Indirect Coal Liquefaction

Transcription

Indirect Coal Liquefaction
Better Solution to Clean Energy System
Yong-Wang Li,
Director, Chief Scientist
Synfuels China
State Key Laboratory of Coal Conversion
Institute of Coal Chemistry
Chinese Academy of Sciences
Taiyuan 030001
Clean Energy system 2005
Synfuels China
First Car Fueled by 100% F-T Super Clean Diesel

EU III / 2.0L diesel engine
Volks Wagen CADDY SDI 2.0
Economic fuel consumption ~5.0 L /100 km
Cetane No. > 70
Extremely low S and N
EU IV emission limit
Main points
Energy status in China
CTL solution
CTL development in China
Future development
Summary
Synfuels China
Synfuels China
Energy status in China
Coal
Reserves
70Million
0
tons
A
60 0
50 0
B
40 0
C
30 0
Oil
20 0
10 0
Gas
0
20 00
20 05
20 10
2020
Year
Production in China 2020:
200 million tons/a
Demands:
A: 610 million tons/a
B: 560 million tons/a
C: 450 million tons/a
Gap:
250-410 million tons/a
• Coal as major primary energy
• Oil insufficiency for the growing demands
• Solutions needed for sustainable development
Synfuels China
CTL Solution
Coal
Syngas
production
Highly
Integrated
System
NOW Electricity
Organic wastes
Syngas
Purification
Biomass
Synthesis
CO2
control
Power
Generation
Liquid fuels Naphtha & Chemicals
Hydrogen
FUTURE
CTL pointing to the sustainable solutions on the basis of GAIFICATION
Less limited life span of CTL initialized production system
Synfuels China
CTL Solution
Fischer-Tropsch Synthesis
• Commercial scale operation
SASOL
HTFT gas-solid fluidized bed
iron
light fractions
LTFT slurry phase /fixed bed iron and cobalt heavy fractions
SHELL
SMDS Fixed bed
•
cobalt
Technology in China: pilot plant proven
Synfuels China iron (main) cobalt (in development)
HFPT® slurry phase-low temperature <250oC heavy fractions
LFPT® slurry phase–high temperature 270-290oC diesel range high
CTL Development In China
CTL in China: Brief history 1950-1962
First BASF FTS technology
Cobalt catalyst at normal pressure
74(X13ton) fixed bed reactors
Î 30000ton Hydrocarbons/ a
Î The plant was removed due to oil
field discovery in 1960s in China
Synfuels China
-1979-1989: Development of iron catalysts
Fixed bed reactor up to single tube tests.
Slurry phase test in laboratory
Synfuels China
-1990-1993:
40 b /d demonstration plant test
Fixed bed reactor with about 2000 tubes
1) Desulfurization was not adequate
2) Extremely low oil price
Synfuels China
Synfuels China
New enhanced development initialized in 1997
Fischer-Tropsch synthesis in slurry phase
Synfuels China
FTS catalyst
group
Engineering
group
Fundamental
Syncrude
workingup
Synfuels China
Synfuels China
FTS catalyst research and development
- Iron based ICC-I (heavy fraction) 230-250oC, slurry phase
- Iron based ICC-II (lighter fraction) 260-280oC, slurry phase
- Cobalt based ICC-III 220 oC~240oC, slurry phase, fixed bed
1 0 0
9 6
80
S P U W
9 2
1 0 0
70
F S C P
Conversion/Selectivity (%)
Transmission (%)
9 6
1 0 0
F M S E
9 6
1 0 0
F M S D
9 6
1 0 0
F M S C
9 6
1 0 0
9 8
F M S B
60
CO con.
H2 con.
CO+H2 con.
CH4 sel.
50
40
+
C5 sel.
C2-C4= sel.
30
20
10
1 0 0
9 6
0
F M S A
9 2
-1 0
-5
0
5
V e lo c ity (m m /s , re la tiv e to α -F e )
1 0
1000
2000
3000
Time on stream (h)
4000
5000
Synfuels China
Process development and integration analysis
- Simulation of Fischer-Tropsch loop for different catalyst systems
- Hydrodynamics of slurry phase FT reactors and related
- Pilot plant design & operation
- Large scale slurry reactor design (4 m~ 8 m)
Synfuels China
Syncrude workup technology
- New hydrogenation catalysts for hydrogenating FTS crudes
- Cracking of FTS wax (new route)
- Oligmerization of light olefins
- Separation engineering
Engineering fundamental
- CFD calculation of three phase reactors
- Quantum calculations on catalytic mechanism
- Thermodymic data
- Kinetics and reactor modeling
Synfuels China
Synfuels China
Pilot plant 2001-2004
- Two types catalysts have been tested
- Slurry phase reaction engineering well proved: reactor & related process
- Product working-up proved
- Design package accomplished for the demonstration plant (3500 b/d)
Demonstration plant (Synfuels China+industries)
- Iron catalyst + slurry phase reactor (~ 5.5m)
- Dry fed entrained flow gasification (2 GSP )
- Diesel 70% Naphtha 18% LPG 12%
- Possible IGCC scheme is considered (If governmental support got)
- Efficiency ~ 43%
Commercial action (Industries+government)
- Two trains 3.2 million ton/year Shenhua Ningmei
- Sasol technology (tendency)
- 2006-2007 initializing
Synfuels China
Preliminary results of the CTL diesel
Index
Co-Mo-S Hy.
Co-Mo-S Cr
Ni Hy
Density kg/L
0.7684
0.7782
0.7664
Viscosity mm2/s, 20
3.172
3.957
3.276
154
138
150
370
385
350
64
66
74
Centane No.
74.1-80.1
66
>78-90
Total aromatics %
0.4
0.7
0
Poly aromatics %
0
0
0
Olefin %
0.5
0
0
Sulfur ppm
<4
<5
<0.5
CFPP oC
-3
-34
-2
Oxidation stability
-
-
<0.3 mg/100ml
Acidity
5.39
-
<0.2mg KOH
/100ml
oC
Initi. boiling point
Final boiling point
Flash point
oC
oC
oC
CTL Future Development
High selective catalysts development
- Narrowing to middle distillates
- Working at high temperature (280oC) but in slurry phase
- Optimizing factors affecting efficiency
Reactor & processes
- Enhancing reaction heat recovery ( 15% energy of syngas )
- Pressure up to 45 bars to increase single train productivity
- Process integration optimization (co-production evaluation)
- Water saving and treatment technologies
New technology for syncrude up-grading
- S free catalyst for hydrogenation & cracking
- Light fraction utilization
- New route for fuel production
- Chemicals from syncrudes
Synfuels China
Synfuels China
CTL Future Development: Co-production
Electricity
Steam (HP, MP,LP)
Steam MP
50 tons
4.911 ton ST coal
(2)
(1)
Oxygen
681375 Nm 3
88.942 ton ST coal
(3)
(7)
Electricity
30000 KWh
9.9 ton ST coal
(5)
Steam (HP-MP)
1200 tons
117.857 ton ST coal
Electricity
446412.827 KWh
147.316 ton ST coal
(4)
Coal 1000 tons
6500 kcal/kg
928.571 ST coal
Syngas
production
Tail gas
66.565 ton ST coal
Syngas
1965125 Nm 3
F-T synthesis
800.087 ton ST coal Product
(6)
(10)
upgrading
(9)
(8)
Steam (LP-MP)
1883 tons
184.925 ton ST coal
Efficiency
Oil 43-45%
FTS thermal: 78-80%;
CTL thermal: 63-65%
Gasification thermal: 90%
Oil products 342.341 tons
528.183 ton ST coal
Energy points:
Air separation & other unrecoverable: 15~25%.
Recoverable: hot gas recovery 10%; tail gas 5.6%; reaction heat 15%.
Synfuels China
Co-generation an introduction
Efficiency
Electricity
Steam (HP, MP,LP)
Steam MP
50 tons
4.911 ton ST coal
(2)
(1)
Oxygen
681375 Nm3
88.942 ton ST coal
Coal 1000 tons
6500 kcal/kg
928.571 ST coal
(3)
(7)
Electricity
30000 KWh
9.9 ton ST coal
(5)
Steam (HP-MP)
1200 tons
117.857 ton ST coal
Electricity
446412.827 KWh
147.316 ton ST coal
Steam (LP-MP)
1883 tons
184.925 ton ST coal
(4)
Syngas
production
Syngas
1965125 Nm3
800.087 ton ST coal F-T
(10)
Product
upgrading
(6)
(8)
Oil_electricity 52-54%
FTS thermal: 78-80%;
CTL thermal: 63-65%
Gasification thermal: 90%
(9) Tai gas
66.565 ton ST coal
(11)
Steam
1200 tons (HP-MP)
1883 tons (LP)
Oil products 342.341 tons
528.183 ton ST coal
IGCC
(12)
Electricity
2898036 MJ
99.1 ton ST coal
Simple Co-production scheme can optimize the energy flows into valuable products
Synfuels China
Summary
CTL in whole has been well proved by large scale production and is an
important and practical option for China’s future liquid fuel supply.
CTL route will bring us to a sustainable way in using our available
sources via syngas.
CTL technology in China is approaching matured and will play important
roles in the growing market.
The super-clean diesel produced via CTL route will largely impose great
benefits from environment improvement.
Co-production solutions should be seriously considered.
Synfuels China
Thanks for your attention