Conceptual design and technoeconomic assessment Pedro Haro - PowerPoint PPT Presentation

Thermochemical Biorefineries based on DME as platform chemical Conceptual design and technoeconomic assessment Pedro Haro Bioenergy Group Chemical and Environmental Engineering Department Seville, June 24 th 2013

Contents Objective History and context Indirect synthesis of ethanol Multiproduction plants using DME Sustainability in multiproduction plants Activities during the visit to KIT Final Conclusions Further work 2 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Objective This thesis aims to propose new concepts of thermochemical biorefineries using DME as a platform chemical and to assess if they are feasible, profitable and sustainable Air/ CO 2 Oxygen (for sequestration) A thermochemical biorefinery is a Fuel(s) THERMOCHEMICAL Feedstock Chemical(s) facility, which processes biomass by BIOREFINERY Material(s) means of pyrolysis and/or gasification to produce fuels, Heat Power chemicals and services Net Heat Net Power Import/export Import/export 3 Pedro Haro Seville Doctoral Thesis June 24 th 2013

History and context In 2009 , the research activity of the Bioenergy Group (process design) was focused on the production of ethanol via thermochemical processing of biomass: DIRECT SYNTHESIS The study of the direct synthesis showed that the process is feasible . However, (just) profitable and there is a high risk , since large investment 400 M € (500 MW th ) and market uncertainties 4 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Indirect synthesis of Ethanol  Objective: improve profitability INDIRECT SYNTHESIS  Search of alternative routes that overcome main limitation of direct synthesis: low selectivity to ethanol  The screening of literature showed all routes use homogeneous catalysts and operate at high pressure (>50 bar)  Acetic acid esterification ( Enerkem ): complex  In process to be commercial (homogeneous catalyst)  DME hydrocarbonylation  Recently discovered (2009, Tsubaki)  Heterogeneous catalyst 5 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Indirect synthesis of Ethanol  Selected route: DME hydrocarbonylation Platform chemical : DME CO Reaction steps: syngas-to-methanol (commercial) CH 3 OCH 3 Eq. (15) H 2 O (DME) methanol-to-DME (commercial) DME-to-ethanol (in progress) CH 3 COOCH 3 (methyl acetate) two catalysts Eq. (4) 220ºC, 15 bar H 2 CH 3 OH Methanol is converted into DME Eq. (12) Eq. (1) GLOBAL REACTION: CO, H 2 (syngas) 4 H 2 + 2 CO  C 2 H 5 OH + H 2 O C 2 H 5 OH (same as in the direct route) 6 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Indirect synthesis of Ethanol  Process design ( i-Ethanol concept ) Paper 2 Methanol METHANOL DME SYNTHESIS SYNTHESIS Water PRODUCT Biomass FEEDSTOCK CLEAN-UP & SEPARATION GASIFICATION PRETREATMENT CONDITIONING Methyl Acetate DME Ethanol PRODUCT DME HYDROCARBONYLATION SEPARATION Main points in the design: • A large excess of CO is required ( CO/DME = 10:1 ) • Selectivity near 100% • No water-ethanol mixture (energy saving) • Less syngas recycle, milder operating conditions 7 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Indirect synthesis of Ethanol  Basis of modeling ( i-Ethanol concept ) Paper 2 Flue gas (CO 2 )  Process simulator: Aspen Plus Cleaning LP steam HP steam Oil Air Water  500 MW th of poplar chips Gasification Biomass Dryer Milling Cyclon HRSG OLGA Scrubber bed Sand & Sand Char Particles -Dust  i-CFB gasifier HRSG Combustor -NH 3 -Alkali Air &Tars Flue gas -HCl -Tars Ash LP steam  Conditioning of raw syngas Purge W Air Syngas to DME Flue gas Hydrocarbonylation (CO 2 )  steam reformer (SR) T=80 ºC Unreacted Syngas Purge Flue gas Combustor Air (CO 2 ) CW CW  Methanol synthesis Guard H 2 O G-L LO-CAT SMR LPMEOH Bed Removal Separation S S MP CO 2  LPMEOH TM Steam Syngas from SMR Unreacted Syngas Raw Methanol  DME synthesis CO 2 Amines Lights Purge  methanol dehydration (Toyo) CW Hydrocarbonylation G-L Stabilizer MeOH-EtOH Ethanol Reactor Separation Column Column  DME hydrocarbonylation Methyl Acetate Dehydration Raw DME Column Reactor Methanol  data from literature (Tsubaki) H 2 O Methanol 8 Process flowchart of the i-Ethanol concept Pedro Haro Seville Doctoral Thesis June 24 th 2013

Indirect synthesis of Ethanol  Results and comparison with the direct route ( i-Ethanol concept ) Paper 2 i-Ethanol Direct synthesis Biomass input (MW th, HHV ) 500 500 Feedstock price ($/d. tonne) 66 66 Energy efficiency (%, HHV) 46 34 Total capital investment (M$ 2010 ) 333 421 Operating cost (k$/MW EthOH ·year) 435 471 Minimum selling price ($/L) 0.56 0.71 [10% internal rate of return: IRR] Data for the direct synthesis taken from BEGUS publications Both cases share the methodology and have been designed as energy self-sufficient 9 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Indirect synthesis of Ethanol  Conclusions  The indirect synthesis has higher efficiency and higher profitability than direct synthesis  However, there is still a risk for the investment  In order to reduce it: diversification of revenue  multiproduction  Regarding the DME hydrocarbonylation route there are potential co-products: DME, methyl acetate (high-value) 10 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Multiproduction plants using a platform chemical  Design and assessment of 12 concepts of thermochemical biorefineries Paper 5  Objective: confirm the potential of multiproduction plants  How?  Assessment of different configurations (concepts) regarding the mix of products and the conditioning of the syngas Co-products Uses Value € /GJ DME 0.7 $/L 22 substitute of diesel, LPG; substitute of naphtha (chemical) Ethanol 0.6 $/L 24 substitute of gasoline; production of chemicals (butanol, ethylene) Methyl Acetate 1.7 $/L 65 solvent; production of plastics Hydrogen 1 $/kg 6 production of electricity; use in transport; refineries 11 Electricity 5 c$/kWh - - Pedro Haro Seville Doctoral Thesis June 24 th 2013

Multiproduction plants using a platform chemical  Description of the concepts Paper 5 System boundaries Process flowchart of the concepts of thermochemical biorefinery Feedstock Syngas clean-up and DME DME Power Gasification pretreatment conditioning conversion synthesis generation CO 2 Tar reformer CO 2 & H 2 removal (TR) DME DME Hydrocarbony -lation Autothermal Biomass DME Dryer & Power Island reformer iCFBG synthesis Milling (ATR) DME Carbonylation DME Steam reformer (SR) Methyl PRODUCTS Electric H 2 Ethanol DME 12 acetate power Pedro Haro Seville Doctoral Thesis June 24 th 2013

Multiproduction plants using a platform chemical  Results and discussion Paper 5 275 50.24% 49.07% 250 42.96% 42.97% 43.55% 225 51 42.15% 42.08% 40.02% 39.21% 39.16% 39.14% 200 34.89% 51 175 157 54 54 111 Ethanol 150 157 MA MW 118 125 192 111 DME 192 187 189 100 117 H2 32 118 75 133 Electricity 77 50 32 77 77 61 25 42 5 32 23 24 17 18 0 2 7 8 9 -1 -11 -25 SR-01 SR-02 SR-03 ATR-01ATR-02ATR-03 TR-01 TR-02 TR-03 TR-04 TR-05 TR-06 Energy efficiency of the concepts 13 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Multiproduction plants using a platform chemical 70% Paper 4  Results and discussion 60% 50% _( ℎ , ) Prod 40% Tar reforming Max. production and CO 2 removal of power main product 30% carbono syngas: Prod 20% syngas: P+S 10% 0% 0% 10% 20% 30% 40% 50% 60% 70% 80% 14 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Multiproduction plants using a platform chemical  Results and discussion Paper 5 Cases co-producing methyl acetate 28.74% 30.00% 23.90% 25.00% 23.34% 20.28% 20.00% IRR 15.00% 12.06% 10.44% 9.17% 9.85% 10.00% 7.59% 5.41% 4.57% 5.00% 1.38% 0.00% SR-01 SR-02 SR-03 ATR-01 ATR-02 ATR-03 TR-01 TR-02 TR-03 TR-04 TR-05 TR-06 15 IRR of the concepts Pedro Haro Seville Doctoral Thesis June 24 th 2013

Multiproduction plants using a platform chemical  Conclusions  The concepts co-producing methyl acetate (high-value product) achieve the highest profitability  The energy efficiency of the concepts is similar to BTL/G processes (40%)  However, a sustainability assessment is necessary 16 Pedro Haro Seville Doctoral Thesis June 24 th 2013

Sustainability in multiproduction plants  Sustainability assessment in thermochemical biorefineries  The use of biomass does not necessarily involve sustainability  The co-production of products different to fuels requires new tools  Impact of sustainability on the profitability  The incorporation of BECCS (sale of CO 2 credits)  Achievement of a larger saving than the required (sale of CO 2 credits) Assessment of sustainability (new methodology) and study of the potential impact on profitability (based on Directive 2009/28/EC) 17 Pedro Haro Seville Doctoral Thesis June 24 th 2013