?????????? Coal-to-Olefin Technology in China

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??????????Coal-to-Olefin Technology in China

• ??? Zhongmin Liu
• ??????????????
• Dalian Institute of Chemical Physics, Chinese
  Academy of Science
• zml_at_dicp.ac.cn
• 2009.12.03

2
?? Content

• ?? Background
• ???????? Methanol to Ethylene and Propylene
• DMTO?? DMTO technology
• ???? Economics
• ??? Commercialization
• ????? Methanol to Propylene
• FMTP?? FMTP technology

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???????????????Methanol an important product
linking petrochemicals to coal chemical industry
????Indirect substitution of oil
MTO
Ethene
Olefin
Propene
MTP
???? well developed technology
MeOH
DME
Oil
LPG
Syngas
Coal
MTG
Gasoline
Diesel
????Direct substitution of oil
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?????????MTO Technical Routes for Olefin
Production MTO
Naphtha Feedstock
China US Japan 67 39 93
gt800oC, H2O, C2C3 Yield45
?? ?? C2H4 C3H6
???Naphtha
gt800oC,H2O
??Ethane
????? Coal, Natural Gas
???Syngas
??Methanol
DMTO (MTO)
Well developed technology
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MTO????Characteristic of Methanol to Olefin
reaction

• ?????? Acid catalyzed reaction
• ????100 High conversion
• ???? Low pressure is favorable to light olefin
  selectivity
• ??? Exothermic reaction
• 400-500oC,100 conversion
• ?H -22.4-22.1 KJ/mol methanol
• ???? Fast reaction
• 100 conversion at 0.04s contact time
• ????????????????? Shape selective effect should
  be applied for high olefin selectivity
• First generation of catalyst Modified ZSM-5
• Small pore SAPO molecular sieve could be good
  candidate for developing new catalyst

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?????DMTO????DMTO RD in DICP
Pilot test DICP (Fixed Bed) C2C3C4 85
1993
Lab test DICP C2C3 90
Pilot test Shanghai (Fluidized Bed) C2C3gt80,
1995
Demo Shangxi
Commercialization
2004.08-2006.08
75,85, 973 National Project
From 1980
2006.08-
DICP Xinxing Co LPEC
Shenhua 600KTA Xinxing 200KTA
DICP
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DMTO?? SAPO??????DMTO technology Research on
Small pore SAPO molecular sieves

• ???? UCC patent in 1982 (USP4440871) on SAPOs
• DICP?????SAPO-34?MTO?????
• DICP first demonstrated good performance of
  SAPO-34 in MTO reaction
• Applied Catalysis,Vol.40, No1-2,p316,1988
  Applied Catalysis, vol.64,p31-40, 1990
• DICP?SAPO???????????????????
• Synthesis and mechanism were well studied on
  small pore SAPO molecular sieves
• ???SAPO-34 Focused on SAPO-34
• ????SAPO??? Other small pore SAPOs were also
  synthesized and tested

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SAPO-34???SAPO-34 Molecular Sieve
C2H4 0.39nm C3H6 0.43nm C6H6 0.58nm
SAPO-34 framework CHA-type
Viewed along 010
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SAPO-34???????New methods for SAPO-34 synthesis
Template ???
First patent tetraethylammonium hydroxide USA4440871
DICP triethylamine (TEA), diethylamine (DEA), TEADEA EP1142 833A1
Other Methods dipropylamine, isopropylamine, piperidine, Morpholine
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SAPO-34?????Crystallization mechanism of SAPO-34
Relative Crystallinity 80
Crystal grains with Si(4Al) (2.5h)
Crystal grains with Si(nAl) (26h)
Initial gel (0h)
Rearrangement Condensation
Si substitute for P
Crystal nucleus (0.5h)
Grain growth
Si act directly (80)
2Si Substitute for AlP
Si act directly

• MICROPOROUS AND MESOPOROUS MATERIALS, 115 (3)
  332-337 NOV 1 2008, Synthesis of SAPO-34 with
  only Si(4Al) species effect of Si contents on Si
  incorporation mechanism and Si coordination
  environment of SAPO-34
• PCT/CN2007/002375
• PCT/CN2007/002376, PCT/CN2007/002332,
  PCT/CN2007/002333

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SAPO-34?????Crystallization mechanism of SAPO-34

• ?????Si????????????
• Schematic diagram of crystallization process with
  Si distribution in the crystals

Microporous and Mesoporous Materials,  114 (1-3)
416-423 SEP 1 2008
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???????Development of fluidized catalyst
?????? Spring Dryer for Fluidized Catalyst
Preparation
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??????? Fluidized Reaction System (raiser
reactor, continuous reaction-regeneration) Catalys
t loading amount 10kg
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??????????? Dense Phase Fluidized Reaction
System with Catalyst Recycling and product
separation Catalyst loading amount 20kg
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DMTO Demonstration

• ?? Objective
• ???????,???????????DMTO ???????,??????????????????
  ????????
• To develop DMTO technology for the design of
  large scale commercial units
• ???? Partner
• ?????????????? Dalian Institute of Chemical
  Physics
• ???????????? Providing pilot technology for
  design and the catalyst
• ???????????????? Luoyang Petrochemical
  Engineering Company, Sinopec
• ??????????? Engineering design
• ????????????????? Shanxi Xinxing Coal Chemical
  Technology Ltd
• ????????????? Investment, construction,
  management, operation
• ???????????,????????,???????? Joint venture
  company Shanxi Investment Group, Zhengda Coal
  Chemical Ltd, Shanxi Coal and Chemical Group

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???????????? Design and Construction

• 2004?8??????? The project started on August 8 of
  2004
• 2004?10?11?????????????? Feasibility study
  finished and passed on October 11 of 2004
• 2005?2?27????????? Basic design finished and
  passed on February 27 of 2005
• 2005?12???????? Construction finished in December
  of 2005
• ?? Scale 50t/d of MeOH
• ??????????? First unit at such scale for MTO demo
  in the world

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??? DMTO catalyst
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?????????????Hydrothermal stability of the
catalyst
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???????Variables test and optimization
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???? Typical results
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DMTO???????Results DMTO Demonstration test
?? DMTO????? DMTO demonstration
?? ?? MeOH
?? 50?/? 50t/d
????? ??? Fluidized bed
??????? ??99 gt99
???? ??wt 33.73
???? ???wt 79.1
????/?????? 2.96
??? D803C-II01
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DMTO???????????Economics DMTO naphtha cracking
Price of Feed
Naphtha Cracking
DMTO
Coal to Methanol
Methanol Price
Price of Poly-olefin (RMB/t)
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?????????????????????????Relationship between
coal and oil prices at same olefin cost
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DMTO???????Commercialization of DMTO

• ?????? Construction of commercial plant
• ?????? Baotou Project of Shenhua Group
• ?? Scale 600kta olefin
• ??????? (06.12)Approved by NDRC(Dec,06)
• 2010????? Will be operated in 2010
• ???????????? First coal to olefin plant in the
  world
• ????????? The construction of commercially unit
  will be licensed outside China
• ????????????????? Many international olefin
  companies have contact us for the technology
  licensing
• ?CBI-Lummus?? Cooperating with CBI-Lummus

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??????Baotou Project of Shenhua Group
Nov 25, 2009
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?????Methanol to Propylene (MTP)

• FMTP?? FMTP Technology
• ????
• ?????????? China National Chemical Engineering
  Group Co., Ltd
• ???? Tsinghua University
• ???????? Anhui Huainan Chemical Group Co., Ltd

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????Developing Progression

• 19992007????????????
• Catalyst synthesis and technologic research
• 2008.12???????????
• Successful scale-up production of the
  catalyst used in a fluidized bed reactor
• 2009.10 FMTP??????
• Successful FMTP pilot plant test
• ???????MTP??????? First demonstration unit
  in the world on Fluidized MTP

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3????/? FMTP??????30KTA (Methanol) FMTP
Demonstration Plant
Continuously running for 470hr ????470??
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???? Results
????? Methanol Conversion 99.9
?????(C?) Propylene Selectivity (Carbon Based) 67.3
???/??? t Methanol/t Propylene 3.39
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???

• ?????DMTO???FMTP??,????????
• DMTO and FMTP technologies have been
  developed, and demonstration tests were finished
  in China
• DMTO???????,?????????????????
• The application of DMTO technology will leads
  to a first commercial coal to olefin process in
  China

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??Acknowledgement

• ????? National Development and Reforming
  Committee (NDRC)
• ??? Ministry of Science and Technology
• ????? Chinese Academy of Sciences
• ????? Government of Shanxi Province
• ??????? Oil and Chemical Association
• ??????? All partners for technology development
• ???? Shenhua Group
• ??DMTO?FMTP?????? Colleagues on DMTO and FMTP

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Thanks!