25/09/2021 - cyted.org

25/09/2021

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Biorrefinerías: Tipos,

Evolución, Productos y

Procesos de ValorizaciónLuiz Pereira Ramos

Programas de Pós-graduação em Química e em Engenharia Química

Universidade Federal do Paraná (UFPR)

Curitiba, PR, Brasil

[email protected]

Valorización de Residuos,

Bioeconomía Y Economía Circular

Curso Resalvalor, 2021

Luiz Ramos, UFPR

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Contents

❖ Biorefinery definition

❖ Types of biorefineries

❖ Biorefinery processes

❖ Feedstock availability

❖ Examples of biorefinery schemes

❖ Fuels, platform chemicals, and biomaterials

❖ Life cycle analysis

❖ Challenges and perspectives

❖ Conclusion




Luiz Ramos, UFPR

From Wikipedia:

A biorefinery is a facility that integrates biomass conversion processes and

equipment to produce fuels, power, heat, and value-added chemicals from

biomass. The biorefinery concept is analogous to today's petroleum refinery,

which produce multiple fuels and products from petroleum.

A biorefinery takes advantage of the various components in biomass and

their intermediates therefore maximizing the value derived from the

feedstock. A biorefinery could, for example, produce one or several low-

volume, but high-value, chemical or nutraceutical products and a low-value,

but high-volume liquid transportation fuel such as biodiesel or bioethanol. At

the same time generating electricity and process heat, through combined

heat and power (CHP) technology, for its own use and perhaps enough for

sale of electricity to the local utility.

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Biorefinery definition




Luiz Ramos, UFPR

From NREL (National Renewable Energy Laboratory):

A biorefinery is a facility that integrates biomass conversion processes and

equipment to produce fuels, power, and chemicals. Industrial biorefineries

have been identified as the most promising route to the creation of a new

domestic biobased industry.

By producing multiple products, a biorefinery can take advantage of the

differences in biomass components and intermediates and maximize the

value derived from the biomass feedstock. A biorefinery might, for example,

produce one or several low-volume, but high-value, chemical products and a

low-value, but high-volume liquid transportation fuel, while generating

electricity and process heat for its own use and perhaps enough for sale of

electricity. The high-value products enhance profitability, the high-volume

fuel helps meet national energy needs, and the power production reduces

costs and avoids greenhouse-gas emissions.

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Biorefinery definition




Luiz Ramos, UFPR

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Biobased products from biomass

Werpy and Gene (2004) No. DOE/GO-102004-1992. NREL, Golden, CO (US).




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Luiz Ramos, UFPR

Biorefinery types

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CRUDE OIL REFINERY BIOBASED REFINERY

Renewable in million years Seasonal (eventually perennial)

Available in some places Available everywhere in the globe

Contributes to GHG emissions Low carbon footprint

Large scale, high capital cost Amenable to downsizing

Carbon-based material Composed by oxygenated compounds

Requires fractionation Requires depolymerization

Homogeneous Heterogeneous

High density raw material Low density raw materials

>100 years of R&D R&D developments on the rise

Fully commercialized Limited commercialization

Profitable Questionable economic viability

Huge economic power already in place Highly dependent on public policies




Luiz Ramos, UFPR

Type 1 Biorefinery

Almost no processing flexibility, such as a dry-milling ethanol plant

which uses grain as a feedstock or an esterification plant using plant

oils; facility has a fixed processing capability and produces a fixed

amount of fuel, and co-products.

Type 2 Biorefinery

Flexibility in end-product production, like a wet milling technology

using grain feedstocks that can produce various end-products

depending on demand. Products include ethanol, starch, high fructose

syrups, oils and meals.

Type 3 Biorefinery

Flexibility of feedstocks and end-products: use of various types of

feedstocks and processing methods to produce products for the

industrial market.

Kamm and Kamm (2004) Applied Microbiology and Biotechnology 64, 137-145.

Biorefinery types

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Luiz Ramos, UFPR

Biorefinery types

Aristizábal-Marulanda, Cardona-Alzate (2018) Biofuels, Bioproducts and Biorefining, DOI: 10.1002/bbb 9

Type Description

Conventional BiorefineriesBased on existing industries (sugar, vegetable oils,

feed, food, pulp and paper, and (petro)chemical)

Green BiorefineriesUse wet biomass such as green grasses and green

crops

Whole Crop BiorefineriesUses dry or wet milling of biomass. Cereals such as,

corn and wheat

Lignocellulosic BiorefineriesBased on the fractionation of lignocellulosic biomass

composed by cellulose, hemicellulose and lignin

Marine Biorefineries (MBR) Uses marine biomass as microalgae and macroalgae

Two Platform Concept BiorefineriesConsiders platforms as sugars (from lignocellulose)

and syngas (from thermochemical conversion of lignin)

Thermo-Chemical BiorefineriesBased on several technologies as torrefaction,

pyrolysis, gasification, etc.




Luiz Ramos, UFPR

Biorefinery types

Wang et al. (2009) Renewable and Sustainable Energy Reviews 13, 2263-2278. 10

Type Processes FeedstocksProducts

Energy Materials

C6 sugars Hydrolysis, fermentation Starch crops Bioethanol Animal feed

OilPressing, transesterification

Oil crops BiodieselAnimal feed, glycerin

SyngasPretreatment, gasification and alcohol synthesis

Lignocellulosicmaterials

Syntheticbiofuels, FT-fuels

Chemicals(alcohols)

Sugar andsyngas

Biochemical conversion,thermochemical

Biomasses (75%carbs on average)

Conditioning gas, fuels

Chemicals, polymers

C6/C5 sugars,lignin, syngas

Pretreatment, hydrolysis, fermentation,gasification, FT-synthesis

Lignocellulosicmaterials, energycrops

FT-fuels,ethanol

Animal feed




Luiz Ramos, UFPRBiorefinery

Wang et al. (2009) Renewable and Sustainable Energy Reviews 13, 2263-2278. 11

Principles Criteria/dimensions of the assessment

Systems Technical and process design of biorefinery: processing efficiency, mass flow,aims for the potential substitution/displacement of fossil-fuel based productsby biobased products

Consistency In coherence with the national/regional/global strategies on sustainabledevelopment, such as the EU–biofuel and bioeconomy strategy. Resourcemanagement and diversification of use in relation to sustainability goals

Independency Comparative economic and environmental performance of the biomassconversion in biorefinery with respect to alternatives (e.g., thermochemical,combustion, pyrolysis, gasification, liquefaction, etc.). Socio-economic andenvironmental differences with respect to biorefinery pathways but differingthe feedstock supply and the product scenarios (extent of processing)

Measurability Qualitative and quantitative analysis of the process and product system.Quantification of sustainability assessment criteria/indicators (GWP per kg ofbioethanol, annualized cost of producing 1 kg of ethanol, animal feed, potentialemployment generation per kg of ethanol, etc.)

Comparability In relation to the principle of Independency as stated above, ecological andsocio-economic aspects of utilizing various inputs to produce marketableproducts in a biorefinery process




Luiz Ramos, UFPR

Adapted from Lucia and Rojas (2006) In: Proceedings of the CIADICYP Meeting, CD-rom, Santiago, Chile.

Biorefinery processes

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FEED, FOOD, AND

PRODUCTS

SYNGASHYDRO

CARBONS

FOSSILIZATION HARVESTING CONVERSION

COMBUSTIONCOMBUSTION

RESIDUES

CO2

RESIDUES

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Luiz Ramos, UFPR

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Fontesde CO2

Imediato

Renovável

Fóssil

CO2 da fermentaçãode Etanol

Cimento

Biogás

Aço

Biomassagaseificada

Glicerina doBiodiesel

Usinas termoeléctrica (Carvão, Gás, Petróleo)

Fonte: ProQR

Ciclo CO2

Ar Ambiente

CO2CO H2

+

Papel/Celulose

CO2

CO2 CO2 CO2 CO2

Immediate

Renewable

Fossil

Atmosphere

Ethanol

fermentation

Cement

Biogas

Pulp & Paper Steel Thermoelectric

power plant

Glycerin from

biodiesel

Biomass

gasification

CO2 cycle





Luiz Ramos, UFPR

Gases

Nafta

Diesel

Combustíveisde Energia Elétrica

Ar ambiente

Sequestro

Geração de

Energia ElétricaCoSOEC

Hidrotrata-

mento

Upgrade

Fischer-Tropsch

SAF

Atmospheric

CO2

Electricity

generation

CO2 capture

Electricity

generation

heat

HydrotreatmentOxygen BioQAv

Separation


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Luiz Ramos, UFPR


15Tabanelli et al. (2019) In Studies in Surface Science and Catalysis, Elsevier, vol. 178, 125-144.




Luiz Ramos, UFPR

Plant Raw

Material

Crop

residues

Oilseeds

Sugar crops

Woody &

herbaceous

crops

Grains

Pre-

processing

Protein

Oil

Lignin

Ash

Carbohydrates

Syngas

Functional

Unit

Products to

replace

petroleum

based or

petroleum

dependent

products

Recycle or

Disposal

Recycled

within

product

system

or

to other

product

systems

Compost pile

or

landfill

•Fuels

•Chemicals, etc.

•Monomers

•Lubricants

•Polymers

•Feeds & foods

•Electricity

•Fertilizer

•Steam

Final

Processing

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Luiz Ramos, UFPR

Cane energy

360

70

951

185

17

223

9060

30

495

110

385

Production / Productivity Energy Bagasse

(106 ton) / (ton ha-1) (MW year-1) Production Consumption Surplus

(106 ton)

Sugarcane

Cane energy

> 1

64

%

> 1

20

0%

> 4

50

%

13

135

26

93

Fibers / Sugars

(%) / (%)

> 1

64

%

< 3

1%

Gre

en b

iom

ass

(to

nha

-1)

Harvesting (years)

AverageEnergy cane

AverageSugarcane

More productivity

Higher yields

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Luiz Ramos, UFPR

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http://www.time.com/time/magazine/0,9263,7601080407,00.html

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Luiz Ramos, UFPR

Adaptação de Pagliaro et al. (2007) Angew. Chem. Int. Ed., v. 46, p. 4434-4440

PHOTOSYNTHESIS

ANIMAL FEED, PROTEIN OR CARBON SOURCE

MATERIALS

CHEMICALS POLYMERS

CONVERSION

(CATALYSIS)

PHARMA

SYNTHETIC FUELS

ADDITIVES

BIOENERGY

COMBUSTION

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OIL

BEARING

MATERIALS

GLYCEROL

BIODIESEL

MEALS OR RESIDUES




Luiz Ramos, UFPR

Zeman et al. (2019) Catalysts 9 (4), 337. 20


Oils

Fats

Fatty acids

Hydrotreatment

• Hydrodeoxygenation

• Hydroisomerization

• Hydrocracking

Drop-in fuels

• BioQAv

• SAF

• Green diesel

Drop-in fuels from renewable lipids (HVO or HEFA)

HVO production

forecast for 2024

(IEA/Bioenergy):

17 billion liters

PROJECTION

CO-PROCESS

FOSSILE

NEW

2024




Luiz Ramos, UFPR

Processes

Biological

Physical

Thermo-chemical

Chemical

• Fermentation

• Anaerobic digestion

• Aerobic digestion

• Enzymatic conversion

• Hydrolysis, catalytic conversion

• Esterification & transesterification

• Electrolysis, hydrotreatment

• Pulping, fractionation

• Oxidation

• Reforming, methanation

• Pretreatment, extraction

• Separation, distillation

• Milling

• Supercritical fluids

• Combustion

• Gasification

• Pyrolysis

• Hydrothermal upgrading


Galbe and Wallberg (2019) Biotechnology for Biofuels 12, 294. 21




Luiz Ramos, UFPR

Adapted from: Huber, Iborra, and Corma (2006) Chemical Reviews, 106, 4044-4098.

GASIFICATION

PYROLYSIS

HYDROLYSIS

SYNGAS

BIO-OILS

SUGARS

LIGNIN

Fischer-Tropsch

Methanol

Water-gas shift

…………….. Alkanes

…………………….. Methanol

.…………… Hydrogen

Dehydrogenation

Zeolite upgrading

..……... Liquid fuels

..…..…. Liquid fuels

Fermentation

Dehydration

Hydrotreatment

………….….….. Ethanol

…..…………….. Methanol

..…………… Alkanes

or hydrogen

Upgrading……… Ethers (biogasoline)

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Luiz Ramos, UFPR


23Galbe and Wallberg (2019) Biotechnology for Biofuels 12, 294.




Luiz Ramos, UFPR

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GrassesSolvents, pharmaceuticals, adhesives, starch,

resins, binders, polymers, cleaners and ethanol

Oil bearing

materials

Surfactants in soaps and detergents,

pharmaceuticals, inks, paints, resins, cosmetics,

fatty acids, lubricants and biodiesel

WoodPaper, building materials, cellulose for fibers and

polymers, resins, binders, adhesives, coatings,

paints, inks, road, biofuels and roofing pitch

Biorefinery products

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Luiz Ramos, UFPR

Adapted from Lucia and Rojas (2006) In:

Proceedings of the CIADICYP Meeting,

Santiago, Chile 25

BiorefinerySTRUCTURAL

MATERIALS

THERMOCHEMICAL

CONVERSION

RESIDUES AND

ENERGY CROPS

FORESTRY

PRODUCTS

PULP AND PAPER

INDUSTRY

FurnitureSupporting materials

Plastic fillings

Cement additives

Composites

Alcohols, estersChemicals

Polymers

Hydrocarbons

Hydrogen

Pharmaceutics

Bio-oilSynfuels

Energy

Chemical building blocks

syng

as

blac

kliq

uor

co-

prod

ucts

Pulp and paper

Ethanol, butanolOrganic acids

Biomolecules, enzymes

Biomaterials

BIOLOGICAL

CONVERSION

CHEMICAL

CONVERSION




Luiz Ramos, UFPR

The POLYNOL Project - Niklas Berglin - NWBC, October 25, 2012


Electricity

Kraftpulping

Paper/

board

production

Pulp woodLiquid

packaging

board

Renewable

packaging

Energy and

chemicals recovery

Fuels for heavy-

duty vehicles

Polyethylene

& PLA

Ethanol & lactic acidHydrolysis &fermentation

Recoveredignin

Alkalinefractionation

Forestry residues,

energy wood, bagasse CO2

Sulfur-free lignin




Luiz Ramos, UFPR

27Dr. Orlando Rojas, Aalto University / UBC, 2021





Luiz Ramos, UFPR

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Car care

Paint/varnish

Pharmaceutics

Biofuel

Concrete additives

Animal feed

Dyestuff

Batteries

Mining, BriquettingFood

Perfumes

Additives

Pharmaceuticals

Construction

Cosmetics

Food

Tablets

Textiles

Filters

Paint/varnish

Sarpsborg, Norway,

[email protected]

http://www.borregaard.com

Integrated biorefinery production process




Luiz Ramos, UFPR

DROP-IN FUELS IN THE PULP AND PAPER SECTOR

GasificationPyrolysis Liquefaction

Bark, black liquorCO2 emissions

Tall oil Hydrotreatment

Pretreatment

Hydrolysis

Fermentation

SyngasBio-oil

Methanol Ethanol

FT synthesis Water-gas shift Hydrogenation

Syncrude Hydrogen

Upgrading

Oligomerization

Biocrude

Renewable hydrocarbons(green diesel, SAF and

biogasoline)

Reforming

Syngas

FT synthesis

Fiber rejects, sawdust, unclassified chips

Pulping secondary/ waste stream

Pinto, Corazza, and Ramos (2021) BioResources 16 (4), 6553.





Luiz Ramos, UFPR

Hemicellulose

(Pentosans-Xylan)

Cellulose

(Hexosans-Glucan)

Lignin

Biomass

Pre-treatment

Sugars

C5/C6

sugars

(Xylose-

Glucose)

Xyiytol

Chemical pathway from pentoses

Direct Product use

Non-nutritive sweetener

Buiding block for Xylaric acid, glycols

Sorbitol

Chemical pathway from hexoses

Non-nutritive sweetener

Building block for Isosorbide, propylene

glycol

Product’s derivatives

use

Antifreeze, unsaturated polyester resins

PET like polymers, anrifreeze, water

soluble polymers for water treatment

Levulinic acid

Chemical pathway from hexoses/

pentoses

Building block for Methyl

tetrahydrofuran, butyrolactone,

Diphenolic acid

Fuel oxigenates, pesticedes,solvents,

polycarbonate resins

Succinic acid

Biotechnological pathway from hexoses

Building block for Butanediol

(BDO),Tetrahydrofuran (THF), gamma-

Butyrolactone (GBL). pyrrolidones

Fibers such as Lycra, green solvents,

water soluble polymers for water

treatment

3-Hydroxypropionic acid


Building block for 1,3 propane diol,

acrylates

Sorona Fiber, contact lenses, super

adsorbant polymers (Diapers)

Ethanol

Biotechnological pathway from hexoses/

pentoses

Fuel for transport, Building block for

Ethylterbutylether (ETBE), ethyl estersFuel, Fuel Oxigenate,

Ferulic acid

Biotechnological pathway from lignin by

enzymatic depolymerization

Building block for vanilin, polymers Flavouring agents, phenolic resins

OH

Furfural

Chemical pathway from pentoses

Solvent in petrochemical refining,

Building block for Tetrahydrofuran

(THF), Nylon 6 Nylon 6,6

Thermoplastic fibers, resins, solvents O

H

O

Lactic acid


Building block for polylactides such as

polylactide acid (PLA)

Biodegradable Polyethylene-like

polymers

OH

OH

O

Sulfur-free solid fuel

Pelletization of lignin rich solid residueFuel for heat and power generation

Product

http://bpe.epfl.ch/ 30

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Luiz Ramos, UFPR


31Werpy, T.A.; Holladay, J.E.; and White, J.F. 2004. Top Value Added Chemicals From Biomass: I. Results of

Screening for Potential Candidates from Sugars and Synthesis Gas . PNNL-14808, Richland, WA




Luiz Ramos, UFPR


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Luiz Ramos, UFPR


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Luiz Ramos, UFPR

34Suota et al. (2021) BioResources, v. 16, n. 3, p. 6471-6511.

Lignin chemistry




Luiz Ramos, UFPR

35Dr. Orlando Rojas, Aalto University / UBC, 2021




Luiz Ramos, UFPR

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Lignin market

Suota et al. (2021) BioResources, v. 16, n. 3, p. 6471-6511.

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Luiz Ramos, UFPR

Life cycle

http://bioenergy.ornl.gov/papers/misc/bioenergy_cycle.html

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Luiz Ramos, UFPR

What are and how to build LCA models?

• Material/energy inputs & outputs of both products & processes

• Inventory environmental impacts of products & processes

• Benchmark, evaluate & improve environmental footprint

• Methods for doing LCA studies are not universally agreed

• Set clear system boundaries: what exactly are we comparing?

• Multi-product systems must allocate environmental costs among all

products (no environmental burdens assigned to wastes)

• Perform sensitivity analysis: how much do results vary if

assumptions or data change?

Life Cycle Analysis

38




Luiz Ramos, UFPRLCA study case

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Luiz Ramos, UFPR

• Environmental performance of bio-based products

– Example of integrated biorefinery-cropping systems

• Ethanol

• Polyhydroxyalkanoates (PHA)

• Eco-efficiency analysis

– Ethanol and PHA are produced from the same unit of land

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LCA study case

Eco-efficiency = 𝐸𝑐𝑜𝑛𝑜𝑚𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 𝐴𝑑𝑑𝑒𝑑

𝐸𝑛𝑣𝑖𝑟𝑜𝑛𝑚𝑒𝑛𝑡𝑎𝑙 𝐼𝑚𝑝𝑎𝑐𝑡 𝑅𝑎𝑡𝑖𝑜

ERI =𝐸𝑛𝑣𝑖𝑟𝑜𝑛𝑚𝑒𝑛𝑡𝑎𝑙 𝐼𝑚𝑝𝑎𝑐𝑡

𝐸𝑛𝑣𝑖𝑟𝑜𝑛𝑚𝑒𝑛𝑡𝑎𝑙 𝐶𝑟𝑒𝑑𝑖𝑡

EVA = 𝑀𝑎𝑟𝑘𝑒𝑡 𝑉𝑎𝑙𝑢𝑒

𝐶𝑜𝑠𝑡 𝑜𝑓 𝑅𝑎𝑤𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 & 𝐹𝑢𝑒𝑙




Luiz Ramos, UFPR

Corn oil

Corn grainCorn gluten meal

Corn gluten feed

PHA

Soybean oil

Conventional

polymer

Soybean milling Soybean culture

Corn culture

Polymer production

Products Alternative product systems

Crude oil

Nitrogen in urea Ammonia Natural gas

Ethanol/ethanol

fueled vehicle

Gasoline/gaso-

line fueled vehicleCrude oilGasoline

Ethanol production system

PHA production system

Bioelectricity Electricity Coal-fired power plant Coal

Coproduct systems in both production systems41

LCA study case




Luiz Ramos, UFPR

Agricultural

product

Conversion

technologyMain products Main use

Corn grain

Corn stover

Corn grain

Wet milling

Corn stover

process

Wet milling

PHA fermentation

& recovery

•Corn oil

•Corn gluten meal

•Corn gluten feed

•Ethanol

•Electricity

•PHA

Liquid fuel

Edible oil

Animal feed

Export to power grid

Polymer

if applicable

•Ethanol

•Corn oil

•Corn gluten meal

•Corn gluten feed

Corn stoverCorn stover

process

•PHA

if applicable

Ethanol production system

PHA production system

•Electricity

42

LCA study case

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Luiz Ramos, UFPR

Problem Challenge

Scale-up to industrial scale

Requires significant capital investment

Requires strong financial incentive

Investors find too low return on investment

Future situation unclear Laws and regulations not clear

Construction and design Delays in erection of plant

Testing of equipment

Biomass availability All-year round supply of suitable materials

Possibility to run on more than one material

Logistics and supply Storage and transportation must be reliable

Data for process design Transfer of smaller-scale data to industrial scale

Maturity of a process Handling at high pressures and feeding, e.g. for 2G plants

of ethanol causes production stop

43

Biorefinery challenges

Aristizábal-Marulanda and Cardona Alzate (2018) Biofuels, Bioproducts and Biorefining, DOI: 10.1002/bbb




Luiz Ramos, UFPRFinal remarks

❖ A full knowledge about the biomass composition is critical for

the development of biorefineries

❖ Developments in biomass conversion processes must be

accompanied by suitable mass balances based on reliable

analytical tools

❖ Proper statistical analyses are mandatory to validate

experimental results that are based on multivariate systems

❖ LCA and modelling are critical to determine process eco-

efficiencies and evaluate system boundaries

❖ Biorefineries are not facilities but complexes in which thermal

and biochemical conversion processes may well coexist

❖ Feedstock flexibility and multiple end products are mandatory

for sustainable biorefineries

44

Our vision...




Luiz Ramos, UFPR

Thank you!

[email protected]

25/09/2021 - cyted.org

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