THE Next Generation Coal Conference
-
Upload
idownloadbooksforstu -
Category
Documents
-
view
220 -
download
0
Transcript of THE Next Generation Coal Conference
-
7/28/2019 THE Next Generation Coal Conference
1/39
INSTITUTE OFCHEMICAL TECHNOLOGY
Production of Fuels and Chemicals
from Coal:
An Overview of Existing Technologies
and Future Challenges
PD Dr. Yvonne Traa
Newcastle, J uly 13, 2012
-
7/28/2019 THE Next Generation Coal Conference
2/39
2
Common Abbreviations for Reactants To Products
Y. Traa, Chem. Commun. 46 (2010) 2175.
-
7/28/2019 THE Next Generation Coal Conference
3/39
3
Influence of Feedstock
M. Sudiro, A. Bertucco, Int. J . Alternative Propulsion 2 (2008) 13.
Feedstock Fuel produced ona weight basis perunit of feedstock
CO2 emittedper kg ofliquid fuel
Natural gas 67 % 0.9 kg
Coal 33 % 4.8 kg
Wood 17 % 6.1 kg
-
7/28/2019 THE Next Generation Coal Conference
4/39
4
Production of Gasoline and Diesel from Coal
Y. Traa, Chem. Commun. 46 (2010) 2175.
-
7/28/2019 THE Next Generation Coal Conference
5/39
5
Outline
Introduction
Coal conversion techniques
Fischer-Tropsch synthesis
Methanol-based techniques
Direct coal liquefaction
Conclusions and outlook
-
7/28/2019 THE Next Generation Coal Conference
6/39
6
Coal Conversion Processes
Coal, J .C. Crelling et al., in: Ullmanns Encyclopedia of IndustrialChemistry, Wiley-VCH, Weinheim, 2006.
Extraction Pyrolysisor Carbo-
nisation
Directlique-
faction
Gasifi-cation
Com-bustion
Mainproducts
montanwax
coke, coaltar,benzene,gas
gasoline synthesisgas
electricpower, heat
Furtherreactants
- - hydrogen air oroxygen,steam
air oroxygen
Tempera-ture / C
80-90 > 300-1300 400-480 370-1600 1000-1800
Pressure 0.1 MPa 0.1 MPa 15-70 MPa 0.1-3 MPa 0.1-3 MPaCatalyst no no yes usually no no
Increasing severity of process
-
7/28/2019 THE Next Generation Coal Conference
7/39
7
Outline
Introduction
Coal conversion techniques
Fischer-Tropsch synthesis
Methanol-based techniques
Direct coal liquefaction
Conclusions and outlook
-
7/28/2019 THE Next Generation Coal Conference
8/39
8
The Chemistry of Synthesis Gas
Y. Traa, Chem. Commun. 46 (2010) 2175.
-
7/28/2019 THE Next Generation Coal Conference
9/39
9 Y. Traa, Chem. Commun. 46 (2010) 2175.
Scheme of Fischer-Tropsch Synthesis from Coal
-
7/28/2019 THE Next Generation Coal Conference
10/39
10
Reaction Mechanism of Fischer-Tropsch Synthesis
J .-D. Arndt et al., Chem. Ing. Tech. 79 (2007) 521;J . Gaube, H.-T. Klein, J . Molec. Catal. A: Chemical 283 (2008) 60.
Surface polymerisationwith
chain start (e.g., by adsorption of CO and formation of asurface species via reaction with H2),
chain growth (e.g., by insertion of CO and/or CH2units) and
chain termination (e.g., by hydrogenation yielding alkanes or
via the formation of alkenes).
-
7/28/2019 THE Next Generation Coal Conference
11/39
11
Mild Hydrocracking of Fischer-Tropsch Product
V.M.H. Van Wechem, M.M.G. Senden, Stud. Surf. Sci. Catal. 81 (1994) 43.
Mild hydrocracking ofthe Fischer-Tropschproduct maximisesthe yield of middledistillate.
-
7/28/2019 THE Next Generation Coal Conference
12/39
12 I.I. Rahmim, Oil Gas J . 106 (No. 12, 2008) 22.
I.I. Rahmim, Oil Gas J. 106 (No.12, 2008) 22.
Capital cost /106 US-$
Capital costpercentage
Coal and slurry preparation
Coal gasification
Air separation unit
Synthesis gas clean-up
425
1,150
425
850
67 %
Water gas shift and
Fischer-Tropsch synthesis
51012 %
Product upgrading 210 5 %Power generation
Other cost (without CCS)
255
42516 %
Total 4,250 100 %
Typical Cost for 2.5 106 t/a Capacity
-
7/28/2019 THE Next Generation Coal Conference
13/39
13 M.E. Dry, A.P. Steynberg, Stud. Surf. Sci. Catal. 152 (2004) 406.
Carbon Efficiency and Stoichiometry
-
7/28/2019 THE Next Generation Coal Conference
14/39
14
Fischer-Tropsch Synthesis: Status 2008
A. de Klerk, Catal. Today 130 (2008) 439; I.I. Rahmim, Oil Gas J . 106 (No. 12,
2008) 22; M.E. Dry, in Handbook of Heterog. Catal., G. Ertl et al. (Hrsg.), 2.Aufl., Bd. 6, WILEY-VCH, Weinheim, 2008, S. 2965.
SMDS,Malaysia
Oryx GTL,Katar(Sasol,
Chevron)
PetroSA,South Africa
Sasol SynfuelsE & W,Secunda, South
Africa
Sasolburg,South Africa
Productionofsynthesisgas
Partialoxidation ofnatural gas
Natural gas Steamreforming ofnatural gas
CoalNatural gas
Reactor Multitubularreactor
Slurryreactor
Circulatingfluidised bed
Fixed fluidisedbed, i.e.
ebullating bed
Multitubularand slurry
reactor
Catalyst Co/SiO2 ? Co/SiO2/Al2O3 ?
Fe (fused) Fe(fused with K2Oand MgO orAl2O3) ?
Fe (co-precipitationwith Cu) ?
Reactionconditions
LTFT LTFT HTFT HTFT LTFT
Mainproduct
Waxes andparaffins
Diesel Gasoline Gasoline Waxes andparaffins
Capacity 0.7 106 t a-1 1.6 106 t a-1 1.1 106 t a-1 7 106 t a-1 0.3 106 t a-1
-
7/28/2019 THE Next Generation Coal Conference
15/39
15
Scheme of CTL with IGCC and CCS
I.I. Rahmim, Oil Gas J . 106 (No. 12, 2008) 22.
-
7/28/2019 THE Next Generation Coal Conference
16/39
16
Poly-Generation Plants
R.H. Williams et al., Energy Procedia 1 (2009) 4379.
Co-production of electricity and Fischer-Tropsch liquids
(FTL) leads to less costly FTL than via production thatmaximises the output of FTL.
In poly-generation plants, about of the feedstock
carbon can be recovered as CO2 in a concentrated
stream for which CCS costs are small relative to CCScosts for stand-alone power plants.
Co-processing biomass with coal is a cost-effective
way to reduce FTL greenhouse gas emissions,
requiring much less biomass input to realize ultralowemission rates for liquid fuels compared to
conventional non-food biofuels options such as
cellulosic ethanol.
-
7/28/2019 THE Next Generation Coal Conference
17/39
17
Handling H2-Deficient and CO2-Rich Syngas
O.O. J ames et al., Fuel Process. Technol. 91 (2010) 136.R.W. Dorner et al., A l. Catal. A: General 373 (2010) 112.
Fe-based catalysts needed: Water gas shift activity (on Co-basedcatalysts hydrogenation of CO2 yields CH4). Catalysts have to be adapted (e.g., large amounts of K promoter areknown to poison the Fe catalyst, but in CO2 hydrogenation largeramounts of K are beneficial).
-
7/28/2019 THE Next Generation Coal Conference
18/39
18
Greenhouse Gas Emissions
Xie et al., Environ. Sci. Technol. 45 (2011) 3047.
-
7/28/2019 THE Next Generation Coal Conference
19/39
19
Fischer-Tropsch Synthesis and Catalytic CH4 Decomposition
G.P. Huffman, Fuel 90 (2011) 2671.
H2/CO fromgasifier
H2/CO afterCDH
MWCNTproduced(t/d)
CO2emissionsavoided (t/d)
H2O saved(gal/day)
1 2.3 2153 13,575 1,330,836
0.8 2.1 1958 12,343 1,210,057
Calculations of products+environmental savings for a 50,000 bbl/d plant:
-
7/28/2019 THE Next Generation Coal Conference
20/39
20
UCG Combined with Fischer-Tropsch in Australia
h. www.lincenergy.com
-
7/28/2019 THE Next Generation Coal Conference
21/39
21
Brown Coal to Liquids in Australia
http://www.monashenergy.com.au.
The Monash Energy project utilises brown coal, which has a much highermoisture content than black coal. It is this higher moisture content which drivesthe lower efficiency ratings of brown coal fired power plants compared to blackcoal. The cost for lower efficiency is a higher output per unit of greenhouse gasemissions. For this reason, pre-drying of brown coal has long been identified asa potential means of improving the efficiency of combustion in brown coal firedpower plants.
The Monash
Energy Project isthe first to benominated fordevelopmentunder a CleanCoal EnergyAlliance formedbetween AngloAmerican andShell in May2006.
http://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.angloamerican.co.uk/http://www.angloamerican.co.uk/http://www.shell.com/http://www.shell.com/http://www.angloamerican.co.uk/http://www.angloamerican.co.uk/http://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.htmlhttp://www.shell.com/home/content/media/news_and_library/press_releases/2006/clean_coal_alliance_25052006.html -
7/28/2019 THE Next Generation Coal Conference
22/39
22
Outline
Introduction
Coal conversion techniques
Fischer-Tropsch synthesis
Methanol-based techniques
Direct coal liquefaction
Conclusions and outlook
-
7/28/2019 THE Next Generation Coal Conference
23/39
23
Basis: Lurgi MegaMethanol
http://www.lurgi.com/website/fileadmin/user_upload/1_PDF/1_Broshures_Flyer/englisch/0305e_Gas-to-Chemicals.pdf.
-
7/28/2019 THE Next Generation Coal Conference
24/39
24
Influence of the Residence Time on Product Yields
S. Kvisle et al., in Handbook of Heterog. Catal., G. Ertl et al. (eds.),2nd ed., Vol. 6, WILEY-VCH, Weinheim, 2008, p. 2950.
-
7/28/2019 THE Next Generation Coal Conference
25/39
25
Technologies for the Production of Olefins
E. Schwab et al. and H. Zimmermann, in: Preprints of the ConferenceProduction and Use of Light Olefins, DGMK Tagungsbericht 2009-2, S.
Ernst et al. (eds.), DGMK, Hamburg, 2009, p. 25 and p. 7; S. Kvisle et al., in:
Handbook of Heterogeneous Catalysis, 2nd
ed., Vol. 6, G. Ertl et al. (eds.),WILEY-VCH, Weinheim, 2008, p. 2950.
MTO(UOP/Hydro)
MTP(Lurgi)
FTTO(BASF)
Steam-cracking
Reactor fluidised bed fixed bed,DME pre-reactor
not disclosed crackingfurnace
Reactants methanol methanol synthesisgas
steam,naphtha
Temperature 350-600 C 450 C 340 C 820-850 C
Catalyst zeoliteH-SAPO-34
ZeoliteH-ZSM-5
probablyFe-based
none
Regenerationof catalyst
continuously,fluidised bed
fixed bed not disclosed not applicable
npropene/nethene 0.4 to 0.9 ca. 1.0 0.3
-
7/28/2019 THE Next Generation Coal Conference
26/39
26
Lurgis MTP Technology
-
7/28/2019 THE Next Generation Coal Conference
27/39
27
MTP from Coal in China (I)
http://www.dtpower.com/en/content/2011-01/20/content_89753.htm.
-
7/28/2019 THE Next Generation Coal Conference
28/39
28
MTP from Coal in China (II)
http://www.lurgi.com.
Engineering & Construction: A New Lurgi-MTP Unit for China
2011/08/26
Air Liquide is pleased to announce that its Engineering & Construction division has
signed a contract with the Shenhua Ningxia Coal Industry Group (SNCG) in China,
one of the worlds largest coal industrials, to build a 500,000 tpa Methanol-to-Propylene (MTP) plant, following the successful commissioning of the first industrial
scale unit built with the same client.
This will be the third large-scale MTP plant licensed by Lurgi. SNCG, in close
cooperation with the Lurgi team, played an important and constructive role in the
commissioning and startup phases of the MTP-1 first of a kind plant, thereby
contributing to proving at industrial scale the success of the Lurgi MTP technology
Air Liquide will remain the sole owner and licensor of the Lurgi MTP technology
-
7/28/2019 THE Next Generation Coal Conference
29/39
29
UOP/Hydro MTO
www.uop.com.
Total Petrochemicals/UOPs
olefin cracking process:cracking C4+olefins toethene and mainly propene
-
7/28/2019 THE Next Generation Coal Conference
30/39
30
P
http://www.exxonmobil.com/Apps/RefiningTechnologies/files/conference_2011.1204.MTG_World_CTL.pdf.
-
7/28/2019 THE Next Generation Coal Conference
31/39
31
ExxonMobil Research and Engineering: MTG
http://www.exxonmobil.com/Apps/RefiningTechnologies/files/conference_2011.1204.MTG_World_CTL.pdf.
Medicine Bow project, Wyoming
Mingo County project, West Virginia
-
7/28/2019 THE Next Generation Coal Conference
32/39
32
Methanol To Gasoline (MTG)
http://www.exxonmobil.com/Apps/RefiningTechnologies/files/sellsheet_09_mtg_brochure.pdf.
-
7/28/2019 THE Next Generation Coal Conference
33/39
33
Outline
Introduction
Coal conversion techniques
Fischer-Tropsch synthesis
Methanol-based techniques
Direct coal liquefaction
Conclusions and outlook
-
7/28/2019 THE Next Generation Coal Conference
34/39
34
Simplified Scheme of Direct Coal Liquefaction
Y. Traa, Chem. Commun. 46 (2010) 2175.
-
7/28/2019 THE Next Generation Coal Conference
35/39
35
Shenhua: Direct Coal Liquefaction
www.worldcoal.org...coal_liquid_fuels_report...
-
7/28/2019 THE Next Generation Coal Conference
36/39
36
Shenhua: Direct Coal Liquefaction
Two ebullated bed reactors utilising a proprietary
dispersed superfine (nanosized) disposable Fe catalyst
(GelCat) prepared from iron sulfate.
Fixed-bed in-line hydrotreater with Ni-Mo/Al2O3 catalyst.
Feedstock: Bituminous coal.
Reaction conditions: 400 to 460 C, 17 MPa.
J uly 2011: 12 times of coal injection completed
10,670 operating hoursproducts: 550,000 t diesel
247,500 t naphtha
99,000 t LPG
-
7/28/2019 THE Next Generation Coal Conference
37/39
37
Integrated Coal-To-Liquids Process
WO Patent Application WO 2010/135381 A1, 25 November 2010,assigned to Accelergy Corp.
Algae production
-
7/28/2019 THE Next Generation Coal Conference
38/39
38
Possibilities for H2 Replacement during DCL
[1] K.Z. Yang et al., Fuel 76 (1997) 1105.[2] J . Cai et al., Fuel 87 (2008) 3388.[3] Z. Lei et al., Fuel Process. Technol. 91 (2010) 783.
[4] Z. Lei et al., Energy 36 (2011) 3058.[5] Y. Watanabe et al., Fuel 75 (1996) 46.
It has been reported that 40-50 % of the cost of DCL are due to
H2 generation [1]. In addition, H2 generation produces most of the
time large amounts of additional CO2.
CH4 or mixtures of CH4 and H2 can be used as hydrogenation
gas at higher temperatures or with certain catalysts [1,2].
Liquefaction of lignite withNaOH/MeOH at 300C + 13 MPa [3]
MeOH, CaO, FeS at 400C + 4 MPa [4].
Liquefaction in CO/H2
O: CO + H2
O CO2
+ H2
[5].
-
7/28/2019 THE Next Generation Coal Conference
39/39
39
Conclusions and Outlook
The reserves and resources of coal are distributed more evenly and
are significantly larger than those of oil and natural gas. Thus, coal-
based processes are gaining significance. The environmental problems related to coal mining and coal use are
large. Measures for environmental protection have to be taken.
The best option is to use a well balanced energy mix and to use all
energy sources efficiently avoiding unnecessary process steps. The coal conversion techniques discussed offer real alternatives tothe production of fuels and chemicals from crude oil.
Research and development in the area of renewable energy for the
production of electricity and heat should be fostered so that in the longterm the use of coal can be restricted to the production of chemicals
and liquid fuels for heavy-duty vehicles, ships and airplanes.
Because of the much smaller consumption for these purposes ascompared to the consumption for power production, the carbon dioxide
i i ill th b t bl