Fischer-Tropsch synthesis from laboratory to engineering …uscec.wvu.edu/wp-content/uploads/2013/04/Hao-Xu.pdf · · 2013-04-24Fischer-Tropsch synthesis from laboratory to engineering

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


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


CTL processCTL process:

Coal gasification

Fixed-bed or moving bed gasifierFluid-bed gasifierEntrained flow gasifier

shift reactionAcidic gas removalSlurry FTSProduct upgrading

4


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


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


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


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


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


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


Adsorption energetics (left) and C-O bond activation (right) of CO adsorption on Fe5C2 surfaces

11


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


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


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


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



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


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


Develop product upgrading Develop product upgrading technologytechnology

• Cooperate with industrial partner to Develop hydrogenation and hydrocrackingtechnology

Developing hydrogenation and hydrocrackingtechnology in laboratory

17


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


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


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


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


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


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

23


Thank you

Documents

Fischer-Tropsch synthesis from laboratory to engineering …uscec.wvu.edu/wp-content/uploads/2013/04/Hao-Xu.pdf · · 2013-04-24Fischer-Tropsch synthesis from laboratory to engineering