Thermochemical Biorefineries based on DME as platform …grupo.us.es/bioenergia/templates/jubilee/pdf/Thesis presentation Pedro Haro.pdfThermochemical Biorefineries based on DME as

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

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

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

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

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

Pedro Haro

Doctoral Thesis

6

Selected route: DME hydrocarbonylation

Seville

June 24th 2013


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)

Pedro Haro

Doctoral Thesis

7

Seville

June 24th 2013


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 HYDROCARBONYLATIONPRODUCT

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

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


WaterAirOilHP steamLP steam

Biomass MillingDryerGasification

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

WPurge

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

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


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

Pedro Haro

Doctoral Thesis

10

Conclusions

Seville

June 24th 2013


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)

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 of different configurations (concepts)

regarding the mix of products and the conditioning of

the syngas

Paper 5

Pedro Haro

Doctoral Thesis

12

Seville

June 24th 2013


Process flowchart of the concepts of thermochemical biorefinery

Description of the concepts

Methyl

acetate

Powergeneration

DME synthesis

DME conversion

Syngas clean-up and conditioning

GasificationFeedstock

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

powerEthanol

PRODUCTS

Biomass

System boundaries

Steamreformer

(SR)

Paper 5

Pedro Haro

Doctoral Thesis

13

Seville

June 24th 2013

Results and discussion


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

0

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

Pedro Haro

Doctoral Thesis

14

Seville

June 24th 2013



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

of power

Tar reforming

and CO2 removal

Paper 4

Pedro Haro

Doctoral Thesis

15

Seville

June 24th 2013



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

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


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)


Assessment of sustainability (new methodology) and

study of the potential impact on profitability

(based on Directive 2009/28/EC)

Pedro Haro

Doctoral Thesis

18

Seville

June 24th 2013

European methodology


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

Pedro Haro

Doctoral Thesis

19

Seville

June 24th 2013

European methodology


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

Pedro Haro

Doctoral Thesis

20

Seville

June 24th 2013

Results: final use and extra saving


0%

50%

100%

150%

200%

250%

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

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)


Pedro Haro

Doctoral Thesis

22

Seville

June 24th 2013

0%

5%

10%

15%

20%

25%

30%

35%

0 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)


Pedro Haro

Doctoral Thesis

23

Seville

June 24th 2013

Co-feeding results in the largest profitability

when CO2 credit < 20 €/tonne


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 %

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


Paper 7

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

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 Olefins2.1.10

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

EtOHDMEMeOH

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

Pedro Haro

Doctoral Thesis

27

Seville

June 24th 2013

In 2012 I visited the Karlsruhe Institute of Technology


Paper 6

DME synthesis

reactor

P= 35 bar

T= 30 ºC

P= 10 bar

T= 200 ºC

P= 35 bar

SyngasGasoline synthesis

reactorT= 340 ºC

P= 33 bar

Degassing

column

Fuel gas

Decanter

To WWT

Fractionation

column

Fractionation

columnT= 35 ºC

P= 1 bar

P= 2 bar

Fuel gas

Gasoline

Isomerization

reactorT= 30 ºC

P= 32 bar

Gas-liquid-

separator

Fuel gas

P= 32 bar

Gasoline

PSAH2 to isomerization

reactor

H2

DME synthesis

reactor

P= 35 bar

T= 200 ºC

P= 35 bar

SyngasOlefins synthesis

reactorT= 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

columnP= 18 bar

Ethylene

P= 25 bar

Fuel gas

Fractionation

columnP= 16 bar

LPG

Fractionation

column

LPG

Fractionation

columnP= 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

SyngasOlefins synthesis

reactorT= 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

columnP= 18 bar

EthyleneFuel gas

Fractionation

columnP= 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,

olefins and co-production of synthetic gasoline and ethylene

Pedro Haro

Doctoral Thesis

28

Seville

June 24th 2013



Paper 6

Paper 3

System

boundaries

Gasification EthyleneBiomassEthanol

dehydration

Ethanol

synthesis(directly from syngas)

CO2

Villanueva et al. [6]

Gasification EthyleneBiomassEthanol

dehydration

Ethanol

synthesis(via DME)

CO2

Haro et al. [7]

Fermentation(commercial process)

EthyleneBiomassEthanol

dehydration

EU

USA

Brazil

GasificationEthylene,

Propylene &

LPG

Biomass DME-to-olefinsPyrolysis

CO2 CO2

Haro et al. [8]

CASE STUDY 1

CASE STUDY 2

CASE STUDY 3

CASE STUDY 4

CASE STUDY 5

Enzymatic

hydrolysis

EthyleneBiomassEthanol

dehydration

Fermentation

Kazi et al. [10]

Fornell et al. [11]

Gasification Fermentation

Coskata

CO2

CO2




Assessment of the production of ethylene using DME and/or

ethanol as a platform chemical

Pedro Haro

Doctoral Thesis

29

Seville

June 24th 2013



Paper 6

Paper 3




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

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


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)

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)

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

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

Pedro Haro

Doctoral Thesis

Thank you for your attention!

¡Gracias por vuestra atención!

Seville

June 24th 2013

Documents

Thermochemical Biorefineries based on DME as platform …grupo.us.es/bioenergia/templates/jubilee/pdf/Thesis presentation Pedro Haro.pdfThermochemical Biorefineries based on DME as