Biobased Materials And Fuels Via Methanol The Role Of .
Biobased materials and fuels via methanol– The role of integrationJoint Task 33 & IETS workshop at Göteborg, Nov2013Ilkka HannulaVTT Technical Research Centre of Finland
27/11/20132Gasification and Gas Cleaning Process- developed and tested at VTT on 0.5 MW scale-ca. 4000 operating hours with different wood residuesGasification: 4 bar, 850 CFiltration: 550 CReforming: 950 C, 95 % CH4 conv.
27/11/2013Levelised production cost estimates*300 MW biomass @ 17 /MWh, 0.12 ann. factorElectricity 50 /MWh, DH 30 /MWh@5500 h/aTotal Capital Investment estimates: 331-446 M 3Mature technologyNo investment supportNo CO2 creditsNo tax assumptionsGasoline@150 /bblBefore tax, incl.refining margin,1 1.33 (2010)Gasoline@100 /bbl*Liquid transportation fuels via large-scale fluidised-bed gasification of lignocellulosic biomass, Hannula, Ilkka; & Kurkela, Esa 2013. VTT, Espoo. 114 p. app. 3 p. VTT Technology: 91
27/11/2013Levelised production cost estimates*300 MW biomass @ 17 /MWh, 0.12 ann. factorElectricity 50 /MWh, DH 30 /MWh@5500 h/aTotal Capital Investment estimates: 331-446 M 4Mature technologyNo investment supportNo CO2 creditsNo tax assumptionsGasoline@150 /bblBefore tax, incl.refining margin,1 1.33 (2010)Transportation fuels currently cost around 750 /tonneGasoline@100 /bbl*Liquid transportation fuels via large-scale fluidised-bed gasification of lignocellulosic biomass, Hannula, Ilkka; & Kurkela, Esa 2013. VTT, Espoo. 114 p. app. 3 p. VTT Technology: 91
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27/11/2013912 – 1243 /ton6
27/11/20137Light OlefinsOlefins ethylene and propylene form the main petrochemical platform Main plastics (polyethylene and polypropylene), elastromers, rubbers Ethylene is used for monomers like ethylene glycol, ethylene oxide , styrene, vinyl- andfluoromonomers Propylene is used also formonomers like acrylic acid, acrylnitrile, propylene oxide Several base chemicals like acitic acid, surfactants, base oils, etc.Ethylene (C2H4)Propylene (C3H6)
27/11/20138Olefin pshBio nolEthyleneGasificationFermentation
27/11/20139Olefin pshBio nolEthyleneGasificationFermentation
27/11/201310The proposed 2-step conceptMethanol-to-Olefins- MTO was first developed by Mobil in the mid-1980s as a spin-off toMTG in New Zealand.- Technology went unused until the mid-1990’s when UOP & NorskHydro build a pilot plant in Norway.- A successful 100 bbl/d demonstration later operated in Germany.- Since then, Lurgi has also developed its own version (MTP).- Dalian Institute of Chemical Physics has recently developed asimilar process (DMTO).Biomass-to-Methanol- First described by Patart [43] and soon after produced by BASF chemists in Leuna,Germany in 1923. [44]- Low pressure methanol synthesis, pioneered by engineers at ICI has become the exclusiveproduction process since 1960’s- Methanol is the largest product from synthesis gas after ammonia- Can be utilised as chemical feedstock or to supplement liquid fuels.- Can also be converted to various chemicals or used as a portal to hydrocarbon fuelsthrough the conversion to dimethyl ether (DME) or gasoline (MTG).- In 2011 the annual consumption of methanol amounted to 47 million tons
27/11/201311The proposed 2-step conceptMethanol-to-Olefins- MTO was first developed by Mobil in the mid-1980s as a spin-off toMTG in New Zealand.- Technology went unused until the mid-1990’s when UOP & NorskHydro build a pilot plant in Norway.- A successful 100 bbl/d demonstration later operated in Germany.- Since then, Lurgi has also developed its own version (MTP).- Dalian Institute of Chemical Physics has recently developed asimilar process (DMTO).Possibilities for two types ofintegration examined:- Heat integration- Equipment sharingBiomass-to-Methanol- First described by Patart [43] and soon after produced by BASF chemists in Leuna,Germany in 1923. [44]- Low pressure methanol synthesis, pioneered by engineers at ICI has become the exclusiveproduction process since 1960’s- Methanol is the largest product from synthesis gas after ammonia- Can be utilised as chemical feedstock or to supplement liquid fuels.- Can also be converted to various chemicals or used as a portal to hydrocarbon fuelsthrough the conversion to dimethyl ether (DME) or gasoline (MTG).- In 2011 the annual consumption of methanol amounted to 47 million tons
27/11/201312Biomass to Methanol- CFB gasification with O2 at 4 barand 850 C.- Catalytic reforming of tars andhydrocarbons- Rectisol acid gas removal- Highly selective (99.9 %) Cu-ZnOAl2O3 or Cr2O3 based commercialmethanol catalysts- Synthesis conditions 250 Cand 80 bar.- Final purification by conventionaldistillationSimplified layout of the methanol synthesis loop, product recovery and distillation section.
27/11/2013Thermal efficiency tomethanol and by-products13
27/11/2013EQUIPMENT COST ESTIMATESAuxiliary equipmentSite preparationOxygen productionFeedstock pretreatmentGasification islandGasificationHot-gas cleaningCO shiftSyngas coolingCompressionAcid gas removalPower islandHRSG (GI AUX)Aux. boiler fluegas treatm.Steam turbine condenserMethanol synthesisSyngas compresssorSynthesis loopDistillation (minimal)Distillation (chemical-grade)SUM EQUIPMENTCHANGEBase 818107524192452166002121730152144-4.8 %139-3.6 %-8.2 %14Equipment costestimates for a plantprocessing 150 MWof biomasssEquipment sharingpossibilities
27/11/2013ESTIMATES FOR 150 MWbiom PLANTTOTAL OVERNIGHT CAP. COSTTOTAL CAP. INV. (at 5% interest)CHANGEBaseCase21522615w/ Eq. Sharing w/ Min. Dstl.206199217209-4.0 %-3.7 %-7.5 %
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27/11/201318Methanol to Light OlefinsUOP/Hydro’s MTO process Fluidised-bed reactor at 410 C and 3 bar Ethylene and propylene mass ratio 1:1 99.8 % conversion of methanol Coke formation 4.5 wt% of feed MeOH Catalyst continuously regenerated in a combustor Multi-column cryogenic distillation requiredFast-fluidised MTO reactor
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27/11/2013Product integration20
27/11/2013Product integration21
27/11/2013Olefin boosting22
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27/11/2013MTO integrationwith an Ethene Plant27
2827/11/2013UOP/Hydro’s Methanol-to-Olefins processCOMPRESSORTail gasCOMPRESSORPHASESEPARATORREACTOR C1 EtheneC2SPLITTERDE-C2PropeneMethanol crudeUnconv.methanolWATERSTRIPPERWaste waterAirCONDENSATESTRIPPERDRYERC4 streamC3SPLITTERPropaneDE-C3C4 Ethane
27/11/2013Kilpilahti Ethene PlantSource: Öljystä muoveihin (1992), Neste Oyj.29
27/11/2013MTOcrudeKilpilahti Ethene PlantSource: Öljystä muoveihin (1992), Neste Oyj.30
3127/11/2013UOP/Hydro’s Methanol-to-Olefins processCOMPRESSORTail gasCOMPRESSORPHASESEPARATORREACTOR C1 EtheneC2SPLITTERDE-C2PropeneMethanol crudeUnconv.methanolWATERSTRIPPERWaste waterAirCONDENSATESTRIPPERDRYERC4 streamC3SPLITTERPropaneDE-C3C4 Ethane
hanol crudeUnconv.methanolWATERSTRIPPERWaste waterAirMTO crudeREACTOR ®ENERATORCONDENSATESTRIPPERC4 stream32
3327/11/2013Separations when integrated to a refineryMTO CONVERSIONETHENE PLANTCOMPRESSORPHASESEPARATORFluegasQUENCHMTO crudeREACTOR ®ENERATORCAUSTICWASHDRYINGCOOLINGTail C2 OMPRESSORC4 streamDE-C2PRE DE-C1Methanol crudeC3SPLITTERPropaneC3 DE-C3Waste waterC4 C4C4SPLITTERC5
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27/11/2013At what scale?35
27/11/2013Case Example: Crackers ofthe Kilpilahti Refinery in Finland36
27/11/2013Case Example: Crackers ofthe Kilpilahti Refinery in FinlandNaphtha replacement: 2.6 kg/kg MeOH/naphtha10 t/h naphtha 208 kton/a of methanol37
27/11/201338Capital cost estimates for MTOScaling parameterMethanol to OlefinsMethanol conversionProduct separationRefrigeration systemUtilitiesStorageService facilitiesOlefin Cracking ProcessC4 conversionMOGDOlefin conversionCost ence yearReference Included in: Included in:cost in 2010 Stand-alone IntegratedMethanol input, kton/aMethanol input, kton/aMethanol input, kton/aMethanol input, kton/aMethanol input, kton/aMethanol input, 2C4 input, kton/a0.85164674.197200777.810C3 input, kton/a0.85164645.431200747.611Cost factorsInstallationIndirect costsContingencyInterest during const.O&MAnnuity76 %52 %63 %5%6%12 %
27/11/201339Investment cost estimates for MTO
27/11/201340Investment cost estimates for MTO 53 % decrease
27/11/201341Investment cost estimates for MTO20 %decrease
27/11/2013Production cost estimates42
27/11/201343Naphtha replacement: To replace 10 t/h of naphtha requires 208 kton/a of methanol To produce 208 kton of methanol requires 341 kton of biomass Assuming 90% availability gives 232 MW biomass requirementProduction cost estimates for such plant:Base CaseDHw/ Eq. Sharingw/ Min. Dstl. /MWh71706867 /GJ19.819.418.918.5 /tonne395386376369
27/11/2013Assumed product pricesPricesElectricityTailgas (H2)EthanePropaneLPGC4 EthenePropeneGasolineDistillate /MWh /tonne /tonne /tonne /tonne /tonne /tonne /tonne /tonne Counting50120033233233211208299951400130044
27/11/201345Assumed product pricesPricesElectricityTailgas (H2)EthanePropaneLPGC4 EthenePropeneGasolineDistillate /MWh /tonne /tonne /tonne /tonne /tonne /tonne /tonne /tonne Counting50120033233233211208299951400130080% ofgasoline price
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27/11/201347Light olefins 1100 /tonne
27/11/201348Assumed product pricesPricesElectricityTailgas (H2)EthanePropaneLPGC4 EthenePropeneGasolineDistillate /MWh /tonne /tonne /tonne /tonne /tonne /tonne /tonne /tonne Counting50120033233233211208299951400130080% ofgasoline priceDouble counting 120 /MWh?
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27/11/201350Light olefins 1100 /tonne
27/11/201351Summary of the biomass conversion step Two types of integration examined: Equipment sharing Heat integration For synthetic methanol production 16 % increase in overall efficiency can be achieved via heatintegration (depending on the produced fuel and steam cycledesign) 7.5 % decrease in TCI can be achieved via equipment sharing Combined effect to the cost of methanol: 395 --- 369 /tonne(6.6 % decrease)
27/11/201352Summary of the methanol conversion step Significant decrease in TCI can be achieved via equipment sharing 112 --- 52 M (53 % decrease) For Basecase MTO When no incentives are in place Max Olefins yields the lowestproduction cost ”Double Counting” incentive makes Base Case MTO slightly moreattractive than Max Olefins Overall role of integration in the two-step production concept enables 414 --- 331 M (20 % decrease) in TCI and 1510 --- 1196 /tonne (21 % decrease) in Levelised cost of lightolefins.
27/11/201353Methanol sink scenario for FinlandMTO: Base Case- Biofuels: 107 kton/a- Bio-olefins: 67 kton/a
27/11/2013Thank you for your attention!LinkedIn: ihannulaprofiletwitter: @ilkkahannula54
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