proceso general.pdf
TRANSCRIPT
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Integration of biogas and bioethanol process
Piotr Oleskowicz-PopielPhD student
Biosystems Department
Ris DTU National Laboratory for Sustainable Energy
Technical University of Denmark
Email: [email protected]
Co-authorsErik Steen Jensen
Mette Hedegaard Thomsen
Henrik Haugaard-Nielsen
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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)
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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 Project4. Bioprocess modelling (with SuperPro Designer)
What is sustainability?What are the advantages fromthe co-production of biofuels?
First or second generation biofules?
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Bioresources
BiochemicalThermochemical
Extraction
Biorefinery Products
Industrial chemicalsBiofuels
Electricity
Heat
Polymers
MaterialsFertilizers
Food ingredients
Feed
Sustainability assessment
Solar CO2 H2Oenergy N,P,K,
Sustainability assessment
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Multifunctional land use
Land use
Goods
FoodFibersFuels
Chemicals/materialsWater protectionSoil fertilityBiodiversityRecreationBioremediation
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Biomass-to-biofuel pathways
Biomass
Lignocellulosic
biomass
Thermoche
mical/gasifi-
cation
Pretreament and
enz.hydrolysis
Milling and
enz. hydrolysis
Extraction
Sugar
Syngas
TransesterificationOil plants and animal
fat
Sugar- and
starch crops
Residues andorganic waste
Catalysed
synthesis
Fermentation
og destillation
Biodiesel
Fermentationand cleaning
Biogasand H2
Ethanol
BTLF-T diesel
DME
Methanol2G technology
1G technology
Adapted from: Erik Steen Jensen: Lignocellulose-based biofuel production bioresources, technologies and sustainability
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Biomass-to-biofuel pathways
Biofuels in the EU. A vision for 2030 and beyond. Final draft report of the Biofuels Research Advisory Council
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Crops for 1G biofuel
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1G biofuels (ethanol and biodiesel) and associated crops
The use of known 1G crops and cultivations methods is not likelyto 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 (DDGSand rapeseed cake)
Crop residues from food and feed crops can be used for 2Gbiofuels to some extent
Cultivation of marginal soils (including set-aside) with annual cropsincreases the risk for loss of nutrients and transport of pesticides to theaquatic environment.
Some annual crops are problematic from an environmental point
of view e.g. maize and oilseed cultivation are associated with largeleaching losses (table)
Adapted from: Erik Steen Jensen: Lignocellulose-based biofuel production bioresources, technologies and sustainability
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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
Polypeptides
Peptides Mono and disaccharides Volatile acids and glycerine
Organic compounds: volatile
fatty acids, alcohols, lactic acidMineral compounds: CO2,
H2, NH4+/NH3, H2S
Acetic aci d CO2, H2
Methane production:
CH3COOH => CH4 + CO2 (Acetotrophic methanogenesis)
CO2 + H2 => CH4 + H2O (Hydrotrophic methanogenesis)
Hydrolysis
Acidogenes is
Acetogenesis
Methanogenesis
adapted from: Benabdallah El-Hadj T. (2006) ISBN: 84-690-2982-7
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 beenwidely utilized in wastewater treatment
plants.
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Sustainable cycle of Anaerobic Digestion
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.
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
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Utilisation of digestate
To be recycled as fertilizer, digestate musthave a defined content of macronutrients.
Average samples of digestate must also
be analyzed for heavy metals andpersistent organic contaminants, making
sure that these are not exceeding the
detection limits permitted by law.
The application of digestate must be doneon the basis of a fertiliser plan, elaboratedfor each agricultural field. The experience
shows that an environmental and
economic suitable application of digestate
fulfils the phosphorus requirements of thecrops 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 factthat 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 Digestate
Linkoeping
Total solids [%] 4.5
Volatile solids [%TS] 75
pH 8.1
Total-N [kg/m3] 7.2
Ammonia-N [kg/m3] 4.9
P [kg/m3] 0.7
K [kg/m3] 1.0
Pb [mg/kgTS]
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Digestate as a fertilizer
Biogas plant Total N
[kg/ton]
NH4-N/NH
3
[kg/ton]
P
[kg/ton]
Blaabjerg 4,75 3,25 1,1
Blhj 5,30 3,8 0,84
Fangel 5,83 4,38 0,92
Filskov 4,90 3,7 0,94
Hashj 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 0,90Ribe 4,6 3,2 0,9
Sinding-rre 2,6 2,2 1,2
Snertinge 4,3 3,0 1,3
Studsgrd 3,86 2,79 0,86
Thors 4,80 3,6 0,96
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
Average concentrations of nitrogen, ammonia, and phosphorous in digestate from Danishcentralised co-digestion plants
http://www.mst.dk/default.asp?Sub=http://www.mst.dk/udgiv/publikationer/2004/87-7614-282-5/html/kap04.htmhttp://www.mst.dk/default.asp?Sub=http://www.mst.dk/udgiv/publikationer/2004/87-7614-282-5/html/kap04.htmhttp://www.mst.dk/default.asp?Sub=http://www.mst.dk/udgiv/publikationer/2004/87-7614-282-5/html/kap04.htmhttp://www.mst.dk/default.asp?Sub=http://www.mst.dk/udgiv/publikationer/2004/87-7614-282-5/html/kap04.htmhttp://www.mst.dk/default.asp?Sub=http://www.mst.dk/udgiv/publikationer/2004/87-7614-282-5/html/kap04.htmhttp://www.mst.dk/default.asp?Sub=http://www.mst.dk/udgiv/publikationer/2004/87-7614-282-5/html/kap04.htm -
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Safe recycling of digestate
Good agricultural practice - experience from Denmark
Source sorting and separate collection of digestible wastes, preferably inbiodegradable recipients.
Selection / excluding from AD of the unsuitable waste types / loads, basedon 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 endproduct.
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 goodagricultural practice for application of digestate on farmland.
Al Seadi T. ed.: Biogas from AD, Bioexell training manual; Department of Bioenergy; University of Southern Denmark.
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Ethanol fermentation
H(C6H10O5)nOH enzymes n C6H12O6
162 kg 180 kg
n C6H12O6yeast 2n C2H5OH + 2n CO2
180 kg 92kg 88kg Jacqus K. et al.: The Alcohol Textbook. 3rd edition, NothingamUniversity Press, 1999.
From the chemist/engineer point of view From the microbiologist point of view
http
://www.nasa.gov
IBUS
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Biomass to bioethanol
Mandil C. eds.: Biofules for transport. An international perspective. IEA, 2004.
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Lignocellulose degradation
Lignocellulosepre
-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 Characterizationof Products, Ris National Laboratory,
1997, Roskilde, Denmark [Riose-R-
967(EN)]
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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 beforetransport 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 removingmanure from feedlots
http://www.e3biofuels.com
How can we improve the system?
How can we increase sustainability of the process?
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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 Project4. 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
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1. generation 2. generation
The use of known 1G crops andcultivations methods is not likely toinfluence positively the environment but
will increase the competition for land with
other uses (feed and food)
Crop residues from food andfeed crops can be used for 2G
biofuels to some extent
Adapted from: Erik Steen Jensen: Lignocellulose-based biofuel production bioresources, technologies and sustainability
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Lignocellulose degradation
Lignocellulosepre
-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 Characterizationof Products, Ris National Laboratory,
1997, Roskilde, Denmark [Riose-R-
967(EN)]
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2. generation Bioethanol production
Pretreatment
Hemicellulose
Lignin
Cellulose
Distillation
Enzymes Yeast
Enzymes
C5
Microorganism
FermentationHydrolysis
Bio-EthanolC6
Hydrolysis Fermentation
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Co-production Biofuels (EU-project: 2003-2006, Danish project: 2006-2009)
Partners:
Elsam A/S (DONG Energy)
Ris National Laboratory - DTU
The Royal Veterinary and
Agricultural University
TMO Biotech (EU-project)
BioCentrum - DTU (Danish
project)
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 Util isation System (IBUS)Integrated Biomass Util isation System (IBUS)
1.step: Pilot scale reactor with a capacity of 100 kg/h1.step: Pilot scale reactor with a capacity of 100 kg/h
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IBUS 1000 kg/h plant
195-200C
90-100% cellulose
convertibility
50% hemicellulose
recovery
180C + 195C
90-100% cellulose
convertibility
83% hemicellulose
recovery
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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 torun the process!
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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
van Maarschalkerweerd, Ris (2006)
Grain Straw
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How far are we? - Feasibility study
Production cost for straw-based ethanol
0
1
2
3
4
5
6
7
8
20% 30% 40% 50% 60% 70% 80% 90% 100%
Cellulose conversion ratio [% ]
Eth
anolprod.costs
[$/gal
Case 1
Case 2
Case 3
Ref. Jan Larsen, Dong Energy, 28th Symposium on Biotechnology for Fuels and Chemicals, May 2006, Nashville.
Case 1 = C6, stand alone
Case 2 = C6, integrated (with power plant)
Case 3 = C6+C5, integrated
Latest feasibility study based on 1000 ton pr day IBUS ethanol plant located in the US (cost and
income), corn stover 40 EUR/t DM and enzyme cost 0.14 EUR/liter ethanol.
Raw production cost: 0.43 EUR/liter ethanol (2.40 US$/gal)
World market price 0.35 EUR/liter, EU-market price 0.55 EUR/liter [Morgan Stanley Equity Research, oct. 2007]
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AD manure as water and nutrient source
Oleskowicz-Popiel P. et al.: Ethanol production from maize silage as lignocellulosic biomass in anaerobically
digested and wet-oxidized manure. Bioresource Technology. in press
Source: Thomsen A.B., Medina C., Ahrling B.K.: Ris Energy Report
2. Biotechnology in ethanol production. Ris National Laboratory,
Denmark, November 2003.
Pre-treatment (Wet-Oxidation)
Straw, Water or AD Manure
SSF: Enzymes, Yeast
Product: Ethanol
Xylose Fermentation
Product: Ethanol
Anaerobic Digestion
Product: Biogas
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AD manure as water and nutrient source
ferm entation of IBUS straw in pre-tr eated AD manure and w ater
0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8
0 20 40 60 80 100 120 140 160
time [h]
ethanol[g/100g]
Straw+121.0
Straw+121.12
Straw+Water
manure 121.12
2000
2200
2400
2600
2800
3000
3200
3400
0 20 40 60 80 100 120 140 160
t ime [h]
ammonia
[mg/L]
Straw 1 Straw 2 Maize 1 Maize 2
Successful ethanol
fermentation in AD manure as awater and nutrient source
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 Project4. Bioprocess modelling (with SuperPro Designer)
Is there a future for organic farming?
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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 itsdependency of fossil fuels and decrease GHG emission
It might increase sustainability of organic farming
Main stream agriculture
organic
farming
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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 organicagriculture consequence for soil fertility, environment, spread of
animal parasites and socio-economy
work package 1: Co-production of biogas, bioethanol and animalfeed 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. Themethod 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
Co-fermentation of clover grass (commonly grown in OA) with animal manure
Co-fermentation of clover grass with whey (co-production of energy and animalfeed)
The goal is to develop farm-scale, low energy demanding and easy tohandle 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.
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BioConcens
From the energy balance point ofview, 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 thecarbon and nutrients cycle the
intelligent management of organic
residues and crop rotation is
necessary
Design and evaluate a combinedconcept for biomass and bioenergy
production in OA (considering the
soil fertility)
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Initial results the idea does really work
0
10
20
30
40
50
0 10 20 30 40
Time (h)
Ethanolcon
centration
(g/L)
Malted rye, 13% dw
Malted rye, 13% dw
Comm. enz., 13% dw
Comm. enz., 13% dw
0
100
200
300
400
0 5 10 15 20 25 30 35 40
time [day]
[mLCH4
/gVS]
dry grass (low conc.) dry grass (high conc.)
dry clover grass (low conc.) dry clover grass (high conc.)
clover grass silage (low conc.) clover grass silage (high conc.)
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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 Project4. Bioprocess modelling (with SuperPro Designer)
How to designan environmentally friendly process?
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Modeling of a bioprocess
Process concept
Process design anddevelopment
Modeling andsimulation
Literature
Patents
Expert
knowledge
Sustainabilityassessment
Improvements
neededNot
eco-efficientStop
Eco-efficient
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 tryunderstand of the actual production process
as early and as detailed as possible
the modeling of the process underdevelopment and a through assessmenthelps to improve this knowledge
the assessment should include economicand environmental evaluation
the simulation results are used to evaluatethe 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 processand not only to optimize single parts
the created models and the assessmentbased 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 andsocial aspects should be considered
process modeling and simulation enhances our insight andunderstanding of a process and helps to identify potentialimprovements 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:
Heinzle E., et al., (2006)Development of Sustainable Bioprocesses Modelling and Assessment. John Wiley & Sons Ltd.
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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
Computer simulations provide the ability to estimate the effect ofincreasing 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 tosimulate those conditions effectively allows the user to estimate
results of alternative processes with confidence.
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
photo: www.siteselection.com
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Modeling the process - simplified flow diagram
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
150 million l/year plant
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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 existingfermenter 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
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Modeling the process - simplified flow diagram
The actual process contains more than 100 pieces of equipment and unitoperations
The process simulator quantifies the processing characteristic, energy
requirements, and equipment parameters of each major piece of equipmentfor the specified operating scenario.
Volumes, composition, and other physical characteristic of input and outputstreams for each equipment item are identified. This information becomes
the basis of utility consumptions and purchased equipment costs for eachequipment item.
Composition of a raw agricultural feedstock varies by year and location, thiscan be easy adjusted
Different raw materials can be input in the model. although, maybe someextra 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
Thomsen MH: Complex media from processing of agricultural crops for microbial fermentation.
Mini-Review, Appl. Microbiol. Biotechnol (2005) 68: 598-606
The lactic acid fermentation of brown juice in the green crop drying plant as it
was simulated in SuperPro Designer
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Priority of sustainable land and bioresource use