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possible integration of biogas+bioethanol processing - bioenergybaltic

Integration of biogas and bioethanol process

Piotr Oleskowicz-Popiel

PhD student

Biosystems Department

Risø DTU – National Laboratory for Sustainable Energy

Technical University of Denmark

Email: piotr.o.popiel@risoe.dk

Co-authors

Erik Steen Jensen

Mette Hedegaard Thomsen

Henrik Haugaard-Nielsen


Bioresources for bioenergy purposes

Piotr Oleskowicz-Popiel

2000 – 2003: bachelor at Poznan University of Technology,

Department of Chemical Technology, PL

2003 – 2005: MSc in Eng in Industrial Biotechnology,

Aalborg University Esbjerg, DK

2005 – 2007: research assistant, Department of Bioenergy

Aalborg University Esbjerg/University of Southern Denmark

2007 – present: PhD student, Biosystems Department,

National Laboratory for Sustainable Energy

and Technical University of Denmark (Risø DTU)


Integration of biogas and bioethanol process

1. Sustainable production of biofules: biogas and bioethanol

2. Second generation biofuels: IBUS concept

3. BioConcens Project

4. Bioprocess modelling (with SuperPro Designer®)

What is sustainability?

What are the advantages from

the co-production of biofuels?

First or second generation biofules?


Solar CO 2 H 2 O

energy N,P,K,

Sustainability assessment

Biorefinery

Products

Industrial chemicals

Biofuels

Electricity

Heat

Polymers

Materials

Fertilizers

Food ingredients

Feed

Bioresources

Biochemical

Thermochemical

Extraction

Sustainability assessment

4


Multifunctional land use

Land use

Goods

Food

Fibers

Fuels

Chemicals/materials

Water protection

Soil fertility

Biodiversity

Recreation

Bioremediation

5


Biomass-to-biofuel pathways

Biomass

Lignocellulosic

biomass

Thermoche

mical/gasification

Pretreament and

enz.hydrolysis

Syngas

2G technology

Catalysed

synthesis

BTL

F-T diesel

DME

Methanol

Sugar

Fermentation

og destillation

Ethanol

Sugar- and

starch crops

Oil plants and animal

fat

Milling and

enz. hydrolysis

Extraction

1G technology

Transesterification

Biodiesel

Residues and

organic waste

Fermentation

and cleaning

Biogas

and H 2

Adapted from: Erik Steen Jensen: Lignocellulose-based biofuel production –bioresources, technologies and sustainability

6


Biomass-to-biofuel pathways

Biofuels in the EU. A vision for 2030 and beyond. Final draft report of the Biofuels Research Advisory Council

7


Crops for 1G biofuel

8


1G biofuels (ethanol and biodiesel) and associated crops

• The use of known 1G crops and cultivations methods is not likely

to influence positively the environment – but will increase the

competition for land with other uses (feed and food)

• The protein fraction of the biomass can be used for feed (DDGS

and rapeseed cake)

• Crop residues from food and feed crops can be used for 2G

biofuels to some extent

• Cultivation of marginal soils (including set-aside) with annual crops

increases the risk for loss of nutrients and transport of pesticides to the

aquatic environment.

• Some annual crops are problematic from an environmental point

of view – e.g. maize and oilseed cultivation are associated with large

leaching losses (table)

Adapted from: Erik Steen Jensen: Lignocellulose-based biofuel production –bioresources, technologies and sustainability

9


Perennial crops for 2G bioethanol and BTL

10


Lignocellulose - residues and waste

11


Anaerobic Digestion (AD)

Suspended organic matter

Hydrolysis

Proteins Carbohydrates Lipids

Polypeptides

Peptides Mono and disaccharides Volatile acids and glycerine

AD is commonly used for the treatment

of animal manure, organic waste from

agriculture and urban areas and food

industry.

Acidogenesis

Acetogenesis

Organic compounds: volatile

fatty acids, alcohols, lactic acid

Mineral compounds: CO 2

,

H 2

, NH 4+

/NH 3

, H 2

S

Acetic acid CO 2

, H 2

Microbiological conversion of organic

matter to methane in the absence of

oxygen. The process is also known as

the biogas process and has been

widely utilized in wastewater treatment

plants.

Methanogenesis

Methane production:

CH 3

COOH => CH 4

+ CO 2

(Acetotrophic methanogenesis)

CO 2

+ H 2

=> CH 4

+ H 2

O (Hydrotrophic methanogenesis)

adapted from: Benabdallah El-Hadj T. (2006) ISBN: 84-690-2982-7

12


Sustainable cycle of Anaerobic Digestion

Anaerobic digestion is a natural

process during which bacteria

break down the carbon in

organic material

The biogas plant has

three main products:

-biogas (source of energy)

-liquid fertilizer

-fiber for compost

Al Seadi T.: Good practice in Quality Management of AD Residues; Task 24 – Energy from Biological Conversion of

Organic Waste; Department of Bioenergy; University of Southern Denmark.

13


Utilisation of digestate

• To be recycled as fertilizer, digestate must

have a defined content of macronutrients.

Average samples of digestate must also

be analyzed for heavy metals and

persistent organic contaminants, making

sure that these are not exceeding the

detection limits permitted by law.

• The application of digestate must be done

on the basis of a fertiliser plan, elaborated

for each agricultural field. The experience

shows that an environmental and

economic suitable application of digestate

fulfils the phosphorus requirements of the

crops and completes the nitrogen

requirements from mineral fertiliser.

Al Seadi T. ed.: Biogas from AD, Bioexell training manual; Department of Bioenergy; University of Southern Denmark.

14


Digestate as a fertilizer

Highly efficient fertiliser can be achieved

from co-digestion of cow manure (high in

potassium), pig manure (high in

phosphorous), and suitable agricultural

wastes and by-products. Due to the fact

that the digestate is nutritionally defined, it

can be used very efficiently. Application of

digestate as bio-fertiliser decreases

nutrients loss as well as pollution of water

from nutrients. Additionally, it results in

saving energy consumption for production

of chemical fertiliser. To obtain all these

benefits though it is necessary to apply

what is called a “good agricultural practice”

Nordberg A., Edstrom M.: Waste management in

northern Europe: experiences from the Linkoeping

biogas plant. European workshop: Impact of Waste

Management Legislation on Biogas Technology,

Tulln, Austria, September 12-14, 2002.

Parameter

Total solids [%] 4.5

Volatile solids [%TS] 75

pH 8.1

Total-N [kg/m 3 ] 7.2

Ammonia-N [kg/m 3 ] 4.9

P [kg/m 3 ] 0.7

K [kg/m 3 ] 1.0

Digestate

Linkoeping

Pb [mg/kgTS]


Digestate as a fertilizer

Average concentrations of nitrogen, ammonia, and phosphorous in digestate from Danish

centralised co-digestion plants

http://www.mst.dk/default.asp?Sub=http://www.

mst.dk/udgiv/publikationer/2004/87-7614-282-

5/html/kap04.htm - Danish Environmental

Protection Agency, Danish Ministry of the

Environment

Biogas plant

Total N

[kg/ton]

NH 4

-N/NH 3

[kg/ton]

P

[kg/ton]

Blaabjerg 4,75 3,25 1,1

Blåhøj 5,30 3,8 0,84

Fangel 5,83 4,38 0,92

Filskov 4,90 3,7 0,94

Hashøj 5,05 3,9 0,78

Lemvig 4,28 3,02 1,2

Lintrup 5,00 3,26 1,3

Nysted 4,84 3,79 0,90

Ribe 4,6 3,2 0,9

Sinding-Ørre 2,6 2,2 1,2

Snertinge 4,3 3,0 1,3

Studsgård 3,86 2,79 0,86

Thorsø 4,80 3,6 0,96

16


Safe recycling of digestate

Good agricultural practice - experience from Denmark

• Source sorting and separate collection of digestible wastes, preferably in

biodegradable recipients.

• Selection / excluding from AD of the unsuitable waste types / loads, based

on the complete declaration of each load: origin, content of heavy metals

and persistent organic compounds, pathogen contamination, other potential

hazards etc.

• Periodical sampling and analysing of the biomass feedstock.

• Extensive pre-treatment/on site separation (especially for unsorted waste).

• Process control (temperature, retention time etc.) to obtain a stabilised end

product.

• Pasteurization / controlled sanitation for effective pathogen reduction.

• Periodical sampling, analysing and declaration of digestate.

• Including digestate in the fertiliser plan of the farm and using a “good

agricultural practice” for application of digestate on farmland.

Al Seadi T. ed.: Biogas from AD, Bioexell training manual; Department of Bioenergy; University of Southern Denmark.

17


Ethanol fermentation

IBUS

http://www.nasa.gov

H(C 6 H 10 O 5 ) n OH enzymes n C 6 H 12 O 6

162 kg 180 kg

n C 6 H 12 O 6 yeast 2n C 2 H 5 OH + 2n CO 2

180 kg 92kg 88kg

From the chemist/engineer point of view

Jacqus K. et al.: The Alcohol Textbook. 3rd edition, Nothingam

University Press, 1999.

From the microbiologist point of view

18


Biomass to bioethanol

Mandil C. eds.: Biofules for transport. An international perspective. IEA, 2004.

19


Lignocellulose degradation

Lignocellulose

pre-treatment

cellulose*

carboxylic acids + CO 2 + H 2 O

+ lignin degradation products

hemicellulose*

*source: Bjerre A.B., Skammelsen

Schmidt A.: Development of Chemical

and Biological Processes for Production

of Bioethanol: Optymalization of the Wet

Oxidation Process and Characterization

of Products, Risø National Laboratory,

1997, Roskilde, Denmark [Riose-R-

967(EN)]

20


Bioethanol and Biogas potential

Petersson et al.: Potential bioethanol and biogas production using lignocellulosic biomass from winter rye, oilseed rape and

faba bean. Biomass and Bioenergy 31 82007) 812-819.

21


Biogas and Bioethanol potential

Petersson et al.: Potential bioethanol and biogas production using lignocellulosic biomass from winter rye, oilseed rape and

faba bean. Biomass and Bioenergy 31 82007) 812-819.

22


Real life example

The principles:

-About one-third of the corn—the starch—is converted

into ethanol, and another one-third into thin stillage,

which is used in the anaerobic digesters for heat and

biogas. The other one-third, a combination of protein,

oils, and fibers called distiller's grain, is usually sold as

feed for cattle. However, this grain is wet when it exits

the ethanol plant, and traditionally equipment costing

several million dollars must be used to dry it before

transport in order to prevent spoilage

-Corn byproducts, including cellulose from the corn

stalks, also go into the biogas brew.

- the water pollution problems are solved by removing

manure from feedlots

How can we improve the system?

How can we increase sustainability of the process?

http://www.e3biofuels.com

23


Integration of biogas and bioethanol process

1. Sustainable production of biofules: biogas and bioethanol

2. Second generation biofuels: IBUS concept

3. BioConcens Project

4. Bioprocess modelling (with SuperPro Designer®)

First or second generation biofules?

Based on: Mette Hedegaard Thomsen

Biomass & Bioenergy Conference, 27th-29th of February 2008, Tallinn, Estonia


1. generation 2. generation

The use of known 1G crops and

cultivations methods is not likely to

influence positively the environment – but

will increase the competition for land with

other uses (feed and food)

Crop residues from food and

feed crops can be used for 2G

biofuels to some extent

Adapted from: Erik Steen Jensen: Lignocellulose-based biofuel production –bioresources, technologies and sustainability

25


Lignocellulose degradation

Lignocellulose

pre-treatment

cellulose*

carboxylic acids + CO 2 + H 2 O

+ lignin degradation products

hemicellulose*

*source: Bjerre A.B., Skammelsen

Schmidt A.: Development of Chemical

and Biological Processes for Production

of Bioethanol: Optymalization of the Wet

Oxidation Process and Characterization

of Products, Risø National Laboratory,

1997, Roskilde, Denmark [Riose-R-

967(EN)]

26


2. generation Bioethanol production

Enzymes

Microorganism

C5

Pretreatment

Hemicellulose

Hydrolysis

Enzymes

Fermentation

Yeast

Cellulose

C6

Bio-Ethanol

Lignin

Hydrolysis

Fermentation

Distillation

27


Co-production Biofuels (EU-project: 2003-2006, Danish project: 2006-2009)

Objective: Co-production of electricity and bioethanol

Goal: Construction and testing of a pilot scale pretreatment reactor system

with a planned capacity of 1000 kg of biomass per hour.

Integrated Biomass Utilisation System (IBUS)

1.step: Pilot scale reactor with a capacity of 100 kg/h

Partners:

Elsam A/S (DONG Energy)

Risø National Laboratory - DTU

The Royal Veterinary and

Agricultural University

TMO Biotech (EU-project)

BioCentrum - DTU (Danish

project)


IBUS 1000 kg/h plant

195-200ºC

90-100% cellulose

convertibility

50% hemicellulose

recovery

180ºC + 195ºC

90-100% cellulose

convertibility

83% hemicellulose

recovery


Advantages of the IBUS process

• Simple and fast process

• Enzymes and hot water

• Process time < 100 h

• Can be upscaled

• Energy efficient

• No milling

• High dry matter (40%)

• Power plant integration

• Flexible biorefinery

• The lignin fraction contains sufficient energy to

run the process!


Cut wheat straw

Heat pretreated wheat straw

31


High dry matter liquefaction of fibre fraction

Larsen et al, 2006

32


GHG balance for IBUS

Grain

Straw

van Maarschalkerweerd, Risø (2006)

33


How far are we? - Feasibility study

Production cost for straw-based ethanol

Ethanol prod. costs [$/gal]

8

7

6

5

4

3

2

1

0

20% 30% 40% 50% 60% 70% 80% 90% 100%

Case 1

Case 2

Case 3

Case 1 = C6, stand alone

Case 2 = C6, integrated (with power plant)

Case 3 = C6+C5, integrated

Cellulose conversion ratio [%]

Ref. Jan Larsen, Dong Energy, 28th Symposium on Biotechnology for Fuels and Chemicals, May 2006, Nashville.

Latest feasibility study based on 1000 ton pr day IBUS ethanol plant located in the US (cost and

income), corn stover 40 EUR/t DM and enzyme cost 0.14 EUR/liter ethanol.

Raw production cost: 0.43 EUR/liter ethanol (2.40 US$/gal)

World market price 0.35 EUR/liter, EU-market price 0.55 EUR/liter [Morgan Stanley Equity Research, oct. 2007]


AD manure as water and nutrient source

Pre-treatment (Wet-Oxidation)

Straw, Water or AD Manure

SSF: Enzymes, Yeast

Product: Ethanol

Xylose Fermentation

Product: Ethanol

Source: Thomsen A.B., Medina C., Ahrling B.K.: Risø Energy Report

2. Biotechnology in ethanol production. Risø National Laboratory,

Denmark, November 2003.

Anaerobic Digestion

Product: Biogas

Oleskowicz-Popiel P. et al.: Ethanol production from maize silage as lignocellulosic biomass in anaerobically

digested and wet-oxidized manure. Bioresource Technology. in press

35


AD manure as water and nutrient source

fermentation of IBUS straw in pre-treated AD manure and water

ethanol [g/100g]

1,8

1,6

1,4

1,2

1

0,8

0,6

0,4

0,2

0

0 20 40 60 80 100 120 140 160

time [h]

Straw+121.0

Straw+121.12

Straw+Water

manure 121.12

Successful ethanol

fermentation in AD manure as a

water and nutrient source

3400

3200

ammonia [mg/L]

3000

2800

2600

2400

2200

2000

0 20 40 60 80 100 120 140 160

time [h]

Straw 1 Straw 2 Maize 1 Maize 2

Nitrogen uptake during ethanol

fermentation.

AD manure can be recirculated

several times as a N-source

36


Integration of biogas and bioethanol process

1. Sustainable production of biofules: biogas and bioethanol

2. Second generation biofuels: IBUS concept

3. BioConcens Project

4. Bioprocess modelling (with SuperPro Designer)

Is there a future for organic farming?


BioConcens

• Biomass and Bioenergy Production in Organic Farming –

Consequences for Soil Fertility, Environment, Spread of Animals

Parasites and Socio-Economy.

• The production of biofules in organic agriculture can reduce its

dependency of fossil fuels and decrease GHG emission

• It might increase sustainability of organic farming

organic

farming

Main stream agriculture

38


• DARCOF – The Danish Research Centre for Organic Farming:

”The remit of DARCOF is to coordinate research for organic farming,

with a view to achieving optimum benefit from the allocated

resources. Its aim is to elucidate the ideas and problems faced in

organic farming through the promotion of high quality research of

international standard.”

http://www.darcof.dk

• DARCOF III – research programme “International research

cooperation and organic integrity”:

BioConcens http://www.bioconcens.elr.dk/uk/

39


• BioConcens – Biomass and bioenergy production in organic

agriculture – consequence for soil fertility, environment, spread of

animal parasites and socio-economy

• work package 1: Co-production of biogas, bioethanol and animal

feed from organic raw materials:

1. biogas potentials of raw materials

2. co-production of biogas and fodder protein

3. co-production of biogas and bioethanol

40


BioConcens

41


BioConcens – co-production of biogas and bioethanol

• Bioethanol from starch can be substitute for diesel or gasoline. The

method for bioethanol production from rye grain by utilizing the

inherent amylase activity of the seed is going to be developed (to

avoid GMO based enzymes)

• Usage of natural enzymes and whey permeate as nutrients and

process water in bioethanol fermentation will decrease production

cost and increase sustainability of the process. Application of the

effluent into the biogas process will be the additional advantage.

42


BioConcens – co-production of biogas, bioethanol and fodder

• The goal is to develop farm-scale, low energy demanding and “easy to

handle” technology for production of bioethanol from rye grain. To keep the

frame of organic farming natural enzymes will be applied (commercial

enzymes will be used only for reference experiments). The remaining

compounds will be recycled into biogas process.

• Co-fermentation of clover grass (commonly grown in OA) with animal manure

• Co-fermentation of clover grass with whey (co-production of energy and animal

feed)

43


BioConcens

• From the energy balance point of

view, the most relevant utilization of

feedstocks and co-products will be

modelled in SuperPro Designer

(Intelligen, INC)

• Bioenergy from organic sources

should not negatively influence the

carbon and nutrients cycle – the

intelligent management of organic

residues and crop rotation is

necessary

• Design and evaluate a combined

concept for biomass and bioenergy

production in OA (considering the

soil fertility)

44


Initial results – the idea does really work

Ethanol concentration (g/L)

50

40

30

20

10

0

Malted rye, 13% dw

Malted rye, 13% dw

Comm. enz., 13% dw

Comm. enz., 13% dw

0 10 20 30 40

Time (h)

400

300

[mL CH4 / gVS]

200

100

0

0 5 10 15 20 25 30 35 40

time [day]

dry grass (low conc.)

dry clover grass (low conc.)

clover grass silage (low conc.)

dry grass (high conc.)

dry clover grass (high conc.)

clover grass silage (high conc.)

45


Integration of biogas and bioethanol process

1. Sustainable production of biofules: biogas and bioethanol

2. Second generation biofuels: IBUS concept

3. BioConcens Project

4. Bioprocess modelling (with SuperPro Designer ® )

How to design

an environmentally friendly process?


Modeling of a bioprocess

Process concept

Process design and

development

Modeling and

simulation

Literature

Patents

Expert

knowledge

Improvements

needed

Sustainability

assessment

Not

eco-efficient

Stop

Eco-efficient

Industrial application

adapted from:

Heinzle E., et al., (2006)Development of

Sustainable Bioprocesses – Modelling and

Assessment. John Wiley & Sons Ltd.

47


Modeling of a bioprocess

• in process development we should try

understand of the actual production process

as early and as detailed as possible

• the modeling of the process under

development and a through assessment

helps to improve this knowledge

• the assessment should include economic

and environmental evaluation

• the simulation results are used to evaluate

the process and to guide the R&D effort to

the most promising directions and the most

urgent problems

• it is important to look at the whole process

and not only to optimize single parts

• the created models and the assessment

based on these models include a certain

inherent uncertainty; this uncertainty has to

be considered and quantified

48


Modeling of a bioprocess

• besides the economic structure of a process, environmental and

social aspects should be considered

• process modeling and simulation enhances our insight and

understanding of a process and helps to identify potential

improvements as well as possible difficulties

• in process development, simulation can supplement experiments

49


Modeling of a bioprocess

Define goal & process boundaries

Collect data (internal and external)

Define bioreactions

Identify process flow diagram (unit operations and streams)

Define unit operation models

Perform simulations

Make inventory analysis and assessment

adapted from:

50

Heinzle E., et al., (2006)Development of Sustainable Bioprocesses – Modelling and Assessment. John Wiley & Sons Ltd.


Modeling of a bioprocess

• What are required amounts of raw materials and utilities?

• What is the required size of process equipment and supporting utilities?

• Can the product be produced in an existing facility or a new plant is required?

• What is the total capital investments?

• What is the manufacturing cost?

• What is the optimum batch size?

• How long does the single batch take?

• How much product can be generated per year?

• What is the demand for raw materials, labor, utilities, etc.?

• Which process step can be a bottleneck?

• What changes can increase throughout?

• What is the environmental impact of the process?

• Which design is the best among several possible alternatives?

adapted from:

Petrides D., Bioprocess Design and

Economics. Oxford University Press, 2003.

51


Modeling of a bioprocess

• After a model for the entire process is developed on the computer,

tools like SuperPro Designer ® can be used to ask and readily answer

”what if” questions and carry out sensitivity analysis with respect to

key design variables.

• SuperPro Designer ® - simulation program that is able to estimate

both process and economic parameters.

52


Modeling of a bioprocess

• Computer simulations provide the ability to estimate the effect of

increasing costs of raw materials or utilities, variations in material

compositions, and the incorporation of new technologies

• Beginning with a base-case scenario and designing the model to

simulate those conditions effectively allows the user to estimate

results of alternative processes with confidence.

photo: www.siteselection.com

Kwiatkowski J.R. et al: Modeling the process and costs of fuel ethanol production by the corn dry-grind process.

Industrial Crops and Products 23 (2006) 288-296

53


Modeling the process - simplified flow diagram

150 million l/year plant

Kwiatkowski J.R. et al: Modeling the process and costs of fuel ethanol production by the corn dry-grind process.

Industrial Crops and Products 23 (2006) 288-296

54


Modeling the process - simplified flow diagram

• Grain receiving

• Liquefaction, saccharification, and fermentation – all the reaction,

volumes, residence times, agitation/pumping power required, and

other operating parameters may be adjusted to imitate an existing

fermenter or make use of experimental data. The model will scale

the unit to accommodate any change in raw material plant

throughput

• distillation and ethanol recovery

• stillage processing

• final products – fuel ethanol (with app. 5% denaturant – gaoline),

DDGS (an animal feed rich in protein – 27.8%)

Kwiatkowski J.R. et al: Modeling the process and costs of fuel ethanol production by the corn dry-grind process.

Industrial Crops and Products 23 (2006) 288-296

55


Modeling the process - simplified flow diagram

• The actual process contains more than 100 pieces of equipment and unit

operations

• The process simulator quantifies the processing characteristic, energy

requirements, and equipment parameters of each major piece of equipment

for the specified operating scenario.

• Volumes, composition, and other physical characteristic of input and output

streams for each equipment item are identified. This information becomes

the basis of utility consumptions and purchased equipment costs for each

equipment item.

• Composition of a raw agricultural feedstock varies by year and location, this

can be easy adjusted

• Different raw materials can be input in the model. although, maybe some

extra unit operation need to be given

Kwiatkowski J.R. et al: Modeling the process and costs of fuel ethanol production by the corn dry-grind process.

Industrial Crops and Products 23 (2006) 288-296

56


Cost model description

• Equipment costs

• Feedstock costs

• Product values

• Utility costs

• Capital costs

• Annual production and unit costs

• Sensitivities

Kwiatkowski J.R. et al: Modeling the process and costs of fuel ethanol production by the corn dry-grind process.

Industrial Crops and Products 23 (2006) 288-296

57


Lysine flow sheet

The lactic acid fermentation of brown juice in the green crop drying plant as it

was simulated in SuperPro Designer

Thomsen MH: Complex media from processing of agricultural crops for microbial fermentation.

Mini-Review, Appl. Microbiol. Biotechnol (2005) 68: 598-606

58


Priority of sustainable land and bioresource use

Erik Steen Jensen

59

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