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3 2 (3): 191-199
2 0 1 0 9 JOURNAL OF ENGINEERING STUDIES Sep., 2010


收稿日期: 2010−08−10; 修回日期: 2010−08−28
基金项目: (863) (No. 2006AA06Z371) (No. 082702)
作者简介: (1984−)
(1966−) Email: lizengxi@gucas.ac.cn
(1975−)
DOI: 10.3724/SP.J.1224.2010.00191
甲醇制低碳烯烃技术研究进展
王茜
1
,李增喜
1
,王蕾
2

(1. 100049
2. 100190)
摘 要:甲醇制低碳烯烃(MTO)技术提供了一种以煤制甲醇为原料生产烯烃的途径。本文重点讨
论了国内外 MTO 工艺的发展概况、工艺流程和使用现状,介绍了催化剂研究进展和 MTO 工艺的反应
机理,对 MTO 技术应用及其制约条件进行了初步分析,并根据我国的实际情况对其开发应用前景进
行了展望。
关键词:甲醇制低碳烯烃(MTO);工艺;催化剂
中图分类号 TQ519 文献标识码 A 文章编号 1674-4969(2010)03-0191-09
1 引 言
( )
[1]
[2]
( )
/
[3]
[4]
[1]

[5]

(Methanol to Olefin MTO)
[6]
[7]
[3, 6]

2 甲醇制低碳烯烃催化剂
MTO
MTO
192 , 2 (3): 191-199 (2010)


MTO
ZSM-5 SAPO-34

2.1 ZSM-5
1977 (Mobil)
Chang
[8]
ZSM-5 MTO
ZSM-5
0.55 nm( 1)
ZSM-5
C
4
+



图1 ZSM-5 结构示意图
[9]



MTO
ZSM-5
[10-12]
ZSM-5
MTO 化剂在高温条件
下的稳定性及对乙烯的选择性。
2.2 SAPO-34
1984 (UCC)
(SAPO-n n
)
[13]
SAPO-34
MTO
100% 100%
60% C
5
(UOP) SAPO-34
ZSM-5 MTO

SAPO-34
PO
4
AlO
4
SiO
4
0.43 nm−0.50 nm
2



图2 SAPO-34 结构示意图
[14]


SAPO-34
90% ZSM-5
MTO
SAPO-34
1000°C 20% 600°C
MTO
SAPO-34 MTO
SAPO-34
SAPO-34
193


MTO
[3]

3 甲醇制低碳烯烃工艺
MTO (Mobil)
(BASF) (Exxon)
(UOP) (Hydro)
MTO
[15]

MTO/MTP
(
UOP/ Hydro ) (MTO)
(DMTO)
(SMTO) (Lurgi)
(MTP)
(FMTP) 5
[7, 16-18]

3.1 UOP/Hydro MTO
(UOP)
(Hydro) UOP/Hydro MTO
MTO
( 80%−82%) ( 95%)
AA ( >99%)
[7]
3

SAPO-34
MTO-100 350−550°C 0.1 MPa−
0.5 MPa
(
0.75−1.50)
[19]

1995 UOP Hydro
0.75 t/d
90 100%
80% 450
1
UOP/Hydro MTO 500 kt
91%
[20]




图3 MTO 工艺流程示意图
194 , 2 (3): 191-199 (2010)


表 1 甲醇制烯烃装置(UOP/Hydro MTO )物料平衡表
(kt) (kt) (%)
2370 − −
− 500 48.0
− 345 33.0
− 100 9.6
H
2
C
1
-C
3
− 37 3.5
C
5
− 25 2.4
COx − 5 0.5
− 30 3.0
− 1328 −

2008 1 31 Eurochem
Viva Lekki
3300 kt/a MTO
UOP/Hydro MTO UOP
(OCP) MTO-OCP
800 kt 2012
3.2 DMTO
20 80
MTO 90
(TEA)
(DEA) TEA
(TEAOH) SAPO
SAPO-34 SAPO /
(DMTO )
4
MTO
50%−80%
DO123 2006
2
DMTO
50 t/d 99.8%
78.16%
1 : 1
1.5−0.8 1150 h
2006 8
3.3 SMTO
2000
MTO MTO
2004 2006 SAPO-34
2005 2006
FCC
FCC
(SMTO)
100 t/d SMTO



图4 DMTO 工艺流程示意图
195


2006 9
2007 11

2 MTO
UOP UOP
UOP 66.7
MTO
[18]

3.4 (Lurgi) MTP
(Lurgi) 20 90
MTP
(LPG)
(Sudchmie) ZSM-5
(<0.01%
)
( )
MTP 5 3
2
0.13 MPa−0.26 MPa 380−480°C
2002 1
TJeldbergodden
360 kg/h
11000 h 99%
71%

表2 MTO 工业示范装置技术比较
[18]

UOP/Hydro
MTO DMTO SMTO
FCC -
SAPO-34
MTO-100 DO123 −
(%) 99 99.18 99
+ (%) 78 78.71 78.24
(t/d) 0.75 50 100
1995.6 2006.2 2007.11



图5 MTP 工艺流程示意图
196 , 2 (3): 191-199 (2010)


3.5 FMTP
1999
[19]
SAPO-34
MTO
FMTP 2006 7 13
(FMTP)
30 kt
10 kt 800 t 1.6
2009 3 2009 10 9 15
470 h
4 甲醇制低碳烯烃反应机理

CH
3
OH 1/2CH
3
OCH
3
+1/2H
2
O+10.090 kJ
CH
3
OCH
3
2CH
2
+H
2
O+18.698 kJ
CH
2
CH
2
+15.968 kJ
[4]

C C
β H
C C MTO
20
[22]
C C
(Carbene) 鎓 (Oxium ylide)
(Hydrocarbon Pool) (Carbenium ion)


4.1 鎓

[23]

鎓 鎓
鎓 鎓
Stevens

( 6)



图6 氧鎓离子机理示意图

4.2
Kolboe
[24]
MTO
hydrocarbon pool
hydrocarbon pool
hydrocarbon pool
13
C
197


12
C ( )
13
C
hydrocarbon pool
hydrocarbon pool
[25, 26]
hydrocarbon-pool
/
Haw
[27, 28]
MAS NMR
hydrocarbon-pool
( 7)



图7 烃池机理示意图

5 国内甲醇制低碳烯烃技术应用及其制约
条件分析
20000 kt/a 1
2
DMTO (
) 2006 12
1800 kt/a 600 kt/a 300 kt/a
300 kt/a 2008
2010
MTP
132 1670 kt/a
520 kt/a 2006 8
MTP 2007
GSP
2007 2010

MTP
1680 kt/a 500 kt/a
2006 8 2010
Lurgi MTP
(460 kt/a) (200 kt/a)
(3.60 kt/a) 180

43%
[4]
[29]

[30]

6 前景和展望
50%
198 , 2 (3): 191-199 (2010)


MTP MTO

MTO
l1.66% MTO
1000s kt/a (
) 3018 kt
2332 kt
20%
MTO

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Progress in the Research on Methanol-to-Olefin
Technology
Wang Qian
1
, Li Zengxi
1
, Wang Lei
2

(1. Graduate University of Chinese Academy of Sciences, Beijing 100049;
2. State Key Laboratory of Multiphase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190)
Abstract: The methanol-to-olefin (MTO) technology offers an alternative for the conversion of coal to
light olefins by using coal methanol as raw material. This paper introduces the development, processing and
present status of methanol-to-olefins technology both at home and abroad. It also covers the progress on the
catalysts research and reaction mechanism of MTO. The paper also analyzes the application and the
restriction of MTO technology and provides some prospect according to the actual conditions in China.
Key words: methanol-to-olefin(MTO); technology; catalysts
王大洲