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  • Biobased Materials and Fuels Via Methanol - The Role of Integration

    Diunggah oleh

    ilkkahannula
    29 tayangan41 halaman
    Light olefins are the basic building blocks of petrochemical industry. They are produced by steam cracking of hydrocarbon feedstocks like naphtha or natural gas / shale gas liquids. Rising prices of petroleum feedstocks, together with demand for bio-based feeds on selected markets, have driven technology development to unlock production routes to olefins from alternative feedstocks such as ethanol and methanol. As methanol can be produced from any gasifiable carbonaceous source, including lignocellulosic biomass, the Methanol-to-Olefins route opens up a possibility to produce 100 % bio-based plastics and chemicals. Large-scale production of synthetic biofuels like methanol requires a fairly complex process that combines elements from power plants, refineries and woodprocessing industry. When such plants are built, it is advisable to integrate them with existing processes to minimise capital footprint and to ensure the efficient utilisation and exchange of heat, steam and byproducts. This work evaluates the thermodynamic and economic potential of a two-step production of olefins from biomass via methanol. The production of biomethanol takes place in the vicinity of affordable biomass resources in a plant that is energy integrated with a woodprocessing industry or a district heating network. The subsequent conversion of methanol to olefins takes place at a refinery site where separation columns of an existing ethene plant are utilised to partly fractionate the MTO crude. This study includes conceptual design, process description, mass and energy balances and production cost estimates. Particular emphasis is given to the effects of energy integration and equipment sharing separately for both conversion steps. The process simulation work is done using Aspen Plus® chemical process modelling software. The analysis builds on the author’s prior work with simulation of pressurised oxygen-gasification of biomass and detailed evaluation of large-scale biomass-to-liquids processes.

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    Biobased materials and fuels via methanol – The role of integration

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    Light olefins are the basic building blocks of petrochemical industry. They are produced by steam cracking of hydrocarbon feedstocks like naphtha or natural gas / shale gas liquids. Rising prices of petroleum feedstocks, together with demand for bio-based feeds on selected markets, have driven technology development to unlock production routes to olefins from alternative feedstocks such as ethanol and methanol. As methanol can be produced from any gasifiable carbonaceous source, including lignocellulosic biomass, the Methanol-to-Olefins route opens up a possibility to produce 100 % bio-based plastics and chemicals. Large-scale production of synthetic biofuels like methanol requires a fairly complex process that combines elements from power plants, refineries and woodprocessing industry. When such plants are built, it is advisable to integrate them with existing processes to minimise capital footprint and to ensure the efficient utilisation and exchange of heat, steam and byproducts. This work evaluates the thermodynamic and economic potential of a two-step production of olefins from biomass via methanol. The production of biomethanol takes place in the vicinity of affordable biomass resources in a plant that is energy integrated with a woodprocessing industry or a district heating network. The subsequent conversion of methanol to olefins takes place at a refinery site where separation columns of an existing ethene plant are utilised to partly fractionate the MTO crude. This study includes conceptual design, process description, mass and energy balances and production cost estimates. Particular emphasis is given to the effects of energy integration and equipment sharing separately for both conversion steps. The process simulation work is done using Aspen Plus® chemical process modelling software. The analysis builds on the author’s prior work with simulation of pressurised oxygen-gasification of biomass and detailed evaluation of large-scale biomass-to-liquids processes.

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    Attribution Non-Commercial (BY-NC)
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    29 tayangan41 halaman

    Biobased Materials and Fuels Via Methanol - The Role of Integration

    Diunggah oleh

    ilkkahannula
    Light olefins are the basic building blocks of petrochemical industry. They are produced by steam cracking of hydrocarbon feedstocks like naphtha or natural gas / shale gas liquids. Rising prices of petroleum feedstocks, together with demand for bio-based feeds on selected markets, have driven technology development to unlock production routes to olefins from alternative feedstocks such as ethanol and methanol. As methanol can be produced from any gasifiable carbonaceous source, including lignocellulosic biomass, the Methanol-to-Olefins route opens up a possibility to produce 100 % bio-based plastics and chemicals. Large-scale production of synthetic biofuels like methanol requires a fairly complex process that combines elements from power plants, refineries and woodprocessing industry. When such plants are built, it is advisable to integrate them with existing processes to minimise capital footprint and to ensure the efficient utilisation and exchange of heat, steam and byproducts. This work evaluates the thermodynamic and economic potential of a two-step production of olefins from biomass via methanol. The production of biomethanol takes place in the vicinity of affordable biomass resources in a plant that is energy integrated with a woodprocessing industry or a district heating network. The subsequent conversion of methanol to olefins takes place at a refinery site where separation columns of an existing ethene plant are utilised to partly fractionate the MTO crude. This study includes conceptual design, process description, mass and energy balances and production cost estimates. Particular emphasis is given to the effects of energy integration and equipment sharing separately for both conversion steps. The process simulation work is done using Aspen Plus® chemical process modelling software. The analysis builds on the author’s prior work with simulation of pressurised oxygen-gasification of biomass and detailed evaluation of large-scale biomass-to-liquids processes.

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    Attribution Non-Commercial (BY-NC)
    Unduh sebagai PDF, TXT atau baca online dari Scribd
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    dari 41

    Biobased materials and fuels via methanol The role of integration

    Joint Task 33 & IETS workshop at Gteborg, Nov2013 Ilkka Hannula VTT Technical Research Centre of Finland

    21/11/2013

    Gasification and Gas Cleaning Process


    - developed and tested at VTT on 0.5 MW scale -ca. 4000 operating hours with different wood residues

    Gasification: 4 bar, 850C Filtration: 550C Reforming: 950C, ~95 % CH4 conv.

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    Levelised production cost estimates*


    300 MW biomass @ 17 /MWh, 0.12 ann. factor Electricity 50 /MWh, DH 30 /MWh@5500 h/a Total Capital Investment estimates: 331-446 M

    Mature technology No investment support No CO2 credits No tax assumptions

    Gasoline @150$/bbl

    Before 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

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    Levelised production cost estimates*


    300 MW biomass @ 17 /MWh, 0.12 ann. factor Electricity 50 /MWh, DH 30 /MWh@5500 h/a Total Capital Investment estimates: 331-446 M

    Mature technology No investment support No CO2 credits No tax assumptions

    Gasoline @150$/bbl

    Before tax, incl. refining margin, 1=1.33$ (2010)

    Transportation fuels currently cost around 750 /tonne

    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

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    912 1243 /ton

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    Light Olefins
    Olefins 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- and fluoromonomers 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)

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    Olefin routes
    Gas LNG sideproduct Refining sideproduct Condensate Dehydro Oil Naptha

    Steam Cracker

    HDO Fischer Tropsh Biomass Gasification Methanol Synthesis Fermentation MTO Methathesis Bio Naphta Propylene

    Ethanol

    Ethylene

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    The proposed 2-step concept


    - MTO was first developed by Mobil in the mid-1980s as a spin-off to MTG in New Zealand. - Technology went unused until the mid-1990s when UOP & Norsk Hydro 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 a similar process (DMTO).

    Methanol-to-Olefins

    Possibilities for two types of integration examined: - Heat integration - Equipment sharing

    - 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 exclusive production process since 1960s - 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 fuels through the conversion to dimethyl ether (DME) or gasoline (MTG). - In 2011 the annual consumption of methanol amounted to 47 million tons

    Biomass-to-Methanol

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    10

    Biomass to Methanol
    - CFB gasification with O2 at 4 bar and 850 C. - Catalytic reforming of tars and hydrocarbons - Rectisol acid gas removal - Highly selective (99.9 %) Cu-ZnOAl2O3 or Cr2O3 based commercial methanol catalysts - Synthesis conditions 250 C and 80 bar. - Final purification by conventional distillation

    Simplified layout of the methanol synthesis loop, product recovery and distillation section.

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    11

    Thermal efficiency to methanol and by-products

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    12

    EQUIPMENT COST ESTIMATES Auxiliary equipment Site preparation Oxygen production Feedstock pretreatment Gasification island Gasification Hot-gas cleaning CO shift Syngas cooling Compression Acid gas removal Power island HRSG (GI + AUX) Aux. boiler + fluegas treatm. Steam turbine + condenser Methanol synthesis Syngas compresssor Synthesis loop Distillation (minimal) Distillation (chemical-grade) SUM EQUIPMENT CHANGE

    Base Case

    Equipment Sharing

    Minimum Distillation

    36 8 18 10 75 24 19 2 4 5 21 14 6 3 4 26 2 17 0 8
    152

    36 8 18 10 75 24 19 2 4 5 21 6 6 0 0 26 2 17 0 8
    144 -4.8 %

    36 8 18 10 75 24 19 2 4 5 21 6 6 0 0 21 2 17 3 0
    139 -3.6 % -8.2 %

    Equipment cost estimates for a plant processing 150 MW of biomasss

    Equipment sharing possibilities

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    13

    ESTIMATES FOR 150 MWbiom PLANT TOTAL OVERNIGHT CAP. COST TOTAL CAP. INV. (at 5% interest) CHANGE

    BaseCase 215 226

    w/ Eq. Sharing w/ Min. Dstl. 206 199 217 209 -4.0 % -3.7 % -7.5 %

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    Methanol to Light Olefins


    UOP/Hydros 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 required

    Fast-fluidised MTO reactor

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    Product integration

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    Olefin boosting

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    MTO integration with an Ethene Plant

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    UOP/Hydros Methanol-to-Olefins process


    COMPRESSOR COMPRESSOR PHASE SEPARATOR REACTOR & REGENERATOR Fluegas QUENCH CAUSTIC WASH C2H2 REACTOR Tail gas DE-C1 Ethene C2 SPLITTER Propene C3 SPLITTER Propane Ethane

    DE-C2

    Methanol crude Unconv. methanol WATER STRIPPER Waste water Air

    CONDENSATE STRIPPER

    DRYER C4+ stream

    DE-C3

    C4+

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    MTO crude

    Kilpilahti Ethene Plant Source: ljyst muoveihin (1992), Neste Oyj.

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    25

    UOP/Hydros Methanol-to-Olefins process


    COMPRESSOR COMPRESSOR PHASE SEPARATOR REACTOR & REGENERATOR Fluegas QUENCH CAUSTIC WASH C2H2 REACTOR Tail gas DE-C1 Ethene C2 SPLITTER Propene C3 SPLITTER Propane Ethane

    DE-C2

    Methanol crude Unconv. methanol WATER STRIPPER Waste water Air

    CONDENSATE STRIPPER

    DRYER C4+ stream

    DE-C3

    C4+

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    COMPRESSOR PHASE SEPARATOR REACTOR & REGENERATOR Fluegas MTO crude QUENCH

    Methanol crude Unconv. methanol WATER STRIPPER Waste water Air

    CONDENSATE STRIPPER

    C4+ stream

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    Separations when integrated to a refinery MTO CONVERSION


    COMPRESSOR PHASE SEPARATOR REACTOR & REGENERATOR Fluegas MTO crude QUENCH CAUSTIC WASH DRYING COOLING Tail gas C2H2 REACTOR DE-C1 Ethene C2 SPLITTER Ethane C2+ Methanol crude Unconv. methanol WATER STRIPPER Waste water C4+ Air PRE DE-C1 CONDENSATE STRIPPER Propene DE-C2 C3 SPLITTER Propane DE-C3 C4 C4 SPLITTER C5+

    ETHENE PLANT

    H2

    COMPRESSOR C4+ stream

    C3+

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    At what scale?

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    Case Example: Crackers of the Kilpilahti Refinery in Finland

    Naphtha replacement: 2.6 kg/kg MeOH/naphtha 10 t/h naphtha = 208 kton/a of methanol

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    Investment cost estimates for MTO

    ~53 % decrease

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    Investment cost estimates for MTO


    20 % decrease

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    Production cost estimates

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    Naphtha 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 requirement

    Production cost estimates for such plant:

    /MWh Base Case 71 DH 70 w/ Eq. Sharing 68 w/ Min. Dstl. 67

    /GJ 19.8 19.4 18.9 18.5

    /tonne 395 386 376 369

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    Assumed product prices

    Prices Electricity Tailgas (H2) Ethane Propane LPG C4+ Ethene Propene Gasoline Distillate

    /MWh /tonne /tonne /tonne /tonne /tonne /tonne /tonne /tonne /tonne

    Base Case 50 1200 332 332 332 600 829 995 750 700

    Double Counting 50 1200 332 332 332 1120 829 995 1400 1300

    80% of gasoline price

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    Light olefins 1100 /tonne

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    Assumed product prices

    Prices Electricity Tailgas (H2) Ethane Propane LPG C4+ Ethene Propene Gasoline Distillate

    /MWh /tonne /tonne /tonne /tonne /tonne /tonne /tonne /tonne /tonne

    Base Case 50 1200 332 332 332 600 829 995 750 700

    Double Counting 50 1200 332 332 332 1120 829 995 1400 1300

    80% of gasoline price

    Double counting ~120 /MWh?

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    Light olefins 1100 /tonne

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    Summary 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 heat integration (depending on the produced fuel and steam cycle design) 7.5 % decrease in TCI can be achieved via equipment sharing Combined effect to the cost of methanol: 395 ---> 369 /tonne (6.6 % decrease)

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    Summary 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 lowest production cost Double Counting incentive makes Base Case MTO slightly more attractive 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 light olefins.

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    Thank you for your attention!


    LinkedIn: ihannulaprofile twitter: @ilkkahannula

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