Application of Acidic Ionic
Liquid on the
Catalyic Green Process
酸性離子液體在綠色催化製
程之應用
吳榮宗
(台灣中油公司綠能科技研究所)
[雲林科技大學]
2011.11.17
1
Contents
I. What is ionic liquid(IL)?
II. Properties of ionic liquids
III. Application of acidic IL
Lewis acid IL
Bronsted acid IL
IV. Conclusion
2
工業上常用之酸性觸媒
1.傳統酸觸媒
: H2SO4 , AlCl3 , HF
CF3SO3H, PTSA
2.固態酸觸媒
: Zeolite, H3PO4/SiO2
SO42-/ZrO2, SbF5/TiO2
3.高分子酸觸媒 : Amberlyst, Nafion
4.異多體酸觸媒 : H3PW12O40(TPA), TPA/S
5.離子液體酸觸媒: Lewis /Bronsted Acid IL
3
Application Method of Conventional Strong Acid Catalyst
(A) Lewis Acid Ionic Liquid
R
R
NCl
+ AlCl3
NHAl2Cl7
[PHC]
(Water-sensitive, Biphasic System)
(B) Bronsted Acid Ionic Liquid
SO3 + H2SO4
N
N
SO3H[HSO4]
[PPS]
(Water-tolerable, Biphasic System)
(C) Bronsted Acid Ionic Liquid/ Solid
N
[PPS]
SO3 + H3PW12O40
N
SO3H[H2PW12O40]
(Water-tolerable, Biphasic System)
4
What is ionic liquid (IL)?
• ILs are salts composed entirely of ions, typically large organic cations
and small anions, they are liquids at low temperature(<100℃).
• ILs have been known since 1914, but have only been investigated as
acid and transition metal catalysis for 20 years(chloroaluminate IL).
• IL catalysis can be carried out in biphasic system with easy recovery of
homogeneous catalyst and product separation.
• ILs have no detectable vapor pressure and do not emit VOC, providing
a basis for clean manufacturing---”Green Chemistry”.
5
COLORFUL FUTURE
Ionic liquids have a promising future in chemicals synthesis.
6
Typical Structure of Low Temperature IL
Cations:
R2
R2
R1
+
N
R3
N
N
R4
R1
N
R2
R1
R1
R2
R4
P+
R1
R3
R2
S+
R3
R4
Anions: BF4-,PF6-,SbF6-,NO3-,CF3SO3-,(CF3SO3)2N-,
ArSO3-,CF3CO2-,CH3CO2-,Al2Cl7-,HSO47
Properties of Ionic Liquids
• Low Vapor Pressure
• Thermal Stability (up to 300~400℃)
• Immiscible with Some Organic Solvents
• Polarity and Hydrophilicity/Lipophilicity
(Adjustable)
• Superacidity of Chloroaluminate (H0= -18)
(Adjustable)
8
Characteristics of Ionic Liquids
(A)Melting Points
•Melting Points with Different Cations
9
•Melting Points with Different Anions
10
Asymmetry explains the low melting point
11
(B) Solubility
Water-insoluble
[PF6][(CF3SO2)2N][BR1R2R3R4]-
Water-soluble
[BF4][CF3SO3]-
[CH3CO2][CF3CO2]-, [NO3]Br-, Cl-, I-,
[Al2Cl7]-, [AlCl4]-
12
(C)
Thermal
Stability
13
(D)Acidity and Coordination Ability
basic/strongly
coordinating
neutral/weakly
coordinating
Cl-
AlCl4CuCl2-
AcNO3-
Al2Cl7Al3Cl10SbF6BF4PF6-
SO42AlCl3
N
R1
N
R 2 Cl
basic/strongly
coordinating
acid/noncoordinating
Cu2Cl3Cu3Cl4AlCl3
N
R1
N
R2
AlCl4-
neutral/weakly
coordinating
N
R1
N
R2
Al2Cl7-
acid/noncoordinating
14
Acid Strength of IL
15
CH3CN與CH3CN-IL 之 FT-IR光譜
L acid
B acid
16
離子液體PC1之pyridine FT-IR
吸收光譜(X=0.50, 0.65)
L-acid site
B+L-acid site
PHC, X=0.65
X=0.50
B-acid site
absorbance
扣除主要pyridine吸收之IR光譜
cm-1
17
Synthesis of Ionic Liquid
NR3
Step I
+ R’X
[R’R3N]+XStep IIa
+Lewis acid MXy
[R’R3N]+[MXy+1]-
Step IIb
1. +Metal salt M+A-MX(precipitation)
2. +Bronsted acid H+A-HX(evaporation)
3. Ion exchange resin
[R’R3N]+[A]18
Application of Ionic Liquids
19
Catalytic Research on Ionic Liquids
1. Ionic Liquid Acid Catalysis(B & L acid)
•
•
•
•
Isomerization(Cycloalkane/n-Alkane)
Alkylation(Aromatic/Isobutane with C4 Olefin)
Polymerization(C4 Olefin)
Esterification(FAME)/ Transesterification
2. Ionic Liquid Organometallic Catalysis
• Dimerization(C4 Olefin)/Oligomerization
• Hydrogenation/Oxidation/Hydroformylation
• Heck/Suzuki/Acylation/Esterification
3. Ionic Liquid Nanometal Catalysis
• Selective Hydrogenation
• PDMA/ Butadiene/ Isoprene/Cyclopentadiene
20
Acidic Ionic
Liquid Catalysis
21
Acidic Ionic Liquid Catalysis
(A)Lewis Acid Ionic Liquid
•
•
•
•
Polymerization of Butene
Alkylation of Olefin(C4 Olefin/i-C4)
Alkylation of Aromatics(Olefin/Aromatic)
Isomerization of Cycloalkane(JP-10 &
Adamantane)
(B)Bronsted Acid Ionic Liquid
• Esterification of Bio-diesel Synthesis
• Esterification of Polyol(Glycol & Glycerol)
22
(A)Lewis Acid Ionic Liquid
Polymerization of Butene
Adavantage of acidic ionic liquid process:
(i) Ease of separation of the product polymer from the
catalytic component, further undesirable reaction
could be avoided.
(ii) The product formed need not to be water-washed,
because of low level of the catalytic IL in the product.
(iii) The catalyst can be recycled and thereby reduces
operation cost.
(iv) The higher molecular weight of polymer could be
obtained with high yield, even at higher temperature.
23
(A)Lewis Acid Ionic Liquid
Alkylation of Olefin(i-C4/C4=)
C4= + i-C4  i-C8(Alkylate fuel )
Conventional process:
HF :(UOP &Phillips) /Toxic
H2SO4:(Stratco &Kellogg) /Corrosion &
waste acid treatment
Acidic Ionic Liquid process( Biphasic process):
[BMIM]Cl-AlCl3 (Chauvin , 1994)
24
Alkylation
of
C4 Olefin
with i-C4
Ionikylation
Process
BMIC/AlCl3
/CuCl
25
(A)Lewis Acid Ionic Liquid
Alkylation of Aromatics
C6H6 + C2H4=  C6H5-C2H5  C6H5-C2H4 ( Styrene )
(AlCl3 or ZSM-5)
C6H6 + C3H6=  C6H5-iC3H7  C6H5-OH ( Phenol )
(AlCl3 or ZSM-5)
C6H6 + C12H24=  C6H5-C12H25 ( LAB )  ( Detergent )
[BMIM]Cl-AlCl3
26
(A)Lewis Acid Ionic Liquid
Isomerization of Cycloalkane
Synthesis of JP-10
Synthesis of Adamantane
Supported Ionic Liquid
Pseudo-fixed-bed Ionic Liquid
27
Isomerization of Cycloalkane
( Synthesis of JP-10 )
Acidic IL
endo-THDCPD
(m.p. 77C)
H2
exo-THDCPD(JP-10)
(m.p. <-110C, b.p. 185.6C)
adamantane
(m.p. 267C)
Ni
Pyrolysis
Gasoline
endo-DCPD
(m.p. 22.6C, b.p. 170C)
cyclopentadiene
(b.p. 41.5C)
THDCPD：Tetrahydrodicyclopentadiene
28
Representative Properties of Jet & Missile Fuels
JP-4
Ave. formula C9.5H18.9
W-5
RJ-4
RJ-4I
RJ-5
C10H19
C12H20
C12H20
C14H18
JP-9
JP-10
C10.6H16.2 C10H16
Ave. mol. wt.
133
139
164
164
186
143
136
C：H ratio
0.5
0.53
0.6
0.6
0.78
0.65
0.62
Sp. Gr.
0.77
0.83
0.94
0.94
1.08
0.94
0.94
Freeze pt. ℃
<-72
<-51
<-40
<-65
>0
<-65
<-110
Flash pt. F
-20
150
150
150
230
70
130
Vis. at -40℃
4.5
17
60
28
2000
24
19
Heating
value(K
Btu/gal)
118
125
140
138
161
142
142
0
29
JP-10傳統合成方法
1.硫酸法(H2SO4)
缺點：伴隨開環、裂解及聚合反應，反應後生成
很多黑色焦狀物。
2.氯化鋁(AlCl3)
缺點：反應後，經過鹼洗、水洗，氯化鋁變成不
溶於水的氫氧化鋁，會產生大量油泥狀廢
棄物，且觸媒無法重複使用。
3. Zeolites and Heteropoly Acids
缺點：操作溫度高(185-195℃)，易產生副產品。
30
Experimental
R1
N
N
AlCl3
Cl
R2
R1
N
N
PHC
R2
N
R1
N
R4
R6
N+
N
N
R2
Al2 Cl7
R 1=H, R2=H, X=Cl
R 1=H, R 2=H, X=Br
:
BMIC
: R 3=C4H9, R 4=CH3, X=Cl
HMIC
: R3=C 6H13, R4=CH3, X=Cl
OMIC
: R3=C 8H17, R4=CH3, X=Cl
HDMIC : R 3=C16H33, R 4=CH3, X=Cl
H
R5
:
R1
PHB
XN
R2
BMPC : R 1=C 4H9, R 2=CH3, X=Cl
X-
R3
AlCl4
AlCl3
X-
BMIB
: R 3=C4H9, R4=CH3, X=Br
R7
TEAC
: R5=R 6=R7=C 2H5, X=Cl
31
Synthesis of JP-10
不同離子液體JP-10合成反應活性比較
Conversion of endoTHDCPD
1.0
0.9
0.8
PC-1
0.7
AC-1
0.6
IMC-1
0.5
IMC-4
0.4
PC-2
IMC-3
0.3
IMC-2
0.2
0.1
0.0
0
200
400
600
800
1000
1200
1400
reaction time(min)
X=0.6 , IL/endo-THDCPD=1/12.8(mole ratio) , 50 C
32
離子液體中AlCl3莫耳分率對JP-10合成反應
活性影響
Conversion of endoTHDCPD
effect of AlCl3 mole ratio on conversion of endoTHDCPD
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.40
0.50
0.60
0.65
0.75
0.80
0.86
0
200
400
600
800
1000 1200 1400 1600
reaction time(min)
[IMC-1]AlCl3 , IL/feed=1/12.8 , 50 C
33
Anionic Species in Chloroaluminate IL
with Different AlCl3 Mole Fraction
34
absorbance
不同AlCl3莫耳比值之CH3CN FT-IR光譜(PC-1)
X=0.75
X=0.70
X=0.65
X=0.60
X=0.50
X=0.40
cm-1
35
觸媒再使用活性測定比較(JP-10合成)
1.0
Conversion of endoHDCPD
0.9
0.8
0.7
1st
2nd
0.6
3rd
0.5
0.4
0.3
0.2
0.1
0.0
0
200
400
600
800
1000
1200
1400
reaction time(min)
[IMC-1]AlCl3 , X=0.6 , IL/feed=1/12.8 , 50 C
36
Synthesis of Adamantane
Acidic IL
endo-THDCPD
(m.p. 77C)
H2
Acidic IL
exo-THDCPD(JP-10)
(m.p. <-110C, b.p. 185.6C)
adamantane
(m.p. 267C)
Ni
Pyrolysis Gasoline
endo-DCPD
(m.p. 22.6C, b.p. 170C)
cyclopentadiene
(b.p. 41.5C)
37
金剛烷(Adamantane)
三環癸烷(C10H16), 環狀四面體, 熔點2680C,
密度1.07.
無色, 無毒, 無味晶體, 具潤滑性且易昇華.
用於醫藥,功能性高分子, 潤滑劑, 界面活性劑, 感光
材料, 光纖維材料, 電子材料, 農藥攜帶劑等.
被譽為新一代精細化工原料, 未來可與苯化學相媲美.
38
不同離子液體金剛烷合成反應活性比較
0.400
0.350
reaction time(min)
0.300
PHC
TEAC
0.250
BMIC
0.200
0.150
0.100
0.050
0.000
0
500
1000
1500
conversion of exoTHDCPD
X=0.65 , IL/exo-THDCPD=1/1.28 , 70 C
39
PHC/AlCl3中AlCl3莫耳分率對金剛烷合成反應活性影響
0.4
Conversion of exoTHDCPD
0.35
0.3
0.6
0.25
0.65
0.2
0.7
0.15
0.75
0.1
0.05
0
0
200
400
600
800
1000
1200
1400
1600
Reaction time(min)
[PHC]AlCl3 , IL/feed=1/1.28 , 70 C
40
Reaction Pathway for The Isomerization of Cyclic Alkanes
AlCl3
IS-1
acidic IL
endo-THDCPD
(m.p. 77C)
H2
Ni
endo-DCPD
(m.p. 22.6C, b.p. 170C)
120C
IS-2
X
acidic IL
exo-THDCPD(JP-10)
(m.p. <-110C, b.p. 185.6C)
RO1
(H-transfer)
4-methyloctahydro indene
CR1
(cracking)
acidic IL
adamantane
(m.p. 267C)
RO2
(H-transfer)
decalin(cis/trans)(187-196C)
CR2
(cracking)
cracking products
Pyrolysis Gasoline
cyclopentadiene
(b.p. 41.5C)
41
JP-10及Adamantane合成結論(I)
1.酸性氯化鋁酸鹽離子液體, 可有效應用於endo-THDCPD
異構成exo-THDCPD(JP-10),並進一步異構化成金剛烷
(adamantane).
2.IL中之AlCl3莫耳分率X值, 以0.60~0.65(JP-10)及0.65~0.70
(adamantane)為宜, 反應溫度以
50~60C(JP-10)及60~75C (adamantane)為宜.
3.IL中X值愈高,反應活性愈高,但太高則易產生副產物, 且易
於反應 時生成黃色沉澱物.
42
JP-10及Adamantane合成結論(II)
4.金剛烷合成反應轉化率不宜太高,否則會產生adamantane
沉澱, 造成連續操作上之困擾.
5.反應活性衰退 , 可能是進料中水含量及反應中產生之烯烴
所造成.
6.金剛烷合成反應係先生成一中間產物, 此中間產物可生成
金剛烷, 或經氫轉移反應生成decalin(C10H18), 比例約
78/22~68/32, 溫度愈高比值愈低, 另外於反應液中加入
decalin可降低其生成選擇性.
43
Isomerization of Cyclic Alkanes
1.H2SO4
2.AlCl3
IS-1
X
3.acidic IL
endo-THDCPD
(m.p. 77C)
acidic IL
exo-THDCPD
(m.p. <-110C, b.p. 185.6C)
JP-10
H2
Ni
IS-2
[ US Pat 7488860 (2009) ]
[ CNS Pat I 314141 (2009) ]
[ Fuel, (2011), in press]
acidic IL
adamantane
(m.p. 267C)
Adamantane
[ US Pat 7488859 (2009) ]
[ CNS Pat I 321128 (2010) ]
[Catal. Communi., 10(13), 1747(2009) ]
120C
Pyrolysis Gasoline
endo-DCPD
(m.p. 22.6C, b.p. 170C)
cyclopentadiene
(b.p. 41.5C)
44
(A)Lewis Acid Ionic Liquid
擬固定床式離子液體反應器在
JP-10合成反應之應用
(Pseudo fixed-bed IL reactor)
45
擬固定床式離子液體反應設備
Products
Feed
Feed
Feed
pump
Temp.
controller
(A)未裝填玻璃珠示意圖
(B)反應管裝填玻璃珠
底部示意圖
46
(A)Lewis Acid Ionic Liquid
負載型酸性離子液體
Supported Acidic Ionic Liquid
47
Structure of Supported IL (Impregnation & Grafting)
48
Supported ionic liquids 製備
製備方法
1. 擔體 ＋ ionic liquid
2. 擔體 ＋ ionic liquid(in CH2Cl2), 抽乾CH2Cl2
3. 擔體前處理 ＋ ionic liquid(in CH2Cl2), 抽乾
CH2Cl2
• AlCl3 (in CH2Cl2), washed by CH2Cl2
• AlCl3 ＋ PHC(in CH2Cl2), wash by CH2Cl2
• Me3SiCl(in cyclohexae), reflux and washed by
CH2Cl2
49
Support : silica gel (80-120 mesh)
Ionic Liquid : PHC/AlCl3 (X=0.65)
conversion of endo-THDCPD
Effect of silica gel
1.00
0+0
0.80
0.6+0
0.9+0
0.60
1.2+0
0.40
1.5+0
1.8+0
0.20
0.00
0
60
120
180
240
300
360
reaction time(min)
圖一 擔體(SiO2)不同用量之異構化活性比較
50
Conversion of endo-THDCPD
1
0.9
blank1
0.8
SiO2
0.7
MMT
0.6
γ-Al2O3
0.5
MCM41
0.4
α-Al2O3
amberlyst 15
0.3
0.2
0.1
0
0
60
120
180
240
300
360
reaction time(min)
圖四 使用不同擔體含浸之活性比較
[(CH3)3SiCl表面處理，再含浸PHC/AlCl3]
51
Supported IL結論
• 實驗結果顯示，可以成功的將酸性離子液體負載
於SiO2，Al2O3，MCM-41等擔體上，有效提昇異
構化反應活性。
• 離子液體負載在擔體上，可增加分散性，提高反
應初期轉化速率。
• 擔體表面可能有會破壞氯化鋁酸鹽離子液體的OH基，需進行擔體前處理，以保護離子液體活性。
• 開發兩種擔體前處理方法。
– Me3SiCl(reflux) 、氯化鋁酸鹽離子液體。
[ J. Mol. Catal. A: Chemical, 315(2010)69 ]
52
(B)Bronsted Acid Ionic Liquid
Esterification of Glycol Ether
(Glycol Ether Acetate)
Esterification of Fatty Acid
(Bio-diesel )
Trans-esterification of Glyceride
(Bio-diesel)
53
Zwitterionic precursors
R1
R1
N (CH2)n SO3
R1 N
N (CH2)n SO3
R2 N (CH2)n SO3
R3
兩性化合物結構式
N-Propane sulfone pyridinium[PSPy]
or
Pyridinium propyl sulfobetaine[PPS]
54
N
+
O
O
N
N
S
SO3
O
SO3 + H 2SO 4
N
HSO4
SO3H
Scheme 1 酸性離子液體製備反應式
N-Propane sulfone pyridinium[PSPy][HSO4]
or
Pyridinium propyl sulfobetaine[PPS][HSO4]
55
(C)Bronsted Acid Ionic Liquid HPA
N
+
O
O
N
S
SO3
O
[PPS] or [PSPy]
H2PW12O40
N
SO3 + H3PW12O40
N
SO3H
Scheme 2 離子液體異多體酸製備反應式
(PPS-TPA)
56
[I] 二元醇單烷基醚醋酸酯之合成
(Synthesis of Glycol mono-Alkyl Ether Acetate)
EGEEA
EGnBEA
DEGnBEA
化合物特性：具多官能基之高沸點多功能溶劑，對高分子
材料具較高 溶解力，性能優於乙二醇醚及丙
二醇醚兩大類溶劑。
產 品 用 途 ：汽車噴漆、器具表面塗料、水性塗料、印刷
油墨、木材着色劑等。
57
Esterification of Glycol Ether
EG
H2O
n-BuOH
DEG
Bronsted acid IL
Hydration
TEG + …
EO
85%
n-BuOH
EGnBE
10%
Bronsted acid IL
5%
DEGnBE
Bronsted acid IL
DEGnBEA
TEGnBE + …
O
Catalyst system
•Bronsted acid IL
•HPA/SiO2
HOAc
OH
HO
EO
HO
O
OH
EGnBE(BCS)
OH
O
HO
DEG
EG
O
O
O
O
OH
TEG
O
OH
DEGnBE(BDG,DB)
O
O
O
DEGnBEA 58
[II] 二元醇單脂肪酸酯之合成
(Synthesis of Glycol mono-Fatty Acid Ester)
EGML
EGMP
EGMS
EGMO
PGML
PGMP
PGMS
PGMO
PEGMS
PEGMO
EGMP/ EGMS：潤滑劑、珠光劑、增稠劑、增塑劑、分散劑、乳化劑
廣泛應用於化妝品、醫藥及化工各領域。
合成技術：直接酯化法
間接酯化法
開環酯化法
59
[III] 脂肪酸甲酯(FAME)之合成
(Synthesis of Fatty Acid Methyl Ester )
Linoleic acid
Oleic acid
Stearic acid
Palmitic acid
Myristic acid
Lauric acid
C18:2
C18:1
C18:0
C16:0
C14:0
C12:0
60
Esterification of Fatty Acid
O
C OR
C16:0
palmitic
H3C
7
O
C18:0
stearic
C OR
H3C
8
O
C18:1
oleic
H3C
C
3
OR
3
O
C18:2
linoleic
H3C
C
2
OR
3
R=H, CH3
61
Esterification of Fatty Acid
1.以棕櫚油為主之油脂化學工業，利用離心分離
純化後，可得到純化油脂(CPO) ，約有5wt%混
合脂肪酸殘渣物(PFAD)被分離出。
2.欲由此些殘渣物(PFAD)回收脂肪酸，有其困難
性，且不具經濟效益，可將此混合殘渣物經由
催化反應，轉化成液態燃料 (汽油與生質柴油)
或化學品等。
3.工業上生產生質柴油最常用鹼製程，其反應速
率遠高於酸觸媒，但必須控制進料游離脂肪酸
(FFA)含量避免皂化，本觸媒可用於預酯化游離
脂肪酸後再進入鹼製程。
62
Esterification of Fatty Acid
4.工業上脂肪酸與醇類之酯化製程，大部分使用液態
酸觸媒，如H2SO4、HF及p-toluenesulfonic acid
等，雖可有效進行酯化反應，但仍有大量廢酸液
處理問題。
5.固態酸雖有其優點，但酸性點在結構中，不易被
大分子接近，且有活性衰退現象，耐水性Bronsted
acid IL則可以兼顧固態酸與液態酸之優點。
6.Bronsted acid IL之特性為產物可分層分離，減
少廢酸液處理之困擾，屬於一種綠色催化製程。
63
酯化反應製程
Water & methanol
PPS
& acid
Condenser
Feedstock
Products
Water & methanol
Temp.
controlled
Catalyst recovered
Reaction
Separation
Distillation
64
[IV] Transesterification of Bio-diesel
Synthesis
Triglyceride +Alcohol  Glycerol +Alkyl ester (Bio-diesel)
(Catalyst)
Acid catalyst: H2SO4, RC6H4SO3H, H3PO4, HCl
[CH3OH/Oil = 40; 5% H2SO4; 95 C/9 hr; 97% yield]
[44%FFA feedstock; 1 wt% H2SO4; 77 C/20 hr; 117 C/3 hr;
240 C/70 bar/15 min; 90% yield]
advantage: feedstock could be with higher content of fatty acid & H2O
disadvantage: lower reaction rate, higher reaction temperature,
lower yield, corrosion of facility
Base catalyts: CH3ONa, NaOH, KOH, Na2CO3
[CH3OH/Oil = 6; 1%NaOH; 60 C/1 hr; 90% yield]
advantage: higher reaction rate, lower reaction temperature, no corrosion
disadvantage: higher requirement for vegetable oil (FFA & H2O)
65
Reaction Mechanism of Transesterification
66
Transesterification and Esterification Process (Acid-catalyzed)
67
Transesterification of Bio-diesel Synthesis
Environmental friendly technology:
Solid base : MgO-Al2O3, KF-CaO, K2CO3-Al2O3
Solid acid
:Zr(SO4)2, TiO2-SO42-
Supercritical: higher solubility of CH3OH with oil
(300 C; 20 Mpa)
Ionic liquid : (Bronsted acid ionic liquid)
(CH3OH/Oil =12; 1% IL; 170 C/5 hr ; 90% yield)
( 44%FFA feedstock; 1% H2SO4; 77 C/20 hr;
117 C/3 hr; 240 C/70 bar/15 min)
68
Related Processes & Products for Biodiesel Synthesis
C16:0
FAME
Crude Palm Oil
FFA
(Diesel & Biodiesel Additive)
Esterification
KOH
Transesterification
Biodiesel
FAME
High
Purity
Glycerol
FAME
Supercritical
(Lipase)
MES (Detergent)
GDtBE/GTtBE
Amb
CH3OH / IL
CH3OH
CH3O
H IL
2.Sulfonation
IB
PFAD
Low Acid
Triglyceride
1.Hydrogenation
HOAc
Amb/ IL
GMA/
GDA
HOAc
GTA
IL
IL
Amb
GMtBEA/
GMtBEDA/
GDtBEA
(ester-ether)
(Plasticizer & fuel additive)
Ph-COOH
Crude
Glycerol
IB
GTB
(Plasticizer)
GL
CH3OH / IL
Pre-esterification
High Acid
Triglyceride
(Jatropha )
(Algae)
CH3COOCH3/ IL
Inter-esterification
(Supercritical)
(Lipase)
Biodiesel FAME
GTA
69
Inter-esterification
(Transesterification & Transacylation)
70
Bronsted Acid IL結論
1.利用Bronsted Acid IL (PPS-H2SO4)可有效進行
醇與酸之酯化反應。
2.酯化產物可與酸性離子液體分層分離。
3.酸性離子液體真空除水後,可繼續使用, 減少廢酸
液處理問題。
4.可用來處理鹼性觸媒轉酯化製程之高酸甘油酯進
料(即預酯化製程) 。
5.反應中,可用帶水劑移除反應產生之水,提高轉化率。
71
Application Method of Conventional Strong Acid Catalyst
(A) Lewis Acid Ionic Liquid
R
R
NCl
+ AlCl3
NHAl2Cl7
[PHC]
(Water-sensitive, Biphasic System)
(B) Bronsted Acid Ionic Liquid
SO3 + H2SO4
N
N
SO3H[HSO4]
[PPS]
(Water-tolerable, Biphasic System)
(C) Bronsted Acid Ionic Liquid/ Solid
N
[PPS]
SO3 + H3PW12O40
N
SO3H[H2PW12O40]
(Water-tolerable, Biphasic System)
72
結
論
可以利用離子液體特性
改善傳統
強酸性觸媒應用技術
開發綠色催化製程
Lewis Acid Ionic Liquid
[PHC-Al2Cl7]
Bronsted Acid Ionic Liquid
[PPS-H2SO4；PPS-PTSA；PPS-TPA]
73
Thank you
for your attention
74