Nghiên cứu phản ứng trans este hóa trong sự có mặt của xúc tác chất lòng ion

TAP CHI HOA HQC
DOI: 10.15625/0866-7144.2015-00137

T. 53(3) 322-326

THANG 6 NAM 2015

NGHIEN COU PHAN U'NG TRANS-ESTE HOA
TRONG Sly CO MAT CUA XOC TAC CHAT LONG ION
Pham Thi Nam Binh*, Ding Thi Thuy Hanh, Vfi Thi Thu Hi, DO Thanh Hai, Trtin Van Hien
Phong TNTD Qudc gia ve Cling nghe 1QC - haa dazi, Vien Haa hQc Cong nghi Op Viet Nam
Den Tea soan 17-11-2014; Chip nhan clang 20-6-2015
Abstract
Transesterification reaction between refined coconut oil and methanol was investigated in the present of ionic
liquid 1-(4-sulfonic acid) butyl-3-methylimidazolium methane sulfonate as catalyst. The results show that the methyl
esters content of product exceeds 88 % at 75 °C for 8 hours with methanol/oil/catalyst molar ratio of 12:1:0.15. This
catalyst can be recovered and reused. So it has potential application in transesterification process.
Keywords. FAMEs, ionic liquid, transesterification, coconut oil.
I. MO DAU

Ilea not tren.
Bai bao nay glen thiau cac kat qui nghien ciru
Cong nghe truyen dicing trong san xuat metyleste tong hop, dac trtrng vi thir nghiam hoat tinh Vic tac
cita cac axit beo (FAMEs) irng dung trong san xuat dm met se IL ten ca sec imidazolium tong phan
nhien lieu sinh hoc di tir nguon dau men d6ng, thuc ting trans-este hoa nguyen lieu triolein va dau dira
vat là cong nghe' sir dung Vic tae kiem deng the. tinh luyen.
Cling ngh'e nay rat phut hop vai nhang nguon nguyen
lieu co ham *mg nu& va axit beo W. do thfip. Vai 2. THVC NGHIEM
cac nguyen lieu ca ham ltrqng axit beo cao (thuang
la cac nguyen lieu re tien, khong canh tranh yeti 2.1. H6a chat va thiet bi
nguon lacing th,rc), ding nghe nay cho hieu qua

khong cao. Ben canh do, 'dm tac ding the co nhtrqc
Cac Ma chit dung trong tong hqp IL, triolein va
diem la kh6ng thu h6i duct sau phin img, an mon metanol co nguon gOc tir Sigma-Aldrich va
thiet bi va gfiy o nhiem mei twang nen khOng dap Spectrum China duqc sir dung uvc tiep, kh6ng qua
ling &roc cac tieu chi dm Floa hoc xanh. Vi vay, btrac tinh che.
viec fiat kiem cac cong nghe va Vic tic mai, co kha
DAu dira tinh luyen (tri s6 axit 0,25 mg KOH/g)
nang chuyen hoa clang thai Ca axit beo tar do va co nguon gee tir Cong ty Dalt Ttr?yng An, Viet Nam.
triglyxerit thinh FAMEs tra nen rat can thiet: Theo
Cac IL sau khi tong hop dtrqc dac tnmg cau true
do, cac qua trinh sir dung xfic tac axit di the dtrqc bang phtrang phap ph6 cong huang tir hat nhfin tren
quan tam nghien ciru do chfing di the xfic tac cho ca may Brucker AVANCE-500 MHz va Brucker
AVANCE-250 MHz va dac trung tinh chAt nhiet
hai phan fing este Ma va trans-este h6a [1-7].
Cac nghien ciru tren the giai cho thAy chit long troll may DTG-60H Shimadzu.
ion (IL) vai vai tro Vic tac c6 rat nhieu tru diem nhtr
khong yeu au chat che ve tri se axit trong nguyen 2.2. 'ding hop ILs
lieu ban diu, tach khoi san phfim sau phan tang va
co kha nang tai sir dung nhieu Fan [3-7]. (3 Viet Nam 2.2.1. Tang h9p 1-metylimidazolium hydro sulfat
co met s6 nghien ciru trien khai ve qua trinh san xuat
Nho giQt dung dich ntrac china 0,2 mol
FAMEs sir dung xfic tac di the tren ca ser ding nghe
gOc dm Han Quoc [8, 9]. ve IL, co the ke den met H2Sa4vao 0,2 mol N-metylimidazol (mim) da dtrqc
so nhorn Lie gia nghien ciru tong hop, dac trong va lam lanh san ye 0 °C trong dieu kien co khufiy. Sau
img dung cila IL nhu P. T. S. Nam [10], L. N. Thach de khuAy hiln hop phan img trong, 2 gia a nhiet de
[11, 12], B. T. L. Thiry [13, 14]. Tuy nhien chtra ca phong. Ket tit& phin img, san phfim duqc say a 90
nghien ciru naolien quan den tang hqp va img dung °C dtrai ap suAt 0,1 Bar trong 12 gia de loai be mat.
cac )(ix the IL cho phan (mg este Ilea va trans-este San phfim thu ducc la cac chat long khong mau hoac

322

Pham Thi Nam Binh va Ong sy-

TCHH, T. 53(3), 2015
yang nhat, sanh.

2.2.2. Tong hop 1-ankyl-3-metylimidazolium hydro
sulfa! (C„miniHSO4)

Ket qua khao sat hoot tinh xUc tic cua cac
ILduqc trinh bay teen hinh 1. Ham lucrng metyl este
cua san pham cang Ion thi hoat tinh cua Vic tac IL
ttrang ling cang cao.
30

Phucrng phap tong hop CnmimHSO4 ducrc thvc
hien nhu mo to trong [15].

2.2.3. Tdng hop 1-(4-sulfonic axit)buty1-3metylimidazolium metanesulfonat
mimC4H8S03H.CH3S03va 1-(4-sulfonic axi0butyl3-nietylimidazolium hydrogen sulfat
mimC414503H.HSO4

CA

20

E ft. 10
04

Nho gipt 1,4-butan sulton vao mim theo ty le
mol 1:1 6 nhiet dO phang, sau do khuay hon hcrp
phan ling a 50 °C cho den khi (long ran hoan toan.
Rim chat ran thu throe bang dietyl ete va sAy trong
chan khOng a 60 °C trong 8 gia. Nh6 tir tir dung djch
axit CH3S03H (99,5 %) hoac H2SO4 (98 %) vao chAt
ran thu duqc theo ty le mol 1:1 a 0 °C, sau do khuAy
lion hop u 80 °C cho den khi hoa long hoan toan.
Rira san phAm bang dietyl etc va sAy trong tit say a
60 °C dual ap suAt 0,1 Bar. San pham thu dtrqc la
cac chat long co mau yang nhat, sanh.
2.2. Phan irng trans-este hoa
Phan ling dirge tien hanh trong binh eau 3 ea'
dun* tich 100 ml co trang bi sinh han, nhiet ke va
khuay tir. Tec de khuay duqc giir kh6ng doi (500
yang/phut) trong mpi thvc nghiem.
Nguyen lieu triolein duqc sir dung trong phan
ling trans-este h6a de danh gia hoot tinh cua cac xuc
tac a cling met diet' kien phan ling (75 °C, 1 gia, ty
le mol metanol/triolein/xiic tac = 9/1/0,15). Nguyen
lieu dAu diva tinh luyen &roc sir dung de nghien ciru
phan 1mg trans-este hoa trong sir c6 mat dm IL co
hoot tinh mac tac cao nhat.
Thy trang thirc nghiem ma mau duqc lAy.dinh kY.
Ham
metyl este cita cac mau san pham duqc
xac dinh bang GC-MS theo tieu chuan EN-14103.
Tnrirc khi phan tich, mau san pham &roc xli IY bang
phuong phap chiet vai hon hop ntrac va n-hexan
theo tY le the tich 1:1.

Doi vai cac thkrc nghiem nghien c(ru kha nang
tai sir dung dm xiic tic, x6c tac se' &rot thu hai, tinh
the va sir dung quay yang cho phan ling a cling 1
diet' kien.
3. KET QUA VA THAO LUAN

3.1. Sing luc vac tic IL cho phin irng trans-este
hoa

E

0

cb,s

s

Looi 'dm

Co

s', 5

,

9

Hinh 1: Ket qua khao sat hoot tinh Vic tac cita IL
Co the thAy rang hoat tinh )(Ix tac cua
mimC4H8SO3H.CH3SO3 cao nhAt, sau do den

mimC4H8S03H.HSO4. Cie IL nay c6 hoot tinh cao
hon han so vai cac xac tac IL can .loi. Dieu nay c6
the giai thich la do chang dtrqc "bo sung" tam axit
trong cation (nhom SO3H), dan tai lam tang manh
hoot tinh xtic tac.
Doi vai nhom IL co cling anion HSO4 nhtmg
khac nhau ve d6 dai mach ankyl trong nhom the a
cation, quan sat thAy sir tang hoot tinh xtic tac theo
trot tir dm day sau: HmimHSO4 < C4mimHSO4 <
C6mimHSO4 < C8mimHSO4 < ClomimHSO4.
Nguyen nhan sir tang hoot tinh xuc tac a day hilt la
do sir tang d6 axit khi de dal mach ankyl tang [3].
Nhu vay, trong s6 cac IL dtrac khao sat,
mimC4H8SO3H.CH3SO3 co hoat tinh x6c tac cao
nhat, ham Itrang metyl este dm san pham dot 26,95
% trong thai gian 1 gia. X6c tac nay dirge lira chpn
de nghien ciru phan ang chuyen Ma este tir dau dira
tinh luyen.
3.2. Cic yeu to inh hurting den phin ling trans-

este h6a dttu dira sir dung 'cue tic mim
C4H8SO3H.CH3SO3
3.2.1. T.)) le mol xuc tac/ddu
Ket qua khao sat dtrac bieu din trong hinh 2.
Hieu qua phan 1mg thay doi r6 ret khi tang Itrang
xuc tac. Khi ti le )(lie tac/dau tang tir 0,05 len 0,15,
ham Wang metyl este dm san pham tang tir 32,35.%
len 74,60 %. Ham Itrang metyl este dm san pham
khong tang nhieu khi tang t3 le xac tacklAu len tren

323


TCHH, T. 53(3), 2015

Nghien caw ',hem zing trans-este h6a...

gia trj 0,15. Do do, ti lg mac tic/6'u duqc Iva chon IA
0,15.
_

3.2.3. Nhiet d()
Anh twang cua nhiet d$ den phin (mg &Km the
hien tren dO thi hinh 4.

100
80

4.)

100
.64
▪ 80 al p
60 E.<03
Et.40 -

-

CA

60 -

g cn

20

-

o

ea

1

20 0.05 0.1 0.15 0.25 0.5
0

TS, le mol xzic tac/dAu

45

Hinh 2: Anh hutmg cua tj, le mol mac tac/clAu den
ham Itivng metyl este dm san pham Flan ting
(75 °C, 8 gitr, tj, le mol metanoVdau = 9)
3.2.2.

75

Hinh 4: Anh !luting cua nhiet dij den phan Crng
(8 gitr, tj, le mol metanoUdAu/xac tac = 12/1/0,15)

Hinh 3 trinh bay anh hirtmg cua tj, le mol
metanol/dAu den phan Cmg.
100

§

65

Nhiet (10 phan (mg, °C

mol metanol/dciu

ti)
IC

55

TU. hinh 4 cho thAy, ham lug metyl este dm
sin pham tang khi tang nhiet dp tir 45 °C len 75 °C.
Tai 75 °C, ham luvng metyl este dat gii tri Itm nhAt
(88,71 %). Nhiet dr;) 75 °C là nhiet d'q hoi Itru cua
b6n hqp phan (mg. Do do, 75 °C duqc Iva chon là
nhiet dq thich hop cho phan

80 -

3.2.4. Thai gian phan zing

60 -

Anh huang cua thtri gian den phan ung dirqc
trinh bay teen hinh 5.

0c
g
•
20 E
0

100

9
12
18
6
TS, le mol Me0H/dAu
Hinh 3: Anh hirting cua tj, le mol metanoUdAu den
phan img (75 °C, 8 gitr, tj, le mol mac tack& = 0,15)
3

Khi tang tj, le metanoUdAu tir 3 len 12 thi ham
luqng metyl este dm san phAm tang (tir 54,08 % len
88,71 %). Dieu nay là hop 15, vi trans-este hoa IA
phan Irng thun nghjch,. nen viec cho du. mgt chit
phin Cr
ng se lam can bang djch chuyen ve phia tao
san pham. Ham luqng metyl este dm san pham tang
len kht4 dang ke khi tiep tvc tang tj, le
metanol/dau tir 12 len 18. Han nila, Wong metanol

du quA nhieu se lam cho hon hqp phin ting kho Lich
pha, ding thtri ton nang luqng de gia nhiet va de thu
hoi metanol. Do do, ti le mol metanoUdAu dirqc Iva
chon là 12.

60 -

20 0
0 2 4 6 8 10 12
Thtri gian phin Cmg, gitr
Hinh 5: Sv phi thucjc ham luqng metyl este dm san
phirn vao thtri gian phan Crng
(75 °C, tj, le mol metanoUdiu/Vic tac = 12/1/0,15)
Co the thAy yang tir 2-8 gia., ham lucmg metyl
este cCia san pham tang theo theyi gian phan Ung,
trong do tic d'e tang nhanh nhAt trong khoang theri

324


Pham Thj Nam Binh va cOng su

TCHH, T. 53(3), 2015

Oil Catalyzed by Bronsted Acidic Ionic Liquids. Ind.
Eng. Chem. Res., 46, 7955-7960 (2007).
4. M. Ghiacia, B. Aghabarari, S. Habibollahi, A. Gil.
Highly efficient Bronsted acidic ionic liquid-based
catalysts for biodiesel synthesis from vegetable oils,
Bioresource Technology, 102, 1200-1204 (2011).

3.2.5. Tai sir dung xfic tac
5. Ming Ming Fan, ling Jie Zhou, Qiu Ju Han,
Ping Bo Zhang. Effect of various functional
HiEu qua tai sir dung xtic tac duqc trinh bay
groups on biodiesel synthesis from soybean oils
by acidic ionic liquids, Chinese Chemical Letters,
trong bang 1.
23, 1107-1110 (2012).
6. Kai-Xin Li, Li Chen, Zong-Cheng Yan, Hong-Lin
Bang 1: HiEu qua tai sir dung xiic tac
Wang. Application of Pyridinium Ionic Liquid as a
Ham Itrqng metyl este dm
SO Ian tai sinh
Recyclable Catalyst for Acid-Catalyzed
Transesterification of Jatropha Oil, Catal Lett., 139,
san pham sau phan ang, %
xiic tac
151-156
(2010).
88,71
0
7. Hui Luo, Kai Xue, Weiyu Fan, Chuan Li, Guozhi
87,84
1
Nan, and Zhaomin Li. Hydrolysis of Vegetable Oils
to Fatty Acids Using Bronsted Acidic Ionic Liquids
87,15
2
as Catalysts, Ind. Eng. Chem. Res., 53, 11653-11658
86,99

3
(2014).
86,46
4
8. Vu Thj Thu Ha, Mai Ngoc Chile, J. W. Yoo, Ltru
86,10
Hoang Ngoc, Nguyen Thj Thuy Ha, D8 Monh Himg,
5
Pham Minh TU., Nguyen Cong Long. Nghien ctiu va
trien
khai conk nghe xac lac di the tien lien, hieu qua,
Co the thay rang, sau 6 lAn sir dung ham luqng
it
phcit
thai de san xmat nhien lieu sinh hoc biodiesel,
metyl este dm san pham van dat tren 86 %.
Top chi Khoa hoc va Cong nghe, 49(6), 34-36
(2011).
4. KET LUAN
tai
Thanh Thuy. Isidro cao tang kit
9. Pham
Nghien cult tong nghe dieu the xac tac de son xuer't
Da tong hqp va thir nghiEm hoat tinh xuc tac
diezen sinh hoc B100 truy tiep to nguyen lieu co trj
trong phan .irng trans-este h6a triolein cda 7 chat
phat
so Fat cao theo cling nghe lien tuc, thuac
sinh hoc den nom 2015, tam nhin den
long ion. Ket qua nghien ciru cho thay, chat long ion

trien nhien
nam 2025 (2013).
mimC4H8S03H.CH3S03 c6 hoat tinh xdc tac tot
nhat. Phan img trans-este h6a clau diva tinh luyEn 10. Le Vu Ha, Nguyen Thi Hong Anh, Nguyen Anh
Tuan, Phan Thanh Son Nam. Ionic liquid-promoted
ten Vic tic mimC4H8SO3H.CH3SO3 a nhiEt de• 75
n-arylation
between piperidine and 4-bromonitro
tj, Ig. mol
trong thoi gian 8 Oar,
benzene without catalyst, Vietnam Journal of
metanol/dauhdic tac = 12:1:0,15 cho san pham co
Chemistry, 51(2AB),96-102 (2013).
ham Itrqng metyl este dat tir 86,1-88,71 %. Xuc tic
11. Le Ngoc Thach. Tang hop mat so chat long ion thuac
c6 kha rang tai sir dung nhieu Ian. Nhu vay, day la
nhom alkilmetilimidazolium, sir dung lam mai tritemg
mEt Vic tac c6 tiem nang cho cac qua trinh san xuat
phan zing va dung mOi ly trich, De tai NCCB
FAMEs, dap img cac tiEu chi dm H6a hqc xanh.
Nafosted (2010).
12. Anh Ngoc Tran, Thatch-Nhan Van Do, Loan-Phung
My Le, Thach Ngoc Le. Synthesis of new fluorinated
Cong
trinh
nghien
tau
nay
dint
tai

trq
Liii cam o'n.
imidazolium
ionic liquids and their prospective
bai De san phat trien nhien lieu sinh h9c den nam
function
as
the
electrolytes for lithium-ion batteries,
2015, tam nhin den nam 2025, BO Cong thurnig.
Journal of Fluorine Chemistry, 164, 38-43 (2014).
13. Thi Le Thuy Bui, Wolfgang Korth, Andreas Jess.
TAI 14U THAM KHAO
Influence of acidity of modified chloroaluminate
based ionic liquid catalysts on alkylation of iso1. Stem, et al. Process for the production of esters from
butene with butene-2, Catalysis Communications,
vegetable oils or animal oils alcohols,
25, 118-124 (2012).
US005908946A (1999).
too
14. Bui Thj Le ,Thity. Rao cao D'e tat Nghien
2. Yoo, et al. Ceramic catalyst used in manufacture of
vat lieu chat long ion mang tren mang polymer in
fatty acid alkyl esters and method for preparing high
dung tach CO2 ra khoi cac khi hydrocacbon, ma so
purity fatty acid alkyl esters using the same, US
de tai KCO2.TN03/11-15 (2012).
20120130101A1 (2012).
15. Pham Thj Nam Binh, Nguyen Thj Ha, DIng Thj
3. Qin Wu, He Chen, Minghan Han, Dezheng Wang,

Thuy Honh, V0 Thj Thu Ha. Tang hop va this nghiem
and J infu Wang. Transesterification of Cottonseed
hoot tinh xac tac clic, mat so chjt long ion tren co' set

gian 4 Oa. dau.tien. Tir 8-10 gib, ham luqng metyl
este dm san pham troy nen khong dOi.
Nhtr vay, c6 the dirng phan img sau thai gian 8
gib.

325


TCHH, T. 53(3), 2015

Nghien ctiu pitan ling trans-este Ma...

1-butyl-3-metyltmidazolium trong phan ting este hoa
aril brio. Tap chf Xtic tac %/a HAI) plw, 3(3), 34-39
(2014).
Phu lyc
Dir lieu pile) 11-1-NMR, "C-NMR, va TG-DTA c6a
cac IL tong hqp trong bai bdo.
1-metylimidazolium hydro sulfa!: '1-I NMR (500
MHz, D20): 5 = 3,791 (s, 3H); 7,308 (s, 2H); 8.525
(s, 1H); 13C NMR (125 MHz, D20): S = 35,582;
119,609; 123,092; 135,131. Nhiet d6 phan huy:
363,02 °C.
1-butyl-3-metylimidazolium hydro sulfa!: 'H
NMR (250 MHz, D20): S = 0,91 (t, 31-1); 1,29-1,32
(m, 2H); 1,85 (m, 2H); 3,89 (s, 3H); 4,20 (t, 2H);

7,45-7,50 (s, 2H); 8,74 (s, 1H). Nhiet d6 phan huy
cita C4mimHSO4: 337,29 °C.
1-hexy1-3-metylimidazolium hydro sulfa!: 'H
NMR (500 MHz, D20): 8 = 0,76-0,79 (t, 3H); 1,22
(s, 61-1); 1,77-1,80 (t, 2H); 3,81-3,86 (s, 2H); 4,094,13 (t, 31-1); 7,35-7,40 (m, 2H); 8,62 (s, 1H). Nhiet
d6 phan hay: 320,33 °C.

1-octy1-3-metylimidazolium hydro sulfa!:
'H-NMR (500 MHz, D20): S = 0,76-0,78 (t, 3H);
1,17-1,22 (m, 10H); 1,77-1,80 (t, 2H); 3,81 (s, 3H);
4,09-4,12 (t, 2H); 7,35 (s, 1H); 7,39 (s, 11-1); 8,62 (s,
1H). Nhiet d6 phan buy: 342,48 °C.
1-decy1-3-metylimidazolium hydro sulfat: 11-1
NMR (500 MHz, D20): 5 = 0,74-0,76 (t, 3H); 1,161,22 (m, 14H); 1,78 (s, 2H); 3,83-3,85 (m, 3H);
4,11-4,14 (t, 2H); 7,39 (s, 2H); 8,69 (s, 1H). Nhiet
d6 phan h6y: 342,17 °C.
1-(4-sulfonic axis) butyl-3-metylimidazolium
hydro sulfa!: 'H NMR (500 MHz, D20): 5 = 1,6181,754 (m, 2H); 1,897-2,103 (m, 2H); 2,817-3,215
(t, 2H); 3,802 (s, 3H); 4,119 (t, 2H); 7,316-7,369
(d, 2H); 8,597 (s, 1H). 13C-NMR (125 MHz, D20): 8
= 21,051; 28,208; 35,795; 49,036; 50,194; 122,291;
123,792; 136,063. Nhiet d6 phan h6y: 355,08 °C.
1-(4-sulfonic axis) butyl-3-metylitnidazolium
metanesulfonat:
'H-NMR
(500
MHz,
CDCI3+MeOD): S = 1,877-2,289 (m, 6H); 2,7642,948 (m, 81-1); 7,277-7,624 (m, 2H); 9,194 (s, 1H).
13C NMR (125 MHz, D20): S = 23,619; 28,810;
36,286; 39,369; 49,155; 49,216; 122,684; 123,570;

137,056. Nhiet d6 phan hay: 363,17 °C.

Lien he: Pham Thi Nam Binh
Phong Thi nghiem Tr9ng diem Cong nghe 19c, hoa dAu
S6 2, Phdm NO Lao, Hoan Mem Ha N6i
E-mail: ; Dien thodi: 0943 917 959.

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