biorefining and pulp and paper industry
TRANSCRIPT
BIOREFINING AND PULP AND PAPER INDUSTRY
Valentin I. Popa,
Prof.,PhD,Chem. Eng.Technical University Iasi,Romania
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
Conversion
With 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
PulpingChips
Residues
Extraction/Hydrolysis
Hemicelluloses/Sugars
Spent liquor
Fiber additivesBarriersHydrogelFood and pharmaceutical additives
FermentationProteins
Ethanol
Cellulose
Micro and nanoparticles
Cellulose 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 fodder
lignocelluloses
SEPARATION
BARK
EXTRACTION OF SECONDARY COMPOUNDS
Rough mixture ofhemicelluloses + polyphenols
Hcell-OH
PF-OHHcell-OH
softwoods24-26%hardwoods15-20%
-furfural- galacotse- glucose- arabinose- xylose
PF-OH
phenolsubstitute(adhesives)
softwoods10-12%
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
CH2OH PF OH+
PF O CH2 CHO
CH2OH PF OH+
O CH2PF CH CH2 O
OH
PF OH prepolymer crosslinking
LIGNOCELLULOSE
CHEMICALDESTRUCTION
(acid hydrolysis)
THERMALDESTRUCTION
(pyrolysis)
BIOCHEMICALDESTRUCTION
CELLULASEENZYMES
partial destruction
totaldestruction
sugars
proteins alcohol
proteinaceous lignocelluloseshydrolysis lignin
60 30 10gas(CO2COCH4H2) 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
Hemicelluloses based products
Cellulose based products
Nanofibrils
Lignin based products
1. Lignins as antibacterials
2. Lignins as antioxidants and photoprotectors
3. Lignins in reduction of carcinogenesis
4. Anti-HIV properties of lignins
5. Lignin as spermicide
Lignin
LIGNIN
Macrophages are specialized phagocytic cells that attack foreign substances, infectious
microbes and cancer cells through destruction and ingestion
Today’s kraft pulp mill
Lignin +degradedcarbohydrates
(mainly hemicelluloses)Cooking chemicals
and energyrecovery
Cellulosic + CO2 + H2Ofibers
Tall oil and turpentine
Paper and board
Kraft cook
Extra energy
Bleaching
Softwood :40% cellulose30% lignin25% hemicelluloses5% extracts…
Schematic representation of dissolving pulp production based on the Kraft
process
Hydrolysis CookingWood chips
Hemicellulose sugars
Steam
Recaustization
Brownstock Washing
Concentration & Burning
White liquor
Steam
Bleaching
Drying
Dissolving pulp
Black liquor
One possibility of tomorrow’s kraft biorefinery mill
Lignin +degradedcarbohydrates
Cooking chemicalsand energy
recovery
Cellulosic + CO2Fibers + H2O
Tall oil and turpentine
Extracted hemicellulosesas monomers or oligomers
BioethanolChemicals, Materials ..
Paper, boardMaterials (eg whiskers), ..
Extraction process
Kraft cook Bleaching
Biorefining and pulp and paper industry
Simplified flowsheet of the concept for ethanol
and lignin production in a converted pulp mill.
Procedure LignoBoost/Sweden
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.
• Valentin I.Popa -Hemicelluloses in pharmacy and medicine in Polysaccharides in medicinal and pharmaceutical application, Edited by Valentin I.Popa, Smithers, 2011
• Valentin I.Popa, Lignin in biological systems in Polymeric biomaterials, 2 vol, Founding Editor: Severian Dumitriu, Editor: Valentin I.Popa, 2013, CRC Press
Valentin I. Popa, Chapter 1-Biorefining and the pulp and paper industry in the book:
• Pulp production and processing: From papermaking to high-tech products
Editor: Valentin I.Popa, Smithers, 2013
THANK YOU VERY MUCH FOR YOUR ATTENTION!