhom etilenoxil hoac nhom hidroxi tir cac dau thirc \at da duge
ihue hien nhieu \ a i so lugng Ion. Trong so rat nhieu cac che pham eua dau ihue
vat, mot dan xuat dae trung va duge su dung rong rai nhal la cae san pham ehua
oxi nhu eac hgp chat chua nhom etilenoxil hoac nhom hidroxi. No la ihanh phan
khong the thieu Irong nhieu san pham nhu chat lay rua, chal hoal dong be mat, lam
duo'c pham... Iu\ nhicMi o Viet nam, van de na\' chua duoc dau tu mzhien cuu
nhieu.


MMIL'IU)!

pincn

trans-Verbenol

Verbenon

PiiiocatA col

Hien na\', xi su phat IricMi ben vung vc van dc moi truang, cac du liiat va
dieu le eiia cong nghiep san xuat xanh dang cang tro ncn chat che ho'n. Nhirng
ihaeh thirc dau tien doi \ oi ncn cong nghiep san xuat hoa chat linh khict la phai lim
ra cac qua trinh sach eo hieu qua cao va han ehe toi da lugng san pham phu, hoac
phai tao ra cae to hgp cong nghe sir dung san pham phu cua qua trinh nay la
nguycn lieu cho qua trinh khac. Vi du crackinh xiie tae eua qua trinh loe dau vai
muc dich tang ham krgng xang, tang tii so oetan eua xang thuang co nhieu san
pham olefin nhe, \ i \ a} phai eo cong nghe hoa dau di kem voi cac qua trinh san
xuat PI-. PP. PVC, ... Mol trong cae phuo'ng phap do la su dung cac vat lieu xiie
lac chon loe \oi lirng qua trinh .
1.3 Phiin lin^ oxi hoa dau thuc vat va iin dung
1.3 J. lin}^ (f{'fii! ^'ff^f ^/^/'' ^/'''^" 'T'^
Co xap \i 150 Irieii tan dau va mf)' du'Oc san xuat IrcMi loan the gioi \ao nam
2003. Thanh phan chinh cua dau thirc \'al la este ciia axit beo voi glixeri. I'iiy theo
Ihanh phan cau tao cua axil beo chua trong dau qu\et dinh li'ng di.ing cua chung.

7



khi phan u'ng dirng lai cV giai doan epoxi tao cac epoxil co the lam lac nhan'men deo
vii nhu'ng chai on dinh polime...ngoai ra con duoc diing nhu nhu'ng chat trung gian
trong vice san xiiai cac dan xual da dang boi vi ifnh boat dong cao ciia vong epoxi
bi cang ra. Vf du rugu bac
hydroxy lesler.

I, rugu bac 2, cac diolefin.

N-hydroxyalkyllamide,

mercaptoalcohol.

alkoxylalcohol,

aminoalcohol

va

hydroxynitrile co the duo'c san xual theo duong mo vong epoxil \ai cac chai phan
U'ng phii hgp | 2 I . 22|.

1. 4. Cacbohidrat: dae trun \ a lin^ dun cung nhir trong sir san sinh va du trCr nang lugng \ a \at


lieu. Thuoc vao lap cacbohidral la eac chal nhu xenluloza, val lieu khung chu ycu
cua ihuc val, tinh boi, pectin va cae duong nhu glucoza va saccarozo. 0 dong \at

^[()\

H-

-OH

H-

-OH

H2C—OH
H^C OH

Axil D-gluconic

D-glucozo'

Tuang tu eac axit y va 5-hidroxicaeboxylie, cac axil onie ncu tren de taeh nuoc de
lao thanh cac y hoac cS-lacton, vai su uu lien lao thanh y-laclon. Su de bj oxi boa
cua cac andozo' da duac su dung cho nhieu phuong phap phan lich duong eo dicMi
duge cip di^ing pho bicMi truoc day, nhu thuoc thu l-elinh, thuoc thu Tolan
Dung djch T'elinh chira ion phire eua dong laetral, thuoc ihu nay khong ket lua mau
do gach eua CTbO khi oxi boa andozo". Trong moi truong kiem cae xetozo' bi
chuyen thanh i\ndo/.o\ va eac chat nay bi oxi hoa boi phue chat dong.
Dung dich Tolan chira ion phire bac amoniacat va cho phan irng duong tinh \d\
'dndo/.a \ a xetozcr.
Cae axit andonie la cac hgp chat dau quan trong de long hgp cae xctozo" cao hon
cung nhu de iboai bien thanh eac andozo* thap hon.
Voi eac tae nhan oxi boa manh hon, thi du axit nitric dam dae, thi a andozo khong
chi nhom andehit ma ca nhom ancol bac mot cung bi oxi boa thanh nhom


Axit ualaetaerie


Phdn im^ len men:
Nha lac dung cua cae enzim khac nhau, phan tu glucoza iham gia \ a a eac qua
trinh phan cat phiic tap (phan irng len men), lao thanh cae san pham cuoi 4:ung nhu
elanol, axil bul}rie, axil lactic, axit xitric..., dong thai co giai phong ra san pham
khi nhu IN, CO2. Tii\' theo ban chat eua san pham thu duge ta phan biet cae phan
ling len men sau:
-

Len men rugu: tao ra san pham la ancol elylie.
cnil 111

CJI,:.(),

> 2C:11.011 ^ CO2

- Len men butyric: san pham la axil butyric
cnzini

C,ll,:0.

>

ClL-CIL-ClL-COOTI-f 2CO: + 2IIi
Axit butyric

-

-,. ,J^^
HO \
NO-

k-

HO • : ^ - - - " C O O
OH

gluconate

.^-OH
-^-COOH
'OH

glucaric acid

OH

--^-VtCOOH

- i CJH
c^uconic add

H0\--~C00H

o
2-keto-gKjconlc acid

Sir o x i hoa " l u c o / o " \i\ eac d a n xuat t r c n cac x u c tae k i m loai

Cac kim loai quv nhu ho Pt, Pd, Au ihuanu duo'c lua ebon lam xiie tae cho
cac phan irng oxi hoii hoan loan |20'^|. Vao cuoi nhung nam 1960, ngudi ta sir
dung xiic tae Pl/Rd cho phan irng xu ly khi thai va xiic tae Pd cho phan irng
axctoxyl hoa olelln. Khi su dung cae he xiie lac kim loai quy nay de lien hanh oxi
hoa chon loe can chii y phai ihire hien qua trinh trong dieu kicn khu (du hidreaebon
va thieu oxi), neu diing du oxi thi cae kim loai qui sc xiie tae cho phan irng oxi hoa
hoa loan nga} a nhiel do ihap (200

250"C^). Xiie tae Ag cung da dirge nghien ciru

\ a irnu duim lir rat lau cho cae phan irnu oxi hoa etilen thanh etilen oxit ha\ oxidehidro hoa elanol thanh axelaldehit. Ag cung duo'c hang BASl' su dung thanh
cong cho phan irng long hgp Ibrmandehit |2P^|. I)a\ cung la xiic tae du\ nhal co
do chon loe cao cho phan irng oxi hoa chon loe etilen de tao hgp chal epoxi (etilen
oxit) trong pha khi. '\\\\ nhieMi, hien na\. khi ma \ an dc moi truong dang ngay cang
"nong", \'iec ban ehe eac san pham phu, eac chat thai la mot yeu cau bat buoc doi
vai cac qu\' trinh cong nghe hien dai huong nghien ciru su dung cac kim loai quy
lam xiic tae cho cac phan irng oxi hoa lai diro'c quam lam nhieu bo'i uu diem cua
loai val lieu na>, do la linh ben. do chon loe cao. ban che cae san pham phu \ a kha
»

nang lai su dung nhieu Ian.
Cian daN. da co mot so lurong nghien ciru trong \iec dung xiic tae eo cau true
xae dinh eiing \oi hidi'operoxil (I b O : boae peroxit hCru eo') nhu la chat oxi hoa cho
phan ung oxi hoa chon loe. Vat lieu mao quan trung binh nhu la zcolit.
aluminophotpliat(AlP()). silieonakiminophotphal (SAPO) eiing \'ai su sap xep eo
Irat tir cua cac kenh mao quan dang dirge nghien ciru rong rai. Nhiing \at lieu na\
14


CO be mat Irong Ian va co cac lam dae trung la eac kim loai boat dong, su phan bo

LMuc tieu:
Muc lieu eua de lai nay la long hgp va dae trung cae be val lieu mao quan trung
binh chira kim loai chuyen liep V2(Vri-MCM-41; Pl/MClVl-41 va danh gia tinh
chat xuc lac cua chiing irong phan irng oxi boa a-pinen, melyl oleat va glucose.
2.Cac noi dung nghien ciiu
- Tdng hgp eac he val lieu MCM-41, Ti-MCM-41, V . ( V r i - M C M 4 l va Pt/MCM41.
- Dae trung cac he \ at lieu long hgp duge bang cac phuong phap val ly va boa ly
hien dai: XRl), Sb;M, Tl-M, 11.-I'PR, ...
- Danh gia tinh chat xiie tae ciia cac he val lieu trong phan ung oxi boa a-pinen
(V20/ri-MCM41),

ctyl

oleal

(Ti-MCM-41 j ,

glucose

(V205/ri-MCM41

va

Pl/MCM-41). San pham phan irng duge phan lich bang cac phuong phap: sac ky
khi - khoi pho ((iC-MS), sac ky long-khoi pho (bC-MS) va sac ky long hieu nang
eao(llP-b(^).
III. PIIUONC PIIAP NCIHEN CIJU
1. Dieu che chat xuc tae:
-


I^huong phap hien \ i dien lu quel (SI:M): xae dinh kich thuoc tinh the, kich
thu'oe hai.

-

Phirong i^tliap hien \ i dien lu truyen qua ( ll-M): xae dinh \'al lieu mao quan
nano, kim k)ai ha} oxil kim loai phan tan kich thirae nano.

6