21 78

2009 8

Vol . 21 No. 78
Aug. , 2009

PROGRESS IN CHEMISTRY

1 ,2 ,3 3 3

( 1. 201208 ;
2. 200137 ; 3. 200433)

,


: TQ217 ; O623. 734 : A : 10052281X ( 2009) 07821636208

Amination of Ethylene Oxide to Ethanolamine

1 ,2 ,3 3 3

Liu Zhongneng Gu Rong Cao Yong Xie Zaiku

( 1. Shanghai Research Institute of Petrochemical Technology , SINOPEC , Shanghai 201208 , China ;
2. Shanghai Gao Qiao Petrochemical Corporation , SINOPEC , Shanghai 200137 , China ;
3. Department of Chemistry , Fudan University , Shanghai 200433 , China)
Feng Ruming

Abstract The selective amination of ethylene oxide to ethanolamine has become a hot spot in amination reactions in
recent years. The preparation of ethanolamine is mainly composed of aqueous ammonia and liquid ammonia methods ,
which belong to typical homogeneous catalysis and heterogeneous catalysis respectively. This article intends to review the
progress in aqueous ammonia method from thermodynamics , kinetics and reaction mechanism. The engineering condition
of aqueous ammonia method in industry is also partly discussed. The latest knowledge of catalyst species , surface acid2
base property and pore structure in the catalyst is summarized in terms of liquid ammonia method. A prospection on the
future research of selective amination is also discussed.
Key words ethylene oxide ( EO) ; ammonia ; ethanolamine ; selective amination
1. 5 Mechanism

Contents

2 Heterogeneous catalysis system

1 Homogeneous catalysis system

1. 1 Reaction between aqueous ammonia and
( aqueous ammonia method)

EO

2. 1 Reaction between liquid ammonia and EO ( liquid

ammonia method)
2. 2 Strong2acid ion exchange resins

1. 2 Thermodynamic research

2. 3 Supported heteropoly acids

1. 3 Kinetics research

2. 4 Microporous solid acid materials

1. 4 Influences affecting the product distribution

3 Conclusions

: 2008 9 , : 2008 10
3 (No. 20080430601)
3 3 Corresponding author e2mail :fengrm @sript. com. cn

 78

[1 4 ]

( EO)
,
[5 , 6 ]
: ( 1) , EO
,

, ,
[7 ]
,
( MEA )
( DEA )
( TEA) , [8 ] ( 2 )
, EO ,
MEA
DEA TEA 2
: ( 1 )
[9 ]
[10 , 11 ]
, ( 2)
, ( 3 )

, LaZSM25 DEA
[13 15 ]
Nippon Shokubai

,
EO C O ,

[2 , 12 ]

,
,

, MEA H298
0

0
- 125. 698kJ mol , DEA H298

- 148. 192kJ mol ,

TEA

0
298

=
=

- 179. 786kJ mol , MEA

DEA

TEA Duldner
[25 ]
:
0
0
MEA H298 = - 107. 236kJ mol , DEA H298 =
0
- 84. 935kJ mol , TEA H298

- 113. 972kJ mol ,

Duldner EO
[39 ]

Lowe EO
,Duldner Lowe
, EO

1. 3 EO
r1 = k1 CNH3 CEO

( 1)

r2 = k2 CMEA CEO

( 2)

r3 = k3 CDEA CEO

( 3)

EO ,
[26 ]
, EO ,
, ,
[27 ]
Miki
[28 ]
Potter EO
, Miki EO
46. 090kJmol , EO
2
k1 = ( 41 + 410 cw ) 100 exp ( - 11000RT)
( cw ) , 40molL ,

1. 1 EO ( )
[16 , 17 ]

, EO
, ,
Knorr

1637

[18 20 ]

, EO ,
[21 , 22 ]

, EO
1 EO ,
EO

( 1) ( 2 ) ( 3 ) 1 515 7 ;
( 2)
( 3)
Potter EO , ( 1)
69. 454kJmol , 10 30 ,
18 30molL , ( 1) ( 2 ) ( 3 )
16 4 ,Stoyanol
[29 ]
, 0. 693molL , ( 1 ) ( 2 )
(3) 1
40
14 ;
[30 ]
,Johnson ( 1) ( 2) ( 3)
1
14
40 ,
, EO You
[31 ]
NH3 EO
48. 185kJ mol ,
k1 = 7845exp ( - 11500RT)

1 EO
Fig. 1 Consecutive reaction of EO with ammonia

1. 2 EO

[23 ]

[24 ]

EO

k2 = ( 8151 - 1051 cw ) k1
k3 = ( 14181 - 1196 cw ) k1
[32 , 33 ]

Aspenplus
, , You

1638

21

[34 ,35 ]

Eastham

, EO ,
+
H OH ( pH = 3 14) EO
[57 ]
, Holubka
[36 ]
Ferrero 3wt % EO
1 1 ( ) , 15 25
, , Ea ( 1 ) =
61. 086kJ mol , Ea ( 2 ) = 65. 689kJ mol , Ea ( 3 ) =
( 2) ( 3)
63. 178kJ mol , ( 1)

1 4 311 Reich 3wt % EO

, 20 60 , Ea ( 1) =
[37 ]

64. 434kJ mol , Ea ( 2 ) = 61. 923kJ mol , Ea ( 3 ) =

2 NH3 EO
( : 350ml , : 2. 0MPa ,

61. 086kJ mol , H2 O 69. 454kJ mol

:70 )

, EO

Fig. 2 The product selectivity as a function of NH3EO molar

,

1. 4 EO
EO , Le
Chatelier , NH3 EO

ratio ( reaction condition : reactor 350ml autoclave , system

,
,
,

1. 4. 1 NH3 EO
EO , 25 28wt %
9919 % EO ,
, NH3 EO ,
2 ,
[8 , 38 40 ]

2 , NH3 EO ,
MEA , TEA
NH3 EO ,DEA
NH3 EO ,

MEA
, NH3 EO , NH3 EO
MEA , NH3
; TEA
NH3 EO , EO , EO
,
TEA EO ;
DEA ,
, DEA
[41 , 42 ]
MEA DEA

pressure :2. 0MPa , temperature :70 )

, NH3 EO ,
MEA
DEA TEA ,

1. 4. 2

,
,
,
,
,
30wt %99wt % , EO 50 %

600 ,99. 5wt % ,

[39 , 43 , 44 ]
[30 ]
2 000
;Johnson
TEA
1. 4. 3
Potter

[28 ]

, 10 30
[45 ]
, Ferrero
10 25 ,
,
[39 ]
, Lowe
, 100 160 ,
[46 ]
MEA BASF ,
80 120 ,DEA NH3 EO
MEA TEA ,
Union Carbide

[47 ]

,
160 190 , ,
[48 ]
MEA BASF ,

 78

1639
+

200 250 , ,

, NH4

TEA NH3 DEA MEA ,

[52 ]
,Dow , EO TEA
, ,
[57 ]
Holubka
,
EO
+
, H ,
EO , ,
, 165. 268kJmol ,
226. 354kJ mol , EO NH3

MEA DEA 15 wt %
,BASF

[49 ]

90 170 MEA

,
,
EO
, MEA
DEA TEA
,
, EO

1. 4. 4
Shell

[50 ]

,
, ,
Mitsui Toatsu
Chemicals

[51 ]

MEA Dow

[52 ]

CO2
Oxiran

[39 ]

,
EONH3 ,BASF

[53 55 ]

,
,
, ,
,
[50 ]

, Shell

1. 5 EO

SN 2 ,
, EO ,
[56 ]
[39 ]
( > 100 ) Oxirian

; H , EO
,
- 70. 291kJ mol ,
; ,
, EO ,
86. 609mol ,
,
Holubka
EO
[58 ]
[59 ]
Delbene Aue , EO
- 923. 827kJmol
- 797. 052kJ mol ,
[60 ]
- 793. 286kJ mol - 857. 72kJ mol , Shibaev
,
95. 814kJ mol ,
EO ; Delbene
Shibaev Holubka

, EO ,
,
, EO NH3
, MEA DEA
,
, ,

[61 ]
, Somorjai ,21

, , EO
,
,

r = k a

2. 1 EO ( )

2
[NH3 ][ EO ] [ ROH] ( R , k a ) ,

, ,
2
,

0. 1 % ,
Stoyanov

[29 ]

1640

21

2. 2
[62 , 63 ]
Weibull
EO

2. 3

, ,
100 ,
EO , NH3 EO = 11 ,

W 0. 3wt % ,
, 150 ,LHSV ( ) 4. 5 ,

MEA 73wt %
EO

:MEA 39. 6wt % , DEA 30. 8wt % TEA 29. 1wt % ,

, ,
, EO
, EO

EO 98. 5 % EO

[64 , 65 ]

Weibull

EO ( HA) ,
,

,
( R ,0 p < 3)
R p NH32 p + HA

R p H42 p N A

[10 , 11 ]

Texaco

EO ,
Keggin 122 , W

10. 34MPa ,NH3 EO = 25. 0

, NH3 EO
,TEA 29wt % ,
TEA ,
,

,
, ,
2
2. 4

reversible adsorption step

EO ,

[12 ]

Phala

[69 ]

,
,

( 0 < q < 2)

Lercher

[67 ]

,
,
,

,
, ,
Weibull EO

,
H ,
Lercher

[66 68 ]

,
, ,
, Vamling

[9 ]

,
Segawa

[70 73 ]

,
,
ZSM25 , Schmal

[74 ]

,Cu ZSM25 HZSM25

,
BrgnstedLewis Zhang

[75 ]

HZSM25 ,

[76 ]

Amberlite 200 127

,Malinonskii

EO NH3

Al2 O3 , 300 350 ,

DEA TEA

, Sile

700 EO NH3
Al2 O3
13X

[77 ,78 ]

350

 78

, , EO
EO

[1 ]

Setoyama

, Mitusubish EO
, La HZSM25 , DEA
,
, La DEA
,
HZSM25
0153 0. 56nm , , TEA
, La , HZSM25
TEA Tsuneki

[79 ,80 ]

, MEA DEA
BrgnstedLewis

BL , EO La
ZSM25
1 La
Table 1 The influence of La loading and reaction time
ZSM25 (SiAl = 28) a time on streamhr = k 2k 1 = k 3k 1 = k 2k 3
LaAl = 0. 017 a
LaAl = 0. 1

LaAl = 0. 12

LaZSM25
, NH3 EO = 719 ,LHSV = 11. 5hr

- 1

100 ,DEA 41. 1wt % , TEA

3. 7wt % , MEA ,
NH3 MEAEO = 80171 , DEA

80wt % Moriya

[81 , 82 ]

La , Y , Ce Nb ZSM2
5 ,SiO2 , Al2 O3 2SiO2 Tsuneki

MEA ,
10 15 , MEA EO
DEA
TEA ; La ZSM25 ,
, EO MEA
, ,
Tsuneki EO LaZSM25
[2 ]

: ,
, ZSM25
,DEA EO TEA ,
DEA Dow

[52 ]

ZSM25 ,

MEA2EG , LaHZSM25
, TEA ,

1641

7. 81

0. 61

12. 8

24

7. 69

1. 53

5. 0

8. 47

0. 211

39. 9

24

8. 33

0. 591

14. 1

8. 70

0. 200

50. 1

24

8. 26

0. 562

14. 7

a SiAl LaAl

3
EO ,
,

, EO ,
, ,
, 70
; ,

,
, ,

, ,

[56 , 83 ]

,
,

, Mitusubish LaZSM25
, NH3 EO = 8 ( ) ,
DEA 48wt % , TEA 1 % ,

100 70
La ,
, EO

, ,

1 Tsuneki La

80 100 , ,

, ,
MEA DEA
EO NH3 EO ,

[9 ]

Vamling 4A
Y
13X SiO2 2Al2 O3 ,

1642

21

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