Green chemicals from biorefineries with glycerol as

Green chemicals from biorefineries with glycerol as feedstock:

a life cycle assessment

Dr Guido Reinhardt, S Gärtner, Dr H Keller, M Krüger, Dr M Müller-Lindenlauf,

N Rettenmaier, Dr A Schorb

8th Intern Conf on Renewable Resources and Biorefineries Toulouse, 4 – 6 June, 2012

ifeu – Institute for Energy and Environmental Research Heidelberg, Germany

2

Glycerol market

500

1.000

1.500

1990 2000 2010

1.000 t glycerol

500

1.000

1.500

€ / t glycerol

World glycerol production World glycerol price

3

Background

R1 – CO – O – CH2

R2 – CO – O – CH

R3 – CO – O – CH2

3 CH3OH

Simplified chemical reaction mechanism to transesterify vegetable oil into biodiesel

Vegetable oil

R1 – CO – O – CH3

R2 – CO – O – CH3

R3 – CO – O – CH3

HO – CH2

HO – CH

HO – CH2

+

Biodiesel Bio- glycerol

4

Background

Conventional glycerol use:

Glycerol use: quo vadis ? Conversion towards green chemicals ?

Bioenergy such as biogas or direct combustion ?

In chemistry, pharmaceutical products, in cosmetic products, in food and feed industry etc

5

Innovative uses for glycerol

Ethanol - use: for chemistry, biofuel

Butanol - use: for chemistry

PDO (1,3-propanediol) - use: for bioplastics

Glycerol

OH OH OH

CH2 CH CH2

OH

CH2 CH2

OH

CH2

CH3

OH

CH2

CH3 CH2 CH2

OH

CH2

6

Ethanol from glycerol

Crude glycerol

Fermentation

DistillationResidual

ferment. broth(organic

compounds)

Ethanol

Fermentation broth

BiogasAnaerobic digestion

Digestate

Filtration Solid biomass

Post fermentation

broth

Glycerol processing

Additives1

1 needs to be clarified

Process energy

7

Butanol from glycerol

8

1,3 propanediol (PDO) from glycerol

9

Glycerol use scenarios

Crude glycerol

Conversion

Ethanol

Butanol (+PDO)

PDO

Direct use for energy

Direct material use

Conventional use

Innovative use

Biogas

Concerning environmental benefits: which pathway is best ?

10

EU FP7 project: GLYFINERY

• Duration: 2008 – 2012 • Total budget: 4.97 M € • Partners:

Technical University of Denmark, Lyngby, Denmark BioGasol Aps, Ballerup, Denmark A&A Biotechnology, Gdynia, Poland Institute for Energy and Environmental Research,

IFEU, Heidelberg, Germany MEROCO, Leopoldov, Slovakia ProChimia Surface, Sopot, Poland

“Sustainable and integrated production of liquid biofuels, green chemicals and bioenergy from glycerol in biorefineries”

11

Goal and scope definition

Inventory analysis

Impact assessment

Interpretation

ISO 14040 & 14044

Life cycle assessment (LCA)


12

Resource extraction

Biofuel Fossil fuel Fertiliser

Fuel Pesticides

Agriculture

Co-products

Credits

Fallow maintenance

Equivalent products

Raw material production

Utilisation

Transport

Processing

LCA: Life cycle comparison

13


Inventory analysis

Impact assessment

Interpretation

ISO 14040 & 14044


Inventory analysis

14

Outputs e.g.:

- CO2

- SO2

- CH4

- NOX - NH3

- N2O - HCl - CO - C6H6

- VOC

Inputs e.g.:

- natural gas - crude oil - brown coal - hard coal - uranium - water

Resource extraction

BiofuelFossil fuelFertiliser

Fuel Pesticides

AgricultureRaw material production

Utilisation

Transport

Processing

LCA: Inventory analysis

15

Example: PDO from glycerol

16


Crude glycerol

Conversion

Ethanol

Butanol (+PDO)

PDO

Product

Process

Reference system


Direct material use

Conventional use

Innovative use Fossil ethanol or gasoline

Fossil butanol

PDO (fossil or made of starch)

Convent. heat / power

Convent. chemical


Biogas Convent. heat / power

Conventional products

same usefulness

17

Example: PDO from glycerol vs. fossil PDO

-2 -1,5 -1 -0,5 0 0,5 1 1,5

t CO2 eq. / t glycerol

Credits Expenditures

Advantages Disadvantages

Net total

Transport glycerol Fermentation material input Fermentation energy Centrifugation and filtration Solvent for extraction Distillation energy Biogas from residues: Expenditures Biogas from residues: Credit power savings Biogas from residues: Credit heat savings Biogas from residues: Credit fertilizer savings Transport product Credit savings of equivalent product Net total

Greenhouse gas emissions

Source: IFEU 2012

18

Results for greenhouse gas savings

PDO from glycerol vs. fossil PDO

Ethanol from glycerol vs. fossil ethanol

Butanol from glycerol vs. fossil butanol

-2 -1,5 -1 -0,5 0 0,5 1 1,5



-2 -1,5 -1 -0,5 0 0,5 1 1,5



-2 -1,5 -1 -0,5 0 0,5 1 1,5




t CO2 eq / t glycerol Bio-ethanol emits more greenhouse gases than fossil based ethanol Source: IFEU 2012

19

-2 -1,5 -1 -0,5 0 0,5 1 1,5



Ethanol from glycerol vs. fossil ethanol

Butanol from glycerol vs. fossil butanol

-2 -1,5 -1 -0,5 0 0,5 1 1,5



-2 -1,5 -1 -0,5 0 0,5 1 1,5




Credits for equivalent product and distillation energy are most important life cycle stages

PDO from glycerol vs. fossil PDO

Source: IFEU 2012

Results for greenhouse gas savings

20


Crude glycerol

Conversion

Ethanol

Butanol (+PDO)

PDO

Product

Process

Reference system


Direct material use

Conventional use


Fossil butanol



Convent. chemical




same usefulness Two different conventional PDO production schemes

21


-2 -1,5 -1 -0,5 0 0,5 1 1,5


Transport glycerol Fermentation material input

Fermentation energy Centrifugation and filtration

Solvent for extraction Distillation energy

Biogas from residues: Expenditures Biogas from residues: Credit power savings Biogas from residues: Credit heat savings Biogas from residues: Credit fertilizer savings

Transport product Credit savings of equivalent product

Net total

Influence of equivalent products

fossil PDO:

PDO: starch

Source: IFEU 2012

22


-2 -1,5 -1 -0,5 0 0,5 1 1,5


Influence of equivalent products

fossil

fossil




Biogas from residues: Expenditures Biogas from residues: Credit power savings Biogas from residues: Credit heat savings Biogas from residues: Credit fertilizer savings


Net total

gasoline Ethanol:

Ethanol:

PDO:

PDO: starch

-2 -1,5 -1 -0,5 0 0,5 1 1,5


Source: IFEU 2012

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Bandwidths PDO from glycerol vs fossil PDO: greenhouse gas balance

Source: IFEU 2012

-2,0 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5

Total bandwidth

worst case

best case

Low fossil credit

Low distillation energy

High distillation energy

Low yield

High yield

Typi

cal s

cena

rio w

ith

t CO 2 eq. / t glycerol


There is not just one single result of a LCA of PDO from glycerol but many, depending on the biorefinery layout, equivalent conventional products, and other system boundaries such as transport.

24

Results: innovative glycerol use options

PDO

Butanol

Ethanol

Source: IFEU 2012

PDO and butanol from glycerol have higher environmental potentials compared to ethanol from glycerol

-2,0 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 2,0

t CO 2 eq / t glycerol


Greenhouse gas emissions in

25


Crude glycerol

Conversion

Ethanol

Butanol (+PDO)

PDO

Product

Process

Reference system


Direct material use

Conventional use


Fossil butanol



Convent. chemical




same usefulness

26

Comparison to other options

-3 -2 -1 0 1 2

Cofermentation, CHP

Monofermentation, CHP

Ethanol

Butanol

PDO

Direct combustion

Direct material use

Biog

asCh

emic

alCo

nv.



Source: IFEU 2012

In general: all use options for glycerol compare similarly except conversion to ethanol (worse) or direct use (better)

Specifically: results for PDO, butanol, biogas & combustion depend on specific conditions

27


Inventory analysis

Impact assessment

Interpretation

ISO 14040 & 14044


Impact assessment

28

Impact category Parameter Substances (LCI) Energy demand Sum of depletable

primary energy carriers

Crude oil, natural gas, coal, Uranium, …

Greenhouse effect

CO2 equivalents Carbon dioxide, dinitrogen monoxide, methane, different CFCs, methyl bromide, …

Acidification SO2 equivalents

Sulphur dioxide, hydrogen chloride, nitrogen oxides, ammonia, …

Eutrophication PO4 equivalents Nitrogen oxides, ammonia, phosphate, nitrate

Photosmog

Ethen equivalents Hydrocarbons, nitrogen oxides, carbon monoxide, chlorinated hydrocarbons, …

Ozone depletion ´CFC11 equivalents CFC, halone, methyl bromide, …

Impact assessment categories

29

Acidification

-6 -4 -2 0 2 4 6 8 10 12

Ethanol: reference gasoline

Ethanol: reference fossil

Butanol: reference fossil

PDO: reference starch

PDO: reference fossil

Direct combustion

Direct material use

Inno

vativ

e op

tions

Conv

.op

tions

kg SO2 eq. / t glycerol

-5 -4 -3 -2 -1 0 1 2 3

PDO: reference fossil

PDO: reference starch

Butanol: reference fossil

Ethanol: reference fossil

Ethanol: reference gasoline

kg SO2 eq. / t glycerol




Biogas from residues: Expenditures Biogas from residues: Credit power savings

Biogas from residues: Credit heat savings Biogas from residues: Credit fertiliser savings



Source: IFEU 2012

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Other environmental impacts Advantages Disadvantages

Climate change

Energy demand

Acidification

Biogas (CHP), coferm.Biogas (CHP), monoferm.

EthanolButanol

PDODirect combustion

Direct material use


EthanolButanol


Direct material use

-800 -600 -400 -200 0 200 400 600


EthanolButanol


Direct material use

IE / 1000 t glycerolSource: IFEU 2012

31

Other environmental impacts

Eutrophication

Photosmog

Ozone depletion


-200 0 200 400

Biogas (CHP), coferm. Biogas (CHP), monoferm.

Ethanol Butanol

PDO Direct combustion Direct material use

IE / 1000 t glycerol

Source: IFEU 2012


Ethanol Butanol



Ethanol Butanol


32

Summary

Glycerol based chemicals: Environmental impacts: • High bandwidths

• PDO and butanol better than ethanol

• Important: - Energy demand of product purification - Yields

Best way of using glycerol: • In the near future: direct material use

• May change if biodiesel production increases massively

• Highest environmental potential: PDO, butanol, biogas via cofermentation & direct combustion

33

Summary

Life cycle assessment (LCA) is a suitable tool to

• Analyse the environmental impacts of both, existing technologies and products as well as future ones

• Identify environmental potentials to optimise environmental benefits and minimise environmental burdens

• Give advice to decision makers about environmental potentials and priorities for optimisations

34

Conclusions & recommendations

• A realisation of innovative glycerol use options is only recommended if the biodiesel production increases substantially.

• Ethanol production from glycerol is not recommendable from environmental perspective.

• Proceed to optimise glycerol conversion to PDO and butanol especially towards more efficient product purification and yield increase.

• Alternative glycerol use options besides the investigated ones should also be evaluated.

35

Outlook 1

Results presented here are reported in detail in following publication:

Download available on:

www.glyfinery.net or www.ifeu.de

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Outlook 2

Environmental Assessment

Economic Assessment

Technological Assessment

Integrated Sustainability Assessment

Final report

Sustainable and integrated production of liquid biofuels, green chemicals and bioenergy from glycerol in biorefinieries: Integrated assessment

Heidelberg, 2012

Deliverable 7.8 Integrated assessment: Final report of the EC funded GLYFINERY project GA no 213506

Results will be presented at the „20th European Biomass Conference and Exhibition“, Milano, Italy, 18 - 22 June 2012. See you there, or give contact details to send a copy to you.

Results presented here

Thank you for your attention!

Acknowledgement The work presented was supported by the European Commission through the FP7 project “Sustainable and integrated production of liquid biofuels, green chemicals and bioenergy from glycerol in biorefineries” (“GLYFINERY”, GA no 213506).

Nils Rettenmaier Dr Achim Schorb

Dr Heiko Keller Sven Gärtner

Dr Maria Müller-Lindenlauf

Martina Krüger

Contact: [email protected] + 49 - 6221 - 4767 - 0 / - 31

Downloads: www.ifeu.de

Dr Guido Reinhardt

Documents

Green chemicals from biorefineries with glycerol as