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Conceptual design and technoeconomic assessment Pedro Haro - - PowerPoint PPT Presentation

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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

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Thermochemical Biorefineries based on DME as platform chemical

Conceptual design and technoeconomic assessment

Seville, June 24th 2013

Pedro Haro

Bioenergy Group

Chemical and Environmental Engineering Department

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Contents

Pedro Haro Doctoral Thesis Seville June 24th 2013 2

Objective History and context Indirect synthesis of ethanol Activities during the visit to KIT Final Conclusions Multiproduction plants using DME Sustainability in multiproduction plants Further work

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Objective

Pedro Haro Doctoral Thesis 3 Seville June 24th 2013

THERMOCHEMICAL BIOREFINERY

Air/ Oxygen CO2

(for sequestration)

Feedstock Fuel(s) Material(s)

Power

Net Power Import/export Chemical(s) Net Heat Import/export

Heat

A thermochemical biorefinery is a facility, which processes biomass by means of pyrolysis and/or gasification to produce fuels, chemicals and services 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

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History and context

Pedro Haro Doctoral Thesis 4 Seville June 24th 2013

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 MWth) and market uncertainties

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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

Pedro Haro Doctoral Thesis 5 Seville June 24th 2013

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Pedro Haro Doctoral Thesis 6

 Selected route: DME hydrocarbonylation

Seville June 24th 2013

Indirect synthesis of Ethanol

CH3OCH3

(DME)

CH3COOCH3 (methyl acetate) CO CH3OH C2H5OH H2 CO, H2

(syngas)

H2O

  • Eq. (1)
  • Eq. (4)
  • Eq. (15)
  • Eq. (12)

Platform chemical: DME Reaction steps:

syngas-to-methanol (commercial) methanol-to-DME (commercial) DME-to-ethanol (in progress) two catalysts 220ºC, 15 bar Methanol is converted into DME

GLOBAL REACTION: 4 H2 + 2 CO  C2H5OH + H2O (same as in the direct route)

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SLIDE 7

Pedro Haro Doctoral Thesis 7 Seville June 24th 2013

Indirect synthesis of Ethanol

 Process design (i-Ethanol concept)

Paper 2

Methyl Acetate

FEEDSTOCK PRETREATMENT GASIFICATION METHANOL SYNTHESIS PRODUCT SEPARATION DME SYNTHESIS CLEAN-UP & CONDITIONING DME Water

Methanol

Ethanol

Biomass

DME HYDROCARBONYLATION

PRODUCT 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
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Pedro Haro Doctoral Thesis 8

 Basis of modeling (i-Ethanol concept)

 Process simulator: Aspen Plus  500 MWth of poplar chips  i-CFB gasifier  Conditioning of raw syngas  steam reformer (SR)  Methanol synthesis  LPMEOHTM  DME synthesis  methanol dehydration (Toyo)  DME hydrocarbonylation  data from literature (Tsubaki)

Seville June 24th 2013

Indirect synthesis of Ethanol

Water Air Oil HP steam LP steam Biomass Milling Dryer Gasification bed Combustor Sand Sand & Char Ash Flue gas Flue gas (CO2) Cleaning Cyclon Particles HRSG OLGA
  • Dust
  • Alkali
  • Tars
Scrubber Air &Tars
  • NH3
  • HCl
HRSG LP steam SMR LPMEOH Raw Methanol LO-CAT S CW Guard Bed S Combustor MP Steam CO2 Air CW G-L Separation Purge Air T=80 ºC W Purge Unreacted Syngas Syngas to DME Hydrocarbonylation H2O Removal Hydrocarbonylation Reactor DME Column Ethanol Methanol Amines CO2 CW G-L Separation Dehydration Reactor H2O Purge Unreacted Syngas Syngas from SMR Stabilizer Column MeOH-EtOH Column Methyl Acetate Lights Raw Methanol Flue gas (CO2) Flue gas (CO2)

Process flowchart of the i-Ethanol concept

Paper 2

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SLIDE 9

Pedro Haro Doctoral Thesis 9

 Results and comparison with the direct route (i-Ethanol concept) Both cases share the methodology and have been designed as energy self-sufficient

Seville June 24th 2013

Indirect synthesis of Ethanol

i-Ethanol Direct synthesis Biomass input (MWth, HHV) 500 500 Feedstock price ($/d. tonne) 66 66 Energy efficiency (%, HHV) 46 34 Total capital investment (M$2010) 333 421 Operating cost (k$/MWEthOH·year) 435 471 Minimum selling price ($/L) [10% internal rate of return: IRR] 0.56 0.71

Data for the direct synthesis taken from BEGUS publications

Paper 2

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Pedro Haro Doctoral Thesis 10

 Conclusions

Seville June 24th 2013

Indirect synthesis of Ethanol

 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)

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Pedro Haro Doctoral Thesis 11 Seville June 24th 2013

 Design and assessment of 12 concepts of thermochemical biorefineries

Multiproduction plants using a platform chemical

Co-products Uses Value €/GJ DME

substitute of diesel, LPG; substitute of naphtha (chemical)

0.7 $/L 22 Ethanol

substitute of gasoline; production of chemicals (butanol, ethylene)

0.6 $/L 24 Methyl Acetate

solvent; production of plastics

1.7 $/L 65 Hydrogen

production of electricity; use in transport; refineries

1 $/kg 6 Electricity

  • 5 c$/kWh
  •  Objective: confirm the potential of multiproduction plants

 How?  Assessment

  • f

different configurations (concepts) regarding the mix of products and the conditioning of the syngas

Paper 5

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Pedro Haro Doctoral Thesis 12 Seville June 24th 2013

Multiproduction plants using a platform chemical

Process flowchart of the concepts of thermochemical biorefinery

 Description of the concepts

Methyl acetate

Power generation DME synthesis DME conversion Syngas clean-up and conditioning Gasification Feedstock pretreatment

Dryer & Milling iCFBG Tar reformer (TR) Autothermal reformer (ATR) CO2 & H2 removal DME Hydrocarbony

  • lation

DME Carbonylation DME synthesis Power Island

H2

CO2 DME DME

DME Electric power Ethanol

PRODUCTS Biomass

System boundaries

Steam reformer (SR)

Paper 5

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Pedro Haro Doctoral Thesis 13 Seville June 24th 2013

 Results and discussion

Multiproduction plants using a platform chemical

Paper 5 23 2 24 7 8 9 61 18 32

  • 11
  • 1

42 77 77 77 17 118 5 133 32 32 118 117 54 54 51 51 192 192 189 187 157 157 111 111 42.97% 42.15% 39.16% 39.21% 40.02% 39.14% 43.55% 50.24% 34.89% 42.96% 49.07% 42.08%

  • 25

25 50 75 100 125 150 175 200 225 250 275 SR-01 SR-02 SR-03 ATR-01ATR-02ATR-03 TR-01 TR-02 TR-03 TR-04 TR-05 TR-06

MW

Ethanol MA DME H2 Electricity

Energy efficiency of the concepts

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Pedro Haro Doctoral Thesis 14 Seville June 24th 2013

 Results and discussion

Multiproduction plants using a platform chemical

0% 10% 20% 30% 40% 50% 60% 70% 0% 10% 20% 30% 40% 50% 60% 70% 80% _( ℎ, ) Prod main product carbono syngas: Prod syngas: P+S

  • Max. production
  • f power

Tar reforming and CO2 removal

Paper 4

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Pedro Haro Doctoral Thesis 15 Seville June 24th 2013

 Results and discussion

Multiproduction plants using a platform chemical

Paper 5

10.44% 12.06% 23.34% 9.17% 9.85% 28.74% 5.41% 7.59% 1.38% 4.57% 23.90% 20.28% 0.00% 5.00% 10.00% 15.00% 20.00% 25.00% 30.00% SR-01 SR-02 SR-03 ATR-01 ATR-02 ATR-03 TR-01 TR-02 TR-03 TR-04 TR-05 TR-06

IRR

Cases co-producing methyl acetate

IRR of the concepts

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Pedro Haro Doctoral Thesis 16 Seville June 24th 2013

 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

Multiproduction plants using a platform chemical

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Pedro Haro Doctoral Thesis 17 Seville June 24th 2013

 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 CO2 credits)  Achievement of a larger saving than the required (sale of CO2 credits)

Sustainability in multiproduction plants

Assessment of sustainability (new methodology) and study of the potential impact on profitability (based on Directive 2009/28/EC)

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Pedro Haro Doctoral Thesis 18 Seville June 24th 2013

 European methodology

Sustainability in multiproduction plants

Paper 7

 E = eec + el + ep + etd + eu – esca – eccs – eccr – eee (g CO2 equivalent / MJ of biofuel)  Allocation co-products (energy content): Em = E’ + sum[xi·(etd,i + eu,i)]  Modification of sustainability methodology  The final use (eu,i) is relevant  Fuels have a net emission in their final use  Retention of carbon in chemicals (assumed as 50% eq. CO2 content)  Extra saving

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Pedro Haro Doctoral Thesis 19 Seville June 24th 2013

 European methodology

Sustainability in multiproduction plants

Paper 7

 E = eec + el + ep + etd + eu – esca – eccs – eccr – eee (g CO2 equivalent / MJ of biofuel)  Allocation co-products (energy content): Em = E’ + sum[xi·(etd,i + eu,i)]  Modification of sustainability methodology  The final use (eu,i) is relevant  Fuels have a net emission in their final use  Retention of carbon in chemicals (assumed as 50% eq. CO2 content)  Extra saving  Extra-avoided emissions: 44.3 t/h of equivalent CO2 Example: TR-01 concept Emission factor (fossil) 83.8 g CO2 equivalent per MJ of total products Limit of emissions (60% saving) 33.5 Emissions cradle-to-grave 9.0 Sequestration or retention of CO2 30.0 Saving 125% Extra saving (w/o seq. or retention of CO2) 24.5 Extra saving 54.5

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Pedro Haro Doctoral Thesis 20 Seville June 24th 2013

 Results: final use and extra saving

Sustainability in multiproduction plants

0% 50% 100% 150% 200% SR-01 SR-02 SR-03 ATR-01ATR-02ATR-03 TR-01 TR-02 TR-03 TR-04 TR-05 TR-06

  • max. transportation FUELS
  • max. Other FUELS
  • max. CHEMICALS

eu = 0 / e_no comb = 0 (Directive)

60% (EU, 2018)

  • Max. transportation fuels
  • Max. bio-chemicals
  • Max. other fuels

Directive

 Directive (EU)  Final use:  As transportation fuels  As chemicals Saving of GHG emissions (%)

BECCS

Paper 7

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Pedro Haro Doctoral Thesis 21 Seville June 24th 2013

 BECCS: results of incorporation to TR concepts  Cost of sequestration: 20 – 30 €/tonne  Conventional power plants: 100 – 200 €/tonne  All concepts have an extra saving of GHG emissions  Impact of sustainability on profitability  Sale of CO2 credits (extra-avoided emissions)  Co-feeding of fossil fuels (natural gas, coal)

Sustainability in multiproduction plants

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Pedro Haro Doctoral Thesis 22 Seville June 24th 2013

0% 5% 10% 15% 20% 25% 30% 35% 5 10 15 20 25 30 35 40 45 50 55 60 65 IRR CO2 credit (€/t)

SR-01 SR-02 SR-03 ATR-01 ATR-02 ATR-03 TR-01 TR-02 TR-03 TR-04 TR-05 TR-06

Transportation and sequestration costs Base case [1]

Sale of CO2 credits (extra-avoided emissions)

Sustainability in multiproduction plants

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Pedro Haro Doctoral Thesis 23 Seville June 24th 2013

Co-feeding results in the largest profitability when CO2 credit < 20 €/tonne Sustainability in multiproduction plants Co-feeding of fossil fuels: SR-01 Extra saving 25.2 g/MJ Co-feeding (coal) 49 MW Increment of IRR 10.44  11.24 %

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Pedro Haro Doctoral Thesis 24 Seville June 24th 2013

 Conclusions  All concepts of thermochemical biorefinery using DME are sustainable (even using European regulation)  Chemicals are not combusted  retention of carbon  A saving larger than 100% could be achieved if chemicals are co- produced and BECCS incorporated  The economic impact is positive due to the large GHG saving

Sustainability in multiproduction plants

Paper 7

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Pedro Haro Doctoral Thesis 25 Seville June 24th 2013

 Up to now the results have shown that:  Multiproduction is interesting in order to reduce the risk (diversification of revenue) and enhances profitability  Hence, a review of other platform chemicals and indirect routes will result in new options for the assessment of multiproduction plants

Thermochemical biorefineries with multiproduction

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Identification of chemical routes using a platform chemical

Pedro Haro Doctoral Thesis 26

 Platform chemicals (from syngas) for thermochemical biorefineries

Seville June 24th 2013

CO, H2 (syngas)

AcOH 2.1.2 2.1 FT, H2, SNG 2.1.4 Methyl Acetate Gasoline Olefins 2.1.10 2.1.8 2.1.9 Ac2O 2.1.6 2.1.7 Diesel Jet Fuel Ethyl Acetate 2.1.7 2.2.4 ButOH EtOH 2.1

EtOH DME MeOH

Chemicals

 Methanol, DME and Ethanol  Methanol and DME are mostly equivalent  The routes are complex (several reaction steps)  MTG and MTO are commercial processes, although using fossil fuels

Paper 1

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Pedro Haro Doctoral Thesis 27 Seville June 24th 2013

 In 2012 I visited the Karlsruhe Institute of Technology

Activities during the visit to KIT

Paper 6

DME synthesis reactor P= 35 bar T= 30 ºC P= 10 bar T= 200 ºC P= 35 bar Syngas Gasoline synthesis reactor T= 340 ºC P= 33 bar Degassing column Fuel gas Decanter To WWT Fractionation column Fractionation column T= 35 ºC P= 1 bar P= 2 bar Fuel gas Gasoline Isomerization reactor T= 30 ºC P= 32 bar Gas-liquid- separator Fuel gas P= 32 bar Gasoline PSA H2 to isomerization reactor H2 DME synthesis reactor P= 35 bar T= 200 ºC P= 35 bar Syngas Olefins synthesis reactor T= 35 ºC P= 32 bar Destillation column Fuel gas P= 11 bar T= 450 ºC P= 4 bar Gas-liquid- separator To WWT P= 39 bar Gas-liquid- separator To WWT Rectisol unit CO2 available for sequestration Dewatering unit To WWT T= 0 ºC P= 30 bar Fractionation column Fractionation column P= 18 bar Ethylene P= 25 bar Fuel gas Fractionation column P= 16 bar LPG Fractionation column LPG Fractionation column P= 22 bar LPG Propylene Gasoline reactor T= 40 ºC P= 1 bar Gas-liquid- separator Fuel Gas Gasoline DME synthesis reactor P= 35 bar T= 200 ºC P= 35 bar Syngas Olefins synthesis reactor T= 35 ºC P= 32 bar Destillation column Fuel gas P= 11 bar T= 450 ºC P= 4 bar Gas-liquid- separator To WWT P= 39 bar Gas-liquid- separator To WWT Rectisol unit CO2 available for sequestration Dewatering unit To WWT T= 0 ºC P= 30 bar Fractionation column Fractionation column P= 18 bar Ethylene Fuel gas Fractionation column P= 16 bar Fuel gas T= 340 ºC P= 29 bar

 As a result of this collaboration:

 Modeling and assessment of the production of synthetic gasoline,

  • lefins and co-production of synthetic gasoline and ethylene
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SLIDE 28

Pedro Haro Doctoral Thesis 28 Seville June 24th 2013

 In 2012 I visited the Karlsruhe Institute of Technology

Activities during the visit to KIT

Paper 6 Paper 3

Gasification Ethylene Biomass Ethanol dehydration Ethanol synthesis (directly from syngas) CO2 Villanueva et al. [6] Gasification Ethylene Biomass Ethanol dehydration Ethanol synthesis (via DME) CO2 Haro et al. [7] Fermentation (commercial process) Ethylene Biomass Ethanol dehydration EU USA Brazil Gasification Ethylene, Propylene & LPG Biomass DME-to-olefins Pyrolysis CO2 CO2 Haro et al. [8]

CASE STUDY 1 CASE STUDY 2 CASE STUDY 3 CASE STUDY 4 CASE STUDY 5

Enzymatic hydrolysis Ethylene Biomass Ethanol dehydration Fermentation Kazi et al. [10] Fornell et al. [11] Gasification Fermentation Coskata CO2 CO2

 As a result of this collaboration:

 Modeling and assessment of the production of synthetic gasoline,

  • lefins and co-production of synthetic gasoline and ethylene

 Assessment of the production of ethylene using DME and/or ethanol as a platform chemical

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SLIDE 29

Pedro Haro Doctoral Thesis 29 Seville June 24th 2013

 In 2012 I visited the Karlsruhe Institute of Technology

Activities during the visit to KIT

Paper 6 Paper 3

 As a result of this collaboration:

 Modeling and assessment of the production of synthetic gasoline,

  • lefins and co-production of synthetic gasoline and ethylene

 Assessment of the production of ethylene using DME and/or ethanol as a platform chemical  Main differences with the previous work (BEGUS)  Different gasification technology (EF)  Different methodology and basis of design (e.g. 1175 MWth straw)  Hence, a comparison of the concepts is not possible

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Pedro Haro Doctoral Thesis 30 Seville June 24th 2013

 Results

 The production of synthetic gasoline and olefins (2 concepts) are not competitive  Production of ethylene using ethanol as a platform chemical  Competitive for sugar cane ethanol (Brazil)  Competitive for ethanol via thermochemical processing (indirect synthesis) Ethanol price 0.45 €/L

Papers 3 and 6

Activities during the visit to KIT

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SLIDE 31

Pedro Haro Doctoral Thesis 31

 20 concepts of thermochemical biorefineries (designed and assessed)

Seville June 24th 2013

Summary (thesis)

 Most concepts use DME as a platform chemical (17); the rest ethanol (3)  Multiproduction plants (14) are designed with regarding different reforming technologies and different co-products  The list of co-products includes: Fuels (transportation, heating), commodities (low-value) and chemicals (high-value)

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Pedro Haro Doctoral Thesis 32

 Identification of chemical routes using a platform chemical  Technoeconomic assessment of the indirect synthesis of ethanol  Technoeconomic assessment of the production of ethylene  Conceptual design of multiproduction plants  Technoeconomic assessment of multiproduction plants using DME  Assessment of sustainability and economic impact

Paper 1 Paper 2 Paper 3 Paper 4 Papers 5 and 6 Paper 7

Seville June 24th 2013

 Summary of the thesis (work done)

Summary (thesis)

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SLIDE 33

 Ethanol can be produced via the DME hydrocarbonylation route: cost-competitive and high efficient (0.56 $/L)  Multiproduction can reduce the risk of investment and improve profitability: especially high-value chemicals (IRR > 20 %)  Co-production of chemicals largely reduces the GHG emissions retention of carbon in final products  Extra saving in thermochemical biorefineries enhances profitability sale of CO2 credits or co-feeding  BECCS is competitive and enhances profitability lower cost of sequestration (20-30 €/tonne)

Pedro Haro Doctoral Thesis 33 Seville June 24th 2013

Final Conclusions

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Further work Experimental research of DME hydrocarbonylation route: 1.- Optimization of operating conditions 2.- Design of reactor (e.g. regeneration of catalyst) Assessment of other routes using DME and others platform chemicals and the screening of other high-value chemicals (currently used in petrochemical industry)

Pedro Haro Doctoral Thesis 34 Seville June 24th 2013

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Pedro Haro Doctoral Thesis

Thank you for your attention! ¡Gracias por vuestra atención!

Seville June 24th 2013