“Green” Product Industry from past to futurePr. Emeritus Xavier Deglise,

IAWS Past-President

LERMaB/Université Henri Poincaré, B.P.239

54506 Vandoeuvre les Nancy Cedex, France

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Opportunities for Green Product Industry

- Fossil fuel pricesFlat or shrinking supply on long term

Soaring demand from Asia

Political uncertainty Middle – East, Nigeria, Venezuela…..

Transportation unsafe (Pirates in Somalia)

But world economical crisis and barrel price likely to be volatile, even drop from 150$ to……50$ within 4 months!

- Climate change, Global Warming (permanent issue)Demand for renewable, carbon-neutral fuels and materials will increase

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Source: Shell Nederland

Very short age of oil

Global Warming due to increasing of atmospheric CO2 (greenhouse effect)

Coming shortage of carbon sources

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?

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Green product industries: Biomass feedstock is converted to multiple products such as chemicals, fuels, and bio-products.

Biomass feedstock:

- Tree species: from eucalypt, poplar, willow to oil palm (palm oil)…and bamboo.

- Annual plants: miscanthus, switchgrass, kenaf, hemp, corn, sorghum, sugarcane.....

- Wood and Agricultural Wastes

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Objectives

Source: Forest Products Biotechnology at UBC

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One of the first Green Products industry was Distillation of wood:

100 wood Chemicals were obtained until the 50’s in France.

Palm oil and latex were and are the main extractives produced in S-E. Asia

In fact we are able to produce all chemicals that we need from Wood!

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Processes involved in G P Industries

- Pretreatment

- Thermo-chemical processes

- Hydrolysis/Saccharification (Acid or Enzymatic)- Use of Industrial Biotechnology enzymes- Extraction- Fractionation - Pulping

Non selective processes

Selective processes

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Bio-products

Source: Forest Products Biotechnology at UBC

Biological

Thermochemical

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Non selective Processes

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Wood upgrading into Energy or Chemicals

Hydrolysis+Fermentation

Fuel cells

EngineTurbine

SNGH2

Fischer-TropschHydrocarbons:

Bio-Oil, Bio-DieselAlcoholsMethanolBio-fuel

Bio-chemicals

Wood

ElectricityHeatGasification

Pyrolysis

DirectLiquefaction

Ethanol

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Pyrolysis products distribution

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Main Thermochemical Processes

Source:A.Dufour…

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Pyrolysis/Gasification Process

Source:A.Dufour…

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Foster Wheeler, Lurgi, GTI Double FB:Kunnii,Batelle, TNEE, Repotec, etc.

Volund, Xylowatt, Mukunda, PRME,

TKE, etc.

FutureEnergy,Choren

• Fixed bed : old technology (~1930, Imbert gasifiers, etc.)

• Fluidized bed (1970-80): Pr. Kaminsky, Pr. Kunnii, etc.

• Choice of the reactor: depends on the scale and on the type of the application

> 10 (?)FT diesel, H2

Entrained Bed

~ 1 to 50Elec., CH4, H2, FT diesel

Fluidized Bed

< 0,2ElectricityDowndraft

Capacity (ton dry biom./h)

ApplicationReactor type

Reactor types for gas production

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Examples: Dual Fluidized Bed, the TNEE process (Deglise et al., 1984)

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Examples: Dual Fluidized Bed, the TUV/Repotec process (Hofbauer et al., 1998, Aichernig et al., 2004)

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Bio-oil production by fast pyrolysis processes

• Reactor type (Bridgwater & Peacocke, 2000)– Fluidized bed (Dynamotive,

Aston, Hamburg, etc.)

– Ablative (Lede et al., 1987, NREL, Aston, etc.)

– Vacuum moving bed (Pyrovac)

– Cyclone (Lede et al., 1980, Broust et al., 2004)

– Rotating cone (Twente)

• Commercial plant:

Dynamotive, chemicals

(food aromas)

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Second generation bio-fuels: co-processing in refineriesor Fischer Tropsch synthesis. New opportunity ?

Source:A.Dufour…

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Van KREVELEN Diagram giving the elementary Composition and yield of Charcoal vs carbonization temperature

It is possible to select which kind of Char you want: high Carbon content high Yield, Activated carbon (or char, or charcoal)

Porosity depends on the heating Rate and of the wood anatomy

Bamboo charcoal plays the role of activated carbon

Solid Bio-Fuel…or Charcoal!

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Selective Processes

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Extractives:

Exudates from pine trees for naval stores industry,:- Tarring of ropes and caulking of seams in wooden ships, - Turpentine and rosin for music instruments, paints and varnishes

obtained also by steam distillation or extraction from pine stumps.

Latex from rubber trees: Natural rubber. Its production is increasing now and the remaining wood is used for furniture…to replace oak.

Extracts of heartwood, bark of various hardwood species, quebracho, oak, chestnut tree…..: Tannins for tanning leather, antioxidants, green glues, Phenolic acids extracted from the bark of various conifers: extenders for synthetic resin adhesives, binders and dispersants

Arabinogalactan, hemicellulose gum extracted from larch, is used in place of gum arabic.

Waxes extracted from Douglas fir bark are used for general wax applications.

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Cellulosic Polymers:High-purity, chemical cellulose or dissolving pulp:

- rayon and cellophane (both regenerated cellulose)

- cellulose esters: acetate and butyrate for fiber, film and molding applications

- cellulose ethers: carboxymethylcellulose, ethylcellulose and hydroxyethylcellulose for use as gums.

Wood Hydrolysis:Conversion of carbohydrate polymers to simple sugars by

reaction with water in the presence of acid catalysts or enzymes.

Two centuries old industry, used on a commercial scale in the United States during World War I, in Germany during World War II, later in USSR and always in Russia.

Glucose is the principal product and can be further converted to ethanol (transportation fuel, 2nd generation) or yeast.

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Silvichemicals from Pulping Liquors:Alkaline and sulphite pulping liquors are burned in the recovery of the

pulping chemicals or silvichemicals:

- Alkali lignin from sulphate or kraft black liquor, Sulphonated lignin precipitated as lignin sulphonates and used as tanning agents, adhesives, binders, dispersants, extender for resins, rubber reinforcement andemulsion stabilizers.

- Tall Oil oleo-resinous products of Kraft pulping process: Volatiles (turpentine), Crude tall oil (fatty acids and resin acids) from acidified black liquor.

- Sugars in spent sulphite liquor fermented with yeast to produce ethanol(used in the 80’s in blended transportation fuels, in USA) and food supplements.

- Mild alkaline oxidation of lignin sulphonates gives vanillin for flavoring applications in most of sweet and dairy products.

- Volatile products from kraft black liquor: dimethyl sulphide (DMS), dimethyl sulphoxide (DMSO), and dimethyl sulphone useful as solvents and chemical reactants.

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1. Knowledge-based products and services • New value-added products e.g. for construction, interior design, information, packaging and health-care purposes

• Utilizing wood-based biopolymers for composites

• Eco-friendly chemicals and polymers

• Creating new functionalities to products/materials

• Combining wood/fibers with other materials

• Creating new innovative wood and fiber structures for different end-uses

• Creating new business models and businesses

New Trends of G P Industries

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Biocomposites need to be lower cost, higher performance, more adaptable, more reliable, lower maintenance, and possess smart material properties:

• Synergistic performance by combining wood, inorganic materials, and natural biofiber,

• Enhanced performance and superior serviceability,

• More durable, dimensionally stable, moisture proof, and fire resistant,

• Possess advanced sensors for warning users when problems are imminent,

• Advanced biomimetic capabilities for fixing itself when problems are encountered, self-repair,

• Renewable, recyclable and sustainable,

• Decrease environmental impacts from processing and use,

• Have both materials and processes engineered to customize and optimize performance.

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2. Bio-refinery concept for efficient utilization of wood raw material

• Integrated suite of processes

• Multiple new added value products from a single plant:- Fuels; Specialty and commodity chemicals - Pure polymers (cellulose, nano-cellulose); Plastics

precursors

• Biological and renewable feedstock rather petroleum-based

• Modification and processing of wood raw material into innovative, eco-efficient products

• Forest, agricultural residues or dedicated plantations

• Effective utilization of side streams

• Development of recyclability characteristics

• Utilization of enabling technologies to improve productivity and reduce capital costs

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Source: FP innovation 2008

For example

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New concept of Bio-refinery

Source: J.E. Winandy et al. Forest Products Journal Vol. 58, No. 6

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3. Sustainable, renewable raw material production

• Techniques for measurement and characterization of properties of wood and fibers

• Tree breeding using traditional or genetic techniques

• Factors affecting wood and fiber properties

• Silvicultural methods, procurement and harvesting

• Optimizing the raw material supply chain

• Optimizing the uses of lands between forest and agriculture

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4. Mixing of renewable and non-renewable sources of carbon.

• “Clean” and even wastes of Biomass will not be sufficient to produce fuels and bulk chemicals.

• 1,6 Billion m3 wood used for energy (45% of total wood collected). Using all this volume for Biodiesel, will fulfill around 10% of the total consumption of diesel.

• Coal is remaining in large quantities mainly in Asia.

• Biomass is scattered and not concentrated like oil or coal. Transportation is compulsory for procurement.

• Better transport pretreated biomass with higher value, than primary biomass.

• Small-scale facilities are often more profitable than large size plants.

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“Green” Coal, Wastes gasification

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Conclusion

Never forget these two rules

Food > Feed > Fuel(3F Rule for Bioenergy!)

Food > Fine chemicals > Feed > Fibers > Frame > Fuel(6F Rule for Wood!)

and think to Wood and Agriculture Wastes, as feedstock!

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Thank you for your attentionQuestions ?