Integration of biogas and bioethanol process Piotr Oleskowicz-Popiel

PhD student Biosystems Department Ris 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 (Ris 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 CO2 H2O Sustainability assessment energy N,P,K, Biorefinery Products

Industrial chemicals Biofuels Electricity Heat Polymers Materials Fertilizers Food ingredients Feed

Bioresources

Biochemical Thermochemical Extraction

Sustainability assessment

Multifunctional land use

Land use

Goods Food Fibers Fuels Chemicals/materials Water protection Soil fertility Biodiversity Recreation Bioremediation

Biomass-to-biofuel pathways
Biomass
Thermoche mical/gasification Syngas Catalysed synthesis BTL F-T diesel DME Methanol

Lignocellulosic biomass Pretreament and enz.hydrolysis

2G technology

Sugar Sugar- and starch crops Oil plants and animal fat Residues and organic waste Milling and enz. hydrolysis Extraction

Fermentation og destillation

Ethanol

1G technology
Transesterification Fermentation and cleaning Biodiesel Biogas and H2
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Adapted from: Erik Steen Jensen: Lignocellulose-based biofuel production bioresources, technologies and sustainability

Biomass-to-biofuel pathways

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

Crops for 1G biofuel

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

Perennial crops for 2G bioethanol and BTL

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Lignocellulose - residues and waste

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Anaerobic Digestion (AD)

Suspended organic matter Proteins Carbohydrates Lipids

Hydrolysis
Polypeptides Peptides Mono and disaccharides Volatile acids and glycerine

Acidogenesis

AD is commonly used for the treatment of animal manure, organic waste from agriculture and urban areas and food industry. 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.

Organic compounds: volatile fatty acids, alcohols, lactic acid

Mineral compounds: CO2, H2, NH4+/NH3, H2S

Acetogenesis
Acetic acid CO2, H2

Methanogenesis

Methane production: CH3COOH => CH4 + CO2 (Acetotrophic methanogenesis) CO2 + H2 => CH4 + H2O (Hydrotrophic methanogenesis)

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

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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.

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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.

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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 Parameter Total solids [%] Volatile solids [%TS] pH Total-N [kg/m3] Ammonia-N [kg/m3] P [kg/m3] K [kg/m3] Pb [mg/kgTS] Cd [mg/kgTS] Cu [mg/kgTS] Cr [mg/kgTS]
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.

Digestate Linkoeping 4.5 75 8.1 7.2 4.9 0.7 1.0 <5.0 0.12 71 5.7 <0.05 5.2 309
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Hg [mg/kgTS] Ni [mg/kgTS] Zn [mg/kgTS]

Digestate as a fertilizer
Average concentrations of nitrogen, ammonia, and phosphorous in digestate from Danish centralised co-digestion plants Biogas plant Blaabjerg Blhj Fangel Filskov Hashj Lemvig Lintrup Nysted Ribe
http://www.mst.dk/default.asp?Sub=http://www. mst.dk/udgiv/publikationer/2004/87-7614-2825/html/kap04.htm - Danish Environmental Protection Agency, Danish Ministry of the Environment

Total N [kg/ton] 4,75 5,30 5,83 4,90 5,05 4,28 5,00 4,84 4,6 2,6 4,3 3,86 4,80

NH4-N/NH3 [kg/ton] 3,25 3,8 4,38 3,7 3,9 3,02 3,26 3,79 3,2 2,2 3,0 2,79 3,6

P [kg/ton] 1,1 0,84 0,92 0,94 0,78 1,2 1,3 0,90 0,9 1,2 1,3 0,86 0,96
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Sinding-rre Snertinge Studsgrd Thors

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

Ethanol fermentation
http://www.nasa.gov Jacqus K. et al.: The Alcohol Textbook. 3rd edition, Nothingam University Press, 1999. IBUS

H(C6H10O5)nOH 162 kg n C6H12O6 180 kg

yeast

enzymes

n C6H12O6 180 kg

2n C2H5OH + 2n CO2 92kg 88kg

From the chemist/engineer point of view

From the microbiologist point of view

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Biomass to bioethanol

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

Lignocellulose degradation
Lignocellulose
pre-treatment

cellulose* hemicellulose*

carboxylic acids + CO2 + H2O + lignin degradation products

*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, Ris National Laboratory, 1997, Roskilde, Denmark [Riose-R967(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.

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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.

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Real life example

The principles:
-About one-third of the cornthe starchis 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?
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http://www.e3biofuels.com

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

Lignocellulose degradation
Lignocellulose
pre-treatment

cellulose* hemicellulose*

carboxylic acids + CO2 + H2O + lignin degradation products

*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, Ris National Laboratory, 1997, Roskilde, Denmark [Riose-R967(EN)] 26

2. generation Bioethanol production

Enzymes

Microorganism

C5
Pretreatment Hydrolysis Fermentation Enzymes Hemicellulose Cellulose Lignin Hydrolysis Fermentation Distillation
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Yeast

C6

Bio-Ethanol

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) Ris National Laboratory - DTU The Royal Veterinary and Agricultural University TMO Biotech (EU-project) BioCentrum - DTU (Danish project)

IBUS 1000 kg/h plant

195-200C 90-100% cellulose convertibility 50% hemicellulose recovery

180C + 195C 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

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High dry matter liquefaction of fibre fraction

Larsen et al, 2006

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GHG balance for IBUS

Grain Straw

van Maarschalkerweerd, Ris (2006)

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How far are we? - Feasibility study

Production cost for straw-based ethanol
8 Case 1 Ethanol prod. costs [$/gal] 7 Case 2 6 Case 3 5 4 3 2 1 0 20%

Case 1 = C6, stand alone Case 2 = C6, integrated (with power plant) Case 3 = C6+C5, integrated

30%

40%

50%

60%

70%

80%

90% 100%

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

Anaerobic Digestion Product: Biogas

Source: Thomsen A.B., Medina C., Ahrling B.K.: Ris Energy Report 2. Biotechnology in ethanol production. Ris National Laboratory, Denmark, November 2003.

Oleskowicz-Popiel P. et al.: Ethanol production from maize silage as lignocellulosic biomass in anaerobically digested and wet-oxidized manure. Bioresource Technology. in press

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AD manure as water and nutrient source

ferm entation of IBUS straw in pre-treated AD m anure and w ater

1,8 1,6 1,4 1,2 1 0,8 0,6 0,4 0,2 0 0 20 40 60 80

ethanol [g/100g]

Straw+121.0 Straw+121.12 Straw+Water manure 121.12

Successful ethanol fermentation in AD manure as a water and nutrient source

140 160

100

120

time [h]

3400 3200 3000 ammonia [mg/L] 2800 2600 2400 2200 2000 0 20 40 60 80 tim e [h] Straw 1 Straw 2 Maize 1 Maize 2 100 120 140 160

Nitrogen uptake during ethanol fermentation. AD manure can be recirculated several times as a N-source

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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

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 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/

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 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

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BioConcens

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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.

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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)
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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)
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Initial results the idea does really work

Ethanol concentration (g/L) 50 40 30 20 10 0 0 10 20 Time (h)
400

Malted rye, 13% dw Malted rye, 13% dw Comm. enz., 13% dw Comm. enz., 13% dw

30

40

300 [mL CH4 / gVS]

200

100

0 0 5 10 15 20 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.) 25 30 35 40

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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
Eco-efficient

Not eco-efficient

Stop

Industrial application

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

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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

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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

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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.

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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.

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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

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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

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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

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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

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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

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Priority of sustainable land and bioresource use

Erik Steen Jensen

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