BIOREFINING AND PULP AND PAPER INDUSTRY

Valentin I. Popa,Prof.,PhD,Chem. Eng.

Technical University Iasi,Romaniavipopa@tuiasi.ro;

vipopa15dece@yahoo.com

WHY BIOREFINING?

• The term biomass is defined as any organic matter that is available on a renewable basis, including dedicated energy crops and tree, agricultural food and feed crop residues, aquatic plants, wood and wood residues, animal wastes and other materials.

• Kamm B., Kamm M., Gruber P.R., Kromus S. Biorefinery system-An Overview. In Biorefineries-Industrial Processes and Products: Status Quo and Future Directions Volume 1., Kamm B., Gruber P.R., Kamm M.Eds. Wiley-VCH: Weinheim, 2006

• The annual production of biomass is about 1.7-2.0 x 10 exp 11 tons; however, only 6x10 exp 9 tons are currently used for food and non-food applications. Food applications are by far the most important (96.5-97 %). The remainder is used in non-food applications for example as feedstock for chemical industry. At present, less than 10 % of the chemicals and raw materials offered by the chemical industry were generated out of biomass

[ Zoeblin H., Dictionary of Renewable Resources, Wiley-VCH: Weinheim, 2001]

Benefits of renewable resourcesutilisation

1. Reduced dependence on imported fossil oil;

2. Reductions in greenhouse gas emissions;3. Building on the existing innovation base to support new developments;

4. A bio-industry that is globally competitive;

5. The development of processes that use biotechnology to reduce energy consumption and the use of renewable materials;

6. Jobs and wealth creation;7. The development of new, renewable materials;

8. New markets for the agriculture and forestry sectors, including access to high-value markets;

9. Underpinning a sustainable rural economy and infrastructure;

10. Sustainable development along the supply chain from feedstocks to products and their end-of-life disposal.

The US Department of Energy defined the term biorefinery as:

“an overall concept of a processing plant where biomass feedstock is converted and extracted into a spectrum of valuable products” (US Department of Energy 1997)

Typically, three stages may be defined in a biorefinery:

• 1. Separation of biomass into its components (fine chemicals and pharmaceutical compounds-polyphenols, proteins, amino acids, pure plant oil, minerals, hemicelluloses, cellulose, lignin) in a primary fractionation/de-polymerization unit.

• 2. Conversion of intermediate fractions to valuable end products (e.g., biofuels) and chemical intermediates is performed in a secondary refinery process. Examples: conventional intermediates (alcohol or acids) and platform chemicals like levulinic acid, lactic acid or phenolic compounds.

• 3. Further (catalytic) processing of the chemical intermediates to high added value end-products.

Extraction/separation

Specific compounds-Hydrocarbons

-Proteins-Sugars-Pigments-Different active compounds

Secondary compounds-Hemicelluloses + polyphenols

Primary compounds-Lignocelluloses

Extraction/separationhemicelluloses, polyphenols, cellulose, lignocelluloses

Direct application

ConversionWith keeping basicstructural units

With destruction of chemical structure

Modified primary, secondary and specific compounds

-Structural units (monosaccharides, phenols, aminoacids)

-Gas-Liquids-Solids

Raw materials for substitution of petrochemicals products with high chemical or energetical value

Direct application

Conversion

Vegetal biomass-Specific compounds

-Secondary compounds-Primary compounds

Rawmaterials

PulpingChipsResidues

Extraction/Hydrolysis

Hemicelluloses/Sugars

Spent liquor

Fiber additivesBarriersHydrogelFood and pharmaceutical additives

FermentationProteinsEthanol

Cellulose

Micro and nanoparticlesCellulose derivatives

- films- fibers- sponges

Lignin - phenols- carbon fiber- binder/adhesives- porous carbon

Saccharinic acids

Pyrolysis- gasification- liquefaction

- wood- annual plants- biomass residues

Extraction

Fatty acidsPharmaceuticalsAntioxidantsBioactive chemicalsHemicellulosesLignocelluloses

Hydrolysis

Lignin Sugars Fermentation

Pulp Paper

biochemicaldegradation

burningadditives

compost fodderlignocelluloses

SEPARATION

BARK

EXTRACTION OF SECONDARY COMPOUNDS

Rough mixture ofhemicelluloses + polyphenols

Hcell-OHPF-OH

Hcell-OHsoftwoods24-26%hardwoods15-20%

-furfural- galacotse- glucose- arabinose- xylose

PF-OH

phenolsubstitute(adhesives) softwoods

10-12%

hardwoods4-6%

- C6 phenols- C6-C1 phenolic acids- C6-C2 acetophenone- C6-C3 coumarone- C6-C1-C6 xanthone- C6-C3-C6 stilbens-(C6-C3)2 lignans

PF O CH2 CHO

CH2 OH PF OH+

PF O CH2 CHO

CH2 OH PF OH+

O CH2PF CH CH2 O

OH

PF OH prepolym er crosslinking

LIGNOCELLULOSE

CHEMICALDESTRUCTION

(acid hydrolysis)

THERMALDESTRUCTION

(pyrolysis)

BIOCHEMICALDESTRUCTION

CELLULASEENZYMES

partial destruction

totaldestructi

on

sugars

proteins

alcohol

proteinaceous lignocelluloseshydrolysis lignin

׀ 30 ׀ 60 10

gas(CO2׀CO׀CH4׀H2) 16-20%liquids-tar 24- 28%

coal 35-40%

sugars

proteins

alcohol

ADVANTAGEOUS AS FUNCTION OF SOURCE AND EQUIPMENT

ADVANTAGEOUS FOR ANY SOURCE

hydrolysis lignin

PROCEDURES

THERMOCHEMICAL CHEMICAL BIOCHEMICAL

BURNING

DISTILLATION

PYROLYSIS

GASIFICATION

H GY AD SR IO F I C A T I O N

A HC YI DD R O L Y S I S

A FE ER RO MB EI N C T A T I O N

A FN EA RE MR EO N B T I A C T I O N

A FL EC RO MH EO N L TI AC T I O N

enzyme acid

gas

liquid

pretreatment

low heatingvalue (LHV)

medium heating value (MHV)

coal

gas

LHV MHV synthesis gas

tarliquid fuel

proteins pentoses

hexoses lignin

compost

CO2

water

fertiliser

gas(CH4)

C2H5OHCO2

waste

electricity

heat steams

coal

gas

tar

HEMICELLULOSES10-20% ON WOOD

GLUCOSE MANNOSE ARABINOSE GALACTOSE XYLOSE ACETIC ACID URONIC ACID

H

ACETONE

ACRYLATES

SINGLE CELLPROTEIN

BUTANOLF

F F

FURFURAL

D

SWEETNER

XYLITOL

HG

2- METHYL FURAN

FURAN LYSINE

TETRAHYDROFURAN

ADIPONITRILENYLON

FURFURYLALCOHOL

TETRAHYDROFURAN

ALCOHOL

GLUTAMIC ACID

POLYURETHANEFOAMS

RESINS AND PLASTICS

NITROGENATED AND

HALOGENATEDDERIVATIVES

DRUGS

Hemicelluloses based products

CELLULOSE40-50% ON

WOODPD PPH

RUMINANT FEED DISSOLVING PULP

CELLULOSE ESTERS

REGENERATED CELLULOSE

CELLULOSE ETHERS

GLUCOSE

BUTYLENE GLYCOL

BUTANOL

ETHANOLF F

LACTICACID

HYDROXYMETHYLFURFURAL

ETHER ETHYLENE MOTOR FUEL

ACETAL DEHYDE CHLOROFORM

POLYETHYLENE

PLASTICS

BUTADIENE

RUBBER

NYLON RESINS

POLYESTERS

LEVULINICACID

PLASTICS DRUGS

ACETONE

ACRYLATES

ITACONICACID

FF DGLUCOSEFRUCTOSESYRUP

METHYLGLUCOSIDES

XANTHAMGUM

SORBITOL SINGLE CELLPROTEIN

GLUCONICACID

SWEETNER

ALKYDRESINS

SURFACTANTS

GLYCEROL

SWEETNER

PROPYLENEGLYCOL

HUMECTANTS

VITAMINEC

F F ISO M F F HG F F

D = DEHYDRATIONF = FERMENTATIONH = HYDROLYSISHG = HYDROGENATION1SO= ISOMERIZATIONM = METHYLATIONPP = PULPING PROCESSPD = PARTIAL DELIGNIFICATION

Cellulose based products

LIGNIN15-30 % ON WOOD

SOLIDFUEL

DISPERSINGAGENTS

IONEXCHANGE

ROADSTABILIZER

VANILLIN BINDERSFOR

PRINTINGCOLORS

FERTILIZER

LOWMOLECULARWEIGHTPHENOLS

PHENOLICRESINS

ADHESIVES

INSULATINGFOAMS

POLYURETHANEFOAMS

RUBBERREINFORCED

CARBONMONOXIDE

METHANOL

CHEMICALS FUEL

ACTIVATEDCARBON

DYESTUFFS

POLYESTERS

Lignin based products

Today’s kraft pulp mill

Lignin +degradedcarbohydrates

(m ainlyhem icelluloses)Cooking chem icalsand energyrecovery

Cellulosic + CO 2 + H2Ofibers

Talloiland turpentine

Paperand board

Kraft cook

Extra energy

Bleaching

Softwood :40% cellulose30% lignin25% hem icelluloses5% extracts…

One possibility of tomorrow’s kraft biorefinery mill

Lignin +degradedcarbohydrates

Cooking chem icalsand energyrecovery

Cellulosic + CO 2Fibers + H2O

Talloiland turpentine

Extracted hem icellulosesas m onom ers or oligom ers Bioethanol

Chem icals, M aterials ..

Paper, boardM aterials (eg whiskers), ..

Extraction process

Kraft cook Bleaching

Biorefining and pulp and paper industry

Simplified diagram of the Kraft process

Delignifi-cation W ashing Bleaching

Drying PulpConcen- tration

Recovery Boiler

Recausti- fiactionLim e

Wood Chips

CaCO 3

Steam to processSmelt

Water Water Chemicals

Black Liquor

CaO

White Liquor

Schematic representation of dissolving pulp production based

on the Kraft process

Hydrolysis CookingWood chips

Hemicellulose sugars

Steam

Recaustization

Brownstock W ashing

Concentration & Burning

White liquor

Steam

Bleaching

Drying

Dissolving pulp

Black liquor

Simplified flowsheet of the concept for ethanol and lignin production in a converted pulp mill.

Alkaline frac.

Lignin separation

Feed Evaporation Recovery boiler

Lim e kilnLignin fuel

pH adjAcid

CO 2

Dewatering

Distillation

Ethanol

Com bustible solids Cooking liquor

Steam turbine Electricity

HP Steam

Sim ultaneous Saccharification and Ferm entation (SSF)

W ater Enzym es Yeast

Caustisizing

To evap. & then to power

boilerLiq.-phase

Pre-Hydrolysis

Alkaline frac.

Lignin separation

Feed Evaporation Recovery boiler

Lim e kilnLignin fuel

pH adjAcid

CO 2

Dewatering

Distillation

Ethanol

Com bustible solids Cooking liquor

Steam turbine Electricity

HP Steam

Sim ultaneous Saccharification and Ferm entation (SSF)

W ater Enzym es Yeast

Caustisizing

To evap. & then to power

boilerLiq.-phase

Pre-Hydrolysis

Alkaline frac.

Lignin separation

Feed Evaporation Recovery boiler

Lim e kilnLignin fuel

pH adjAcid

CO 2

Dewatering

Distillation

Ethanol

Com bustible solids Cooking liquor

Steam turbine Electricity

HP Steam

Sim ultaneous Saccharification and Ferm entation (SSF)

W ater Enzym es Yeast

Caustisizing

To evap. & then to power

boilerLiq.-phase

Pre-Hydrolysis

Alkaline frac.

Lignin separation

Feed Evaporation Recovery boiler

Lim e kilnLignin fuel

pH adjAcid

CO 2

Dewatering

Distillation

Ethanol

Com bustible solids Cooking liquor

Steam turbine Electricity

HP Steam

Sim ultaneous Saccharification and Ferm entation (SSF)

W ater Enzym es Yeast

Caustisizing

To evap. & then to power

boilerLiq.-phase

Pre-Hydrolysis

Nanofibrils

CONCLUSIONS• Biorefinery concept offers an opportunity to revitalize the pulp and paper industry producing high value chemicals and biofuels, developing new technologies and penetrating new markets.

• This situation explains the different proposals at world level concerning the implementation of biorefinery in the pulp and paper industry or to create and develop a new technology.