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DRAFT

Creating Value from Pine-derived Feedstocks September 20, 2011

Innovation Day Chemical Heritage Foundation

Renewable resources. Endless possibilities.


What is a Bio-refinery? 1930 US

Department of Energy

● Bio-refinery is an overall concept of a processing plant where biomass IP feedstocks are converted and extracted into a spectrum of valuable Ownership products. 1984

by 1949

1984-99

“Run for Volume”

American National Renewable Energy Lab ● Bio-refinery is a facility that integrates biomass conversion processes and equipment to produce fuels, power and chemicals from biomass.

1999 2007

International Energy Agency

Transition To Standalone

2007-09 ● Bio-refinery

is the sustainable processing of biomass into a spectrum of marketable products.

2010

“Focus on Value”


Four Features of a Bio-refinery Platforms ● Intermediates, final product of bio-refinery

Products ● Energy Products (energy market) • Bio-diesel, bio-ethanol

● Material Products (materials market) • Chemicals, polymers, animal food

Feedstocks ● Dedicated Crops and Residues (agriculture, aquaculture, forestry)

Processes ● Thermo-chemical, Biochemical, Chemical, Mechanical/physical


A Generic Scheme of a Bio-refinery Feedstock (biomass) Process/Multiple processes

Platform Process/Multiple processes

Platform

Products

(energy or materials)

Process/Multiple processes Products

(energy or materials)


Categories of Bio-refineries 1st generation ● Direct utilization of forms of agricultural biomass • Sugars as a source of bio-ethanol via fermentation • Vegetable oils as a source of bio-diesel via transesterification

2nd generation ● Utilization of lignocellulosic biomass (cellulose, lignin) as a raw material ● Abundant, and reduced dependence on food crops (vs. 1st generation)

3rd generation ● Utilization of agricultural residue, as well as forestry, petrochemical, and urban waste.


“Bio-refining” at Arizona Chemical Arizona Chemical Company ● ● ● ●

The largest producer of pine-derived resins Greatest Crude Tall Oil distillation capacity in the world Largest integrated producer of resins from pine chemicals Largest producer of pine-based adhesive tackifiers

Arizona’s biomass ● By-products of the paper manufacturing process • Crude Tall Oil • Crude Sulfate Turpentine


“Bio-refining” at Arizona Chemical Pine Trees for Paper Mfg.

CTO, CST

(biomass)

Refining (distillation)

Rosin, Fatty acids, Terpenes Chemical Processing/Separation/Refining

“Bio-based” (pine-derived) Products for Various Markets


Crude Tall Oil and Crude Sulfate Turpentine Pulp Digestion

Pine Chips

(Na2S, NaOH)

CST* (Crude Sulfate Turpentine)

Black Liquor Soap *volatile component which is subsequently condensed Soap Skimming

Sulfuric Acid

"Acidulation"

Crude Tall Oil

Fractional Distillation

Tall Oil Rosin Acids

Tall Oil Fatty Acids

Heads,DTO & Pitch


Bio-Refinery Products from a Sustainable Source Pine Trees

Black Liquor Soap (BLS) (heavier fraction)

Crude Sulfate Turpentine (CST) (volatile component)

Crude Tall Oil (CTO) (mixture of rosin and fatty acids)

-pinene -pinene -3-carene Dipentene

Tall Oil Fatty Acids (TOFA) Distilled Tall Oil (DTO) Tall Oil Rosin Pitch


Tall Oil Fatty Acid (TOFA) – a Bio-derived Polymer Building Block Tall Oil Fatty Acids 2 major components: Linoleic and oleic acid Linoleic acid

non-polar end (hydrophobic)

COOH polar end (hydrophylic)

Olefin functionality dimers, isomerized (monomer) epoxidation, drying

Acid functionality esters, amides metal salts

Oleic Acid COOH (monounsaturated)

Stearic Acid COOH (saturated)

TOFA is a reactive fatty acid derived from a non-edible source which finds many industrial uses. In Adhesive applications, TOFA becomes the backbone of high performance polyamide polymers.


TOFA: a non-edible C-18 Fatty Acid with Many Industrial Applications TOFA: a versatile building block suitable for many uses, including polymers, surfactants and lubricants. Tall Oil Fatty Acid Esterification Lubrication Plastisizers Personal Care

Merchant

Dimerization Monomer

Dimer Merchant Polyamides Esters CI

Polyamides

Isostearic

Ink Resins Lubricants Curing Agents Personal Care Hot Melt Adhesives

Stearic Lubricants Personal Care

Emulsifiers Alkyds Ore Flotation CI


Tall Oil Rosin (TOR): Versatile Chemistry with High BRC Rosin derivatives have broad utility in adhesive formulations compatibility, adhesion, formulating versatility.

CH3

CH3

CH3

COOH

CH3

TOR: A building block with carboxylic acid and unsaturation functionality. TOR derivatives have compatibility with aliphatic and polar polymers and broad adhesion characteristics.


What is Rosin Rosin is mainly a mixture of various Carboxylic acids 50 45 40 35 30

% 25

Tall Oil Gum

20

Wood 15 10 5 0 Abietic

Neoabietic

Pimaric Dehydroabietic Palustric

Acid

Isopamaric


Tackifiers from Rosin* *Chemistry: Esterification CH3

CH3

CH3

Glycerol

CH3

Glycerol ester

COOH

Pentaerythritol (PE)

CH2OH

CH2OH

CH2OH

C

CH2OH

HC

PE ester CH2OH

PE

CH2OH

Glycerol

OH


Terpene Chemistry – for Resins for High Performance Adhesives

-pinene

-pinene

limonene/dipentene

delta-3-carene

Resins derived from terpene monomers have narrow, broad or bi-modal MW distribution. Resins perform well in many polymer systems to give favorable shear/tack balance, as well as specific adhesion to many difficult-to-bond substrates. Excellent odor, color and stability attributes.


Tackifiers from Terpenes* *Chemistry: Cationic polymerization

Polyterpene Resins

terpene

styrene -pinene

phenol

Terpene-Phenol Resins

Styrenated Terpene Resins


Value Chain from CST and CTO Tall Oil Fatty Acids (TOFA)

Dimer Acids

Distilled Tall Oil (DTO)

CTO

CST

Polyamide Resins

Metalworking Fluids

Tall Oil Rosin (TOR)

Rosin Resins

Adhesive Tackifiers Ink Binders Roadmarking Tackifiers

Tall Oil Pitch

BioFuels & Performance Blends

Energy, Mining

Sterols

Pharma Food Additives

Terpene Resins

Adhesive Tackifiers Ink Binders Tire Resins

Terpene Monomers

Hot Melt Adhesive Flexo Ink Binders Epoxy Curing Agents


P E T R O L E U M R E F I N E R Y


A Bio-refinery generating Products for Multiple High Value Applications

Innovation Day - Bio Feed Stock Presentation  

Innovation Day - Bio Feed Stock Presentation

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