indirect coal liquefaction - stanford university · ctl in whole has been well proved by large...

Indirect Coal LiquefactionIndirect Coal LiquefactionBetter Solution to Clean Energy SystemBetter Solution to Clean Energy System

YongYong--Wang Li,Wang Li, Director, Chief ScientistDirector, Chief ScientistSynfuelsSynfuels ChinaChinaState Key Laboratory of Coal ConversionState Key Laboratory of Coal ConversionInstitute of Coal ChemistryInstitute of Coal ChemistryChinese Academy of SciencesChinese Academy of SciencesTaiyuanTaiyuan 030001030001

Clean Energy system 2005 Clean Energy system 2005 SynfuelsSynfuels ChinaChina

EEU III / 2.0L diesel engine U III / 2.0L diesel engine VolksVolks WagenWagen CADDY SDI 2.0 CADDY SDI 2.0

EEconomic fuel consumption ~5.0 L /100 kmconomic fuel consumption ~5.0 L /100 km

CCetaneetane No. > 70 No. > 70

EExtremely low S and N xtremely low S and N

EEU IV emission limitU IV emission limit

FFirst Car Fueled by 100% First Car Fueled by 100% F--T Super Clean DieselT Super Clean Diesel


Main pointsEnergy status in China

CTL solution

CTL development in China

Future development

Summary

Main pointsMain pointsEnergy status in ChinaEnergy status in China

CTL solutionCTL solution

CTL development in ChinaCTL development in China

Future developmentFuture development

SummarySummary


ReservesCoal

Oil

Gas 0

100

200

300

400

500

600

700

2000 2005 2010 2020

A

B

C

Year

Million tons

Production in China 2020:Production in China 2020:200 million tons/a200 million tons/a

Demands:Demands:A: 610 million tons/aA: 610 million tons/aB: 560 million tons/aB: 560 million tons/aC: 450 million tons/aC: 450 million tons/a

Gap:Gap:250250--410 million tons/a410 million tons/a

•• Coal as major primary energyCoal as major primary energy

•• Oil insufficiency for the growing demandsOil insufficiency for the growing demands

•• Solutions needed for sustainable developmentSolutions needed for sustainable development

Energy status in ChinaEnergy status in China


CTL SolutionCTL Solution

SyngasSyngasproductionproduction

SyngasSyngasPurificationPurification SynthesisSynthesis

Biomass Biomass Coal Coal Organic wastes Organic wastes

NOW NOW FUTURE FUTURE

CTL pointing to the sustainable solutions on the basis of GAIFICTL pointing to the sustainable solutions on the basis of GAIFICATIONCATIONLess limited life span of CTL initialized production systemLess limited life span of CTL initialized production system

Power Power GenerationGeneration

Electricity Liquid fuels Naphtha & Chemicals HydrogenElectricity Liquid fuels Naphtha & Chemicals Hydrogen

Highly Highly IntegratedIntegrated

SystemSystem

COCO22controlcontrol


CTL Solution CTL Solution FischerFischer--TropschTropsch Synthesis Synthesis

•• Commercial scale operationCommercial scale operationSASOL SASOL

HTFT gasHTFT gas--solid fluidized bed iron light fractionssolid fluidized bed iron light fractions

LTFT slurry phase /fixed bed iron and cobalt heavy fracLTFT slurry phase /fixed bed iron and cobalt heavy fractionstions

SHELLSHELL

SMDS Fixed bed cobaltSMDS Fixed bed cobalt

•• Technology in China: pilot plant provenTechnology in China: pilot plant provenSynfuelsSynfuels China iron (main) cobalt (in development) China iron (main) cobalt (in development)

HFPTHFPT®® slurry phaseslurry phase--low temperature <250low temperature <250ooC heavy fractionsC heavy fractions

LFPTLFPT®® slurry phaseslurry phase––high temperature 270high temperature 270--290290ooC diesel range highC diesel range high


CTL in China: Brief history 1950CTL in China: Brief history 1950--1962 1962

First BASF FTS technologyFirst BASF FTS technology

Cobalt catalyst at normal pressureCobalt catalyst at normal pressure

74(X13ton) fixed bed reactors74(X13ton) fixed bed reactors30000ton Hydrocarbons/ a30000ton Hydrocarbons/ a

The plant was removed due to oil The plant was removed due to oil field discovery in 1960s in Chinafield discovery in 1960s in China

CTL Development In China CTL Development In China


--19791979--1989: Development of iron catalysts 1989: Development of iron catalysts Fixed bed reactor up to single tube tests.Fixed bed reactor up to single tube tests.Slurry phase test in laboratorySlurry phase test in laboratory



--19901990--1993: 1993: 40 b /d demonstration plant test40 b /d demonstration plant testFixed bed reactor with about 2000 tubes Fixed bed reactor with about 2000 tubes

1) 1) DesulfurizationDesulfurization was not adequate was not adequate 2) Extremely low oil price2) Extremely low oil price



New enhanced development initialized in 1997New enhanced development initialized in 1997

FischerFischer--TropschTropsch synthesis in slurry phasesynthesis in slurry phase



SynfuelsSynfuels China China

FTS catalyst FTS catalyst groupgroup

Engineering Engineering groupgroup

SyncrudeSyncrudeworkingupworkingup

FundamentalFundamental



FTS catalyst research and developmentFTS catalyst research and development-- Iron based ICCIron based ICC--I (heavy fraction) 230I (heavy fraction) 230--250250ooC, slurry phaseC, slurry phase-- Iron based ICCIron based ICC--II (lighter fraction) 260II (lighter fraction) 260--280280ooC, slurry phaseC, slurry phase-- Cobalt based ICCCobalt based ICC--III 220 III 220 ooC~240C~240ooC, slurry phase, fixed bedC, slurry phase, fixed bed


- 1 0 - 5 0 5 1 0

9 2

9 6

1 0 0

9 8

1 0 0

9 6

1 0 0

9 6

1 0 0

9 2

9 6

1 0 0

9 6

1 0 0

9 6

1 0 0

Tran

smis

sion

(%)

V e l o c i t y ( m m / s , r e l a t i v e t o α - F e )

F M S A

F M S B

F M S D

F S C P

S P U W

F M S E

F M S C

1000 2000 3000 4000 50000

10

20

30

40

50

60

70

80C

onve

rsio

n/S

elec

tivity

(%)

Time on stream (h)

CO con. H2 con. CO+H2 con. CH4 sel. C5

+ sel. C2-C4= sel.


Process development and integration analysisProcess development and integration analysis-- Simulation of FischerSimulation of Fischer--TropschTropsch loop for different catalyst systemsloop for different catalyst systems-- Hydrodynamics of slurry phase FT reactors and related Hydrodynamics of slurry phase FT reactors and related -- Pilot plant design & operationPilot plant design & operation-- Large scale slurry reactor design (4 m~ 8 m)Large scale slurry reactor design (4 m~ 8 m)



SyncrudeSyncrude workup technologyworkup technology-- New hydrogenation catalysts for hydrogenating FTS New hydrogenation catalysts for hydrogenating FTS crudescrudes-- Cracking of FTS wax (new route)Cracking of FTS wax (new route)-- OligmerizationOligmerization of light olefins of light olefins -- Separation engineering Separation engineering



Engineering fundamentalEngineering fundamental-- CFD calculation of three phase reactorsCFD calculation of three phase reactors-- Quantum calculations on catalytic mechanismQuantum calculations on catalytic mechanism-- ThermodymicThermodymic data data -- Kinetics and reactor modelingKinetics and reactor modeling




Pilot plant 2001Pilot plant 2001--20042004-- Two types catalysts have been testedTwo types catalysts have been tested-- Slurry phase reaction engineering well proved: reactor & relateSlurry phase reaction engineering well proved: reactor & related process d process -- Product workingProduct working--up proved up proved -- Design package accomplished for the demonstration plant (3500 Design package accomplished for the demonstration plant (3500 b/d)b/d)

Demonstration plant (Demonstration plant (SynfuelsSynfuels China+industriesChina+industries))-- Iron catalyst + slurry phase reactor (~ 5.5m)Iron catalyst + slurry phase reactor (~ 5.5m)-- Dry fed entrained flow gasification (2 GSP )Dry fed entrained flow gasification (2 GSP )-- Diesel 70% Naphtha 18% LPG 12%Diesel 70% Naphtha 18% LPG 12%-- Possible IGCC scheme is considered (If governmental support gotPossible IGCC scheme is considered (If governmental support got))-- Efficiency ~ 43% Efficiency ~ 43%

Commercial action (Commercial action (Industries+governmentIndustries+government))-- Two trains 3.2 million ton/year Two trains 3.2 million ton/year ShenhuaShenhua NingmeiNingmei-- SasolSasol technology (tendency)technology (tendency)-- 20062006--2007 initializing2007 initializing


Preliminary results of the CTL diesel

<0.2mg KOH <0.2mg KOH /100ml/100ml

--5.395.39AcidityAcidity<0.3 mg/100ml<0.3 mg/100ml----Oxidation stabilityOxidation stability

--22--3434--33CFPP CFPP ooCC<0.5<0.5<5<5<4<4Sulfur Sulfur ppmppm00000.50.5Olefin %Olefin %000000Poly aromatics %Poly aromatics %000.70.70.40.4Total aromatics %Total aromatics %>78>78--9090666674.174.1--80.180.1CentaneCentane No.No.747466666464Flash point Flash point ooCC

350350385385370370Final boiling point Final boiling point ooCC150150138138154154InitiIniti. boiling point . boiling point ooCC

3.2763.2763.9573.9573.1723.172Viscosity mm2/s, 20 Viscosity mm2/s, 20 ooCC

0.76640.76640.77820.77820.76840.7684Density kg/LDensity kg/LNi Ni HyHyCoCo--MoMo--S CrS CrCoCo--MoMo--S S HyHy..IndexIndex


CTL Future DevelopmentCTL Future Development

High selective catalysts developmentHigh selective catalysts development-- Narrowing to middle distillatesNarrowing to middle distillates-- Working at high temperature (280Working at high temperature (280ooC) but in slurry phaseC) but in slurry phase-- Optimizing factors affecting efficiencyOptimizing factors affecting efficiencyReactor & processesReactor & processes-- Enhancing reaction heat recovery ( 15% energy of Enhancing reaction heat recovery ( 15% energy of syngassyngas ))-- Pressure up to 45 bars to increase single train productivityPressure up to 45 bars to increase single train productivity-- Process integration optimization (coProcess integration optimization (co--production evaluation) production evaluation) -- Water saving and treatment technologies Water saving and treatment technologies New technology for New technology for syncrudesyncrude upup--gradinggrading-- S free catalyst for hydrogenation & crackingS free catalyst for hydrogenation & cracking-- Light fraction utilizationLight fraction utilization-- New route for fuel productionNew route for fuel production-- Chemicals from Chemicals from syncrudessyncrudes


CTL Future Development: CTL Future Development: CoCo--productionproduction

Syngasproduction

F-T synthesisProduct upgrading

ElectricitySteam (HP, MP,LP)

Coal 1000 tons6500 kcal/kg

Oxygen681375 Nm3

88.942 ton ST coalSyngas1965125 Nm3

800.087 ton ST coal

Tail gas66.565 ton ST coal

928.571 ST coal

Steam MP50 tons4.911 ton ST coal

Electricity30000 KWh 9.9 ton ST coal

Oil products 342.341 tons528.183 ton ST coal


Steam (HP-MP)1200 tons117.857 ton ST coal

Steam (LP-MP) 1883 tons184.925 ton ST coal

Electricity446412.827 KWh 147.316 ton ST coal

(1)

(2)

(3)

(4)

(5)

(6)

(9)

(10)

(8)

(7)

(10)Syngasproduction

F-T synthesisProduct upgrading

ElectricitySteam (HP, MP,LP)


Oxygen681375 Nm3


800.087 ton ST coal

Tail gas66.565 ton ST coal

928.571 ST coal








(1)

(2)

(3)

(4)

(5)

(6)

(9)

(10)

(8)

(7)

(10)

Energy points:Air separation & other unrecoverable: 15~25%.Recoverable: hot gas recovery 10%; tail gas 5.6%; reaction heat 15%.

Efficiency

Oil 43-45% FTS thermal: 78-80%; CTL thermal: 63-65%

Gasification thermal: 90%


Syngasproduction

F-TProduct upgrading

Electricity

Steam (HP, MP,LP)


Oxygen681375 Nm3


800.087 ton ST coal

Tai gas66.565 ton ST coal

928.571 ST coal








(1)

(2)

(3)

(4)

(5)

(6)

(9)

(10)

(8)

(7)

(10)

IGCC

Steam1200 tons (HP-MP)1883 tons (LP)

Electricity2898036 MJ 99.1 ton ST coal

(11)

(12)

Syngasproduction

F-TProduct upgrading

Electricity

Steam (HP, MP,LP)


Oxygen681375 Nm3


800.087 ton ST coal

Tai gas66.565 ton ST coal

928.571 ST coal








(1)

(2)

(3)

(4)

(5)

(6)

(9)

(10)

(8)

(7)

(10)

IGCC

Steam1200 tons (HP-MP)1883 tons (LP)

Electricity2898036 MJ 99.1 ton ST coal

(11)

(12)

CoCo--generation an introductiongeneration an introduction

Efficiency

Oil_electricity 52-54% FTS thermal: 78-80%; CTL thermal: 63-65% Gasification thermal: 90%

Simple Co-production scheme can optimize the energy flows into valuable products


SummarySummary

CTL in whole has been well proved by large scale production anCTL in whole has been well proved by large scale production and is an d is an important and practical option for Chinaimportant and practical option for China’’s future liquid fuel supply.s future liquid fuel supply.CTL route will bring us to a sustainable way in using our availCTL route will bring us to a sustainable way in using our available able sources via sources via syngassyngas..CTL technology in China is approaching matured and will play imCTL technology in China is approaching matured and will play important portant roles in the growing market.roles in the growing market.The superThe super--clean diesel produced via CTL route will largely impose great clean diesel produced via CTL route will largely impose great benefits from environment improvement.benefits from environment improvement.CoCo--production solutions should be seriously considered. production solutions should be seriously considered.


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indirect coal liquefaction - stanford university · ctl in whole has been well proved by large...

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