proceso general.pdf

8/13/2019 Proceso general.pdf

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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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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)



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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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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



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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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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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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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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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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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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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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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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



150 million l/year plant


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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%)




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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




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Cost model description

Equipment costs

Feedstock costs

Product values

Utility costs

Capital costs

Annual production and unit costs

Sensitivities




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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

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