1
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
FischerFischer--TropschTropsch synthesissynthesisfrom laboratory to engineering scale upfrom laboratory to engineering scale up
HaoHao XuXu
Institute of Coal Chemistry, Chinese Academy of Institute of Coal Chemistry, Chinese Academy of SciencesSciencesState key laboratory of Coal chemistryState key laboratory of Coal chemistrySynfuelsSynfuels ChinaChina®®
2
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
IntroductionIntroduction::
•Government need
•International technology situations
Sasol: high temperature FTS
Low temperature FTS
Shell: SMDS
•Technology development in China
SynfuelsSynfuels ChinaChina®® : HFPT ICC-IA LFPT ICC-IIA
3
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
CTL processCTL process:
Coal gasification
Fixed-bed or moving bed gasifierFluid-bed gasifierEntrained flow gasifier
shift reactionAcidic gas removalSlurry FTSProduct upgrading
4
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Coal gasificationCoal gasification
Texaco ShellLurgi
Cheap in constructionMethane rich syngas
Coal adaptabilityTar recovery
Water treatment
Expensive in constructionHigh quality SyngasCoal adaptability *
Short time on streamHigh O2 consumption
Expensive in constructionHigh quality SyngasCoal adaptability**
Hot stream quenchingLarge boiler size
outlet
Pressur. water
Quench
inlet
Cooling screen
Burner
Pressur. water
Fuel
Granulated slag
overflowWater
Gas outlet
Cooling jacket
Gas to pilot burnerOxygen
water
GSP
Cheap in constructionHigh quality SyngasCoal adaptability***
Quenching type and heat recovery
BDI SVPFUTURE ENERGY
CHOREN
GSP
5
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Laboratory researchLaboratory research::catalyst development and researchICC-IA catalyst
Changes of conversions and selectivity with time-on-stream in slurry phase reactor (240 -270℃, 1.5-2.0 MPa, 2.0 NL/g-cat./h, H2/CO=0.67)
0 500 1000 1500 2000 2500 3000 35000
10
20
30
40
50
60
70
80
90
100
C O C on version
T im e on stream , h
C5
++C2-4
=
C H4C
onve
rsio
n a
nd
sel
ecti
vity
,%
6
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Laboratory researchLaboratory research::ICC-IIA catalyst
1000 2000 3000 4000 50000
10
20
30
40
50
60
70
80
Con
vers
ion/
Sel
ectiv
ity (%
)
Time on stream (h)
CO con.H2 con. CO+H2 con.CH4 sel.C5
+ sel.C2 -C4 = sel.
Changes of conversions and selectivity with time-on-stream in slurry phase reactor (240 -270℃, 1.5-2.0 MPa, 2.0 NL/g-cat./h, H2/CO=0.67)
7
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
0 100 200 300 400 500 6000
20
40
60
80
0 100 200 300 400 500 6000
20
40
60
80
100
(b)
Time on stream (h)
Conv
ersio
n (%
) CO H
2
ε'-Fe 2.2C χ-Fe 5C 2
iron carbides (ε'-Fe 2.2
C + χ-Fe 5C
2)
spm phases (Fe3+ +Fe2+) Fe
3O
4
(a)
Cata
lyst
com
posit
ion
(%)
Correlative studies of phase transfer and activities of an ICC-IA model catalyst during FTS reaction. (240 -270℃, 1.5-2.0 MPa, 2.0 NL/g-cat./h, H2/CO=0.67)
Catalyst Catalyst characteristizationcharacteristizationXRD,SEM,MES
8
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Quantum chemistry calculationQuantum chemistry calculation
Schematic unit cell of Fe5C2. (Fe: light gray; C: deep gray.)(1)CO adsorption on the surface of Fe5C2(001)、(110)、(100)
9
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Schematic top and front views of Fe5C2(001) (a); top and side views of (110) (b); and top and front views of (100) (c) in a p(1×1) unit cell.
10
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Adsorption energetics (left) and C-O bond activation (right) of CO adsorption on Fe5C2 surfaces
11
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
0 10 20 30 40 50 60
020406080
100120140160180200220240260280300
T = 250 oC
T = 150 oC
T = 50 oC
Ent
halp
y of
vap
oriz
atio
n kJ
/mol
Carbon number
Kinetic and slurry reactor modelKinetic and slurry reactor modelresearchresearchDevelop user databank for FTS
Enthalpy of vaporization at different temperature for n-paraffins, C7 ~ C30 data are from Aspen Plus, C31 - C60 data are fromthis work
12
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
FTS Kinetic researchFTS Kinetic research ::Kinetic research for FeKinetic research for Fe--CuCu--K catalystK catalyst
Ma Ma WenWen--pinpin’’s models model
Wang Wang YiYi--ningning’’ss ModelModel
Zhang Zhang rongrong--lele’’ss modelmodel
13
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
FTS Kinetic research :FTS Kinetic research :Kinetic research for FeKinetic research for Fe--CuCu--K catalystK catalyst
JiJi YuanYuan--yuanyuan’’ss modelmodelYang Yang JunJun’’ss ModelModelTengTeng BoBo--taotao’’ss modelmodel
14
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Develop slurry bubble reactorDevelop slurry bubble reactor
))(( ,,
,,,00,
iLi
igiL
iggiggigg C
mC
akh
CuCudtCd
−−−
=ε
∑−−+−
=j
jjicat
iLi
igiL
iLLiLLiLL R
hSWC
mC
akh
CuCudtCd
,,,
,,,00, ))(( αε
Gas CSTR Liquid CSTR
Gas CSTR Liquid CSTR
Gas CSTR Liquid CSTR
0 10 20 30 40 500.01
0.1
1
10
T = 260oC H2/CO = 1.2
exp. calc.
Mol
ar s
elec
tivity
(%)
for p
araf
fins
Carbon Number
15
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Pilot plant researchPilot plant research
• Construction began in 2001• First run in 2002, 25 days• Modifications in winter of 2002• Three runs in 2003, • Two runs in 2004, 1500 hours• Catalyst, kinetic model and slurry bubble reactor
were tested in the pilot plant.
16
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Develop product upgrading Develop product upgrading technologytechnology
• Cooperate with industrial partner to Develop hydrogenation and hydrocrackingtechnology
Developing hydrogenation and hydrocrackingtechnology in laboratory
17
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
CTL diesel properties (Synfuels China®)
IndexesHydrogenated Fraction RefineryCo-MoS2 catalyst
HydrocrackedCo-MoS2 catalyst
HydrogenatedFractionS-free catalyst
Density kg/L 0.7684 0.7782 0.7664Viscosity /mm2/s, 20 oC 3.172 3.957 3.276Initial boiling point / oC 150 130 185Final boiling point /oC 370 385 330
Disti. Range / oC
5% 185-206.210% 154-188 138-184 213.730% 257 231 232.750% 278 272 252.770% 293 305 278.290% 323 332 310.295% 330 341 322dried 337 349 331.8Flash point /oC 64 66 >70Cetane number 74.1 66 75-90Total aromatics % 0.4 0.7 -Olefin /% 0.5 -Sulfur / ppm < 4 <5 <0.5 CFPP / oC -3 -34 -2
18
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
oxygen and stream
Coal
Acid gas,CO2 so on
Gasification water gasShift reaction
acidic gasremoval slurry FTS
Intermediates
product separation
CO2
Waste water
Tail gas
H2
diesel
Oxygenates
distillation Water
refineryLPG
Naphtha
Process integration researchProcess integration researchCoal gasification
Water gas shift reaction
Acidic gas removal
Slurry FTS
Product upgrading
19
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
Comparison between simulation and industrial resultsComparison between simulation and industrial results
Coal slurry coal gasification GSP coal gasificationIndustrial value simulation Industrial value simula
tionGasification temperature ℃ 1400 1500
Gasification pressure(Mpa) 4.0 3.0
Coal slurry concentration(wt%)
63.96% -
Coal conversion % 98 99.6syngas %(dry base)
H2 44.080 45.0227 27.06 27.06CO 35.102 34.0537 68.36 68.28
CO2 19.970 20.0943 4.06 4.18N2 0.374 0.5195 0.395 0.39
NH3 0.134 0.0034 0.00 0.00H2S 0.150 0.1526 0.04 0.04
others 0.08 0.0994 0 0
20
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
SHELL gasificationIllinois 6# coal
SHELL gasificationTexas Lignite
literature calculation literature calculationGasification temperature ℃ 1699.85 1644.25
Gasification pressure(Mpa) 2.308 2.7
Coal conversion % 99.5 99.32
syngas %(dry base)
CO 64.38 65.57 62.69 63.80H2 27.31 27.23 28.50 28.28
CO2 1.52 1.32 2.86 3.04CH4 0.03 0.06 0.03 0.07Ar 1.12 0.09 1.06 0.09N2 4.17 3.11 4.49 4.27
H2S 1.33 1.26 0.33 0.41COS 0.14 0.13 0.03 0.04
21
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
PolyPoly--generationgeneration::the future of CTL in Chinathe future of CTL in China
Poly-generation based on coal gasification is a promising sustainable strategy
Poly-generation of CTL and co-produce electricity by combined cycle is an efficient way.
The optimization of the poly-generation system should be carefully evaluated.
22
Synfuels China: Institute of Coal Chemistry, CAS中美煤炭气化液化技术研讨会2006-06-15
SummarySummary
•• CTL in china can be a feasible way from viewpoint of technology,resource,economics,and environment
• CTL technology developed in Synfuels China has been tested in pilot plant, can be scaled up to demonstration plant scale. The demonstration plant is been design.
•Poly-generation of oil and electricity,andchemicals is the future of Large CTL